Electrochemical actuator
Abstract
An electrochemical actuator for administering a drug in a body, which has at least one negative electrode (214); at least one positive electrode (212); and a species (218), in which the electrochemical actuator is subjected to an applied voltage or current, characterized in that the application of the voltage or current, or its termination, includes the interleaving of the species (218) into at least one electrode of the electrochemical actuator, resulting in a volumetric or dimensional change of the electrochemical actuator, and because the volumetric or dimensional change causes the administration of a drug in an organism.
Term
0.8 yearsto projected expiry
Projected expiry 26 July 2027, counted from filing; an application has no term until it is granted.
- Priority
- Filed
- Published
- Today
- Projected expiry
18 claims: 7 independent, 11 dependent
- 1REIVINDICACIONES 1.-Un actuador electroquímico para administrar un fármaco en un cuerpo, que comprende:al menos un electrodo negativo (214);al menos un electrodo positivo (212);y una especie (218), en el que el actuador electroquímico se somete a un voltaje o corriente aplicada, caracterizado porque la aplicación del voltaje o corriente, o su cese, incluye la intercalación de la especie (218) en al menos un electrodo del actuador electroquímico, dando como resultado un cambio volumétrico o dimensional del actuador electroquímico, y porque el cambio volumétrico o dimensional provoca la administración de un fármaco en un organismo.
- 2-Un actuador electroquímico como en la reivindicación 1, en el que el actuador es una bomba de infusión que comprende al menos una celda electroquímica que comprende el electrodo negativo (214), el electrodo positivo (212) y la especie (218), y en la que el electrodo negativo (214) y/o positivo (212) sufre un cambio dimensional con la carga y/o descarga para provocar la infusión de un fluido en un cuerpo.
- 3-Un actuador electromecánico como en la reivindicación 2, en el que, con la carga y/o descarga, la especie de intercalación (218) se intercala, desintercala, oxida, reduce, o galvaniza con una primera porción de la celda electroquímica en un grado diferente que con una segunda porción de la celda electroquímica, y la primera porción experimenta un cambio dimensional resultante con relación a la segunda porción, impartiendo de ese modo una tensión diferencial entre las porciones primera y segunda, provocando un desplazamiento de al menos una porción de la celda electroquímica.
- 4-Un actuador electromecánico de la reivindicación 2 ó 3, en el que la especie de intercalación (218) interacciona con una porción inorgánica de al menos un electrodo de la celda electro-química, dando como resultado un cambio dimensional de la celda electroquímica.
- 5-Un actuador electromecánico como en cualquiera de las reivindicaciones anteriores 1-4, en el que uno o ambos electrodos, con la carga o descarga, sufre un cambio de dimensión que comprende flexión, curvado, o abarquillado.
- 6-Un actuador electromecánico como en cualquiera de las reivindicaciones anteriores 1-5, construido y dispuesto para descargarse espontáneamente.
- 7-Un actuador electromecánico como en cualquiera de las reivindicaciones anteriores 1-6, construido y dispuesto para ser cargado en la fábrica, y descargado parcialmente tras el uso, o ya no se carga después de la primera descarga.
- 8-Un actuador electromecánico como en cualquiera de las reivindicaciones anteriores 1-6, construido y dispuesto para ser descargado en la fábrica, y cargado durante el uso.
- 9-Un actuador electromecánico como en la reivindicación 2 y cualquiera de las reivindicaciones anteriores 3-7, en el que la velocidad de infusión es constante o variable.
- 10-Un actuador electromecánico como en la reivindicación 2 y cualquiera de las reivindicaciones anteriores 3-7, en el que la velocidad de infusión se controla controlando la velocidad de descarga de la celda, o variando la resistencia de un circuito externo a través del cual se descarga la celda.
- 11-Un actuador electromecánico como en la reivindicación 2 y cualquiera de las reivindicaciones anteriores 3-10, teniendo la celda electroquímica un ciclo de trabajo, en el que el ciclo de trabajo se controla abriendo y/o cerrando un circuito externo asociado con la celda electroquímica.
- 12-Un actuador electromecánico como en la reivindicación 11, en el que el circuito externo comprende un resistor.
- 13-Un actuador electromecánico como en la reivindicación 2 y cualquiera de las reivindicaciones anteriores 3-12, en el que la infusión comprende infusión subcutánea, infusión intravenosa, o infusión intratecal.
- 14-Un actuador electromecánico como en la reivindicación 2 y cualquiera de las reivindicaciones anteriores 3-13, que comprende además un depósito situado adyacente a la celda electroquímica, comprendiendo el depósito el fluido, en el que, con la carga o descarga, el cambio dimensional aplica una fuerza sobre un depósito (365) y provoca un desplazamiento de volumen del fluido desde el depósito (365), provocando de ese modo la 5 infusión del fluido en el cuerpo.
- 15-Un actuador electromecánico como en cualquiera de las reivindicaciones anteriores 1-13, en el que la especie de intercalación es un protón, ion alcalino, complejo iónico, ion hidroxilo, ion carbonato, ion clorato, ion sulfato, o ion fosfato.
- 16-Un actuador electromecánico como en cualquiera de las reivindicaciones anteriores 10 1-14, en el que al menos uno del electrodo negativo o electrodo positivo comprende uno o más de Al, Au, Ag, Ga, Si, Ge, Ti, Sn, Sb, Pb, Zn, carbono, grafito, carbono duro, carbono mesoporoso, un óxido, óxido de intercalación, óxido estratificado, mineral de arcilla, sulfuro, sulfuro estratificado, TiS2, MoS2 y WS2.
- 17-Un actuador electromecánico como en cualquiera de las reivindicaciones anteriores 1-16, en el que el fluido comprende un líquido, una mezcla de sólido-líquido, una pasta, o un gel. 15 18.-Un actuador electromecánico como en la reivindicación 1-17, en el que el fluido contiene un fármaco.
- 19-Un actuador electromecánico como en la reivindicación 18, en el que el fármaco es insulina.
Independent claims18
205 paragraphs in 8 sections, as filed
p00001Field of the Invention
p00002The present invention provides systems and devices that involve electrochemical performance.
p00003Background of the Invention
p00004Acting generally refers to a mechanism by which an object, or a portion of an object, can be adjusted or moved by converting energy (for example, electrical energy, chemical energy, etc.) into mechanical energy. Actuators can be categorized by the way they are Convert the energy. For example, electrostatic actuators convert electrostatic forces into mechanical forces.
p00006Piezoelectric performance provides high bandwidth and acting authority, but low voltage (typically much less than 1%), and requires high performance voltages. Shape memory alloys (SMA), magnetostrictors, and newly developed ferromagnetic shape memory alloys (FSMA) are capable of increased stress, but produce slower responses, limiting their applicability. The mechanisms of action that are based on the movement of field-induced domains (piezo, FSMA) also tend to have low blocked effort. The above methods of action are based on the use of high density active materials (lead-based oxides, metal alloys), which negatively impact quality factors based on weight. Thus, there is a need for a technology capable of providing high performance energy density, high acting authority (effort), high free tension, and useful bandwidth.
p00007Certain actuation methods that use electrochemistry have been previously described, in which the acting materials that support loads are in the gas or liquid phase and can be expected to have a low elastic modulus and consequently low actuation energy density and actuation effort , compared to the approach of the present invention. Despite the observation of displacement, mechanical work has not been demonstrated.
p00008EP 1621875 A is considered as the closest prior art for the subject matter of claim 1.
p00009Consequently, improved methods and devices are needed.
p00010Summary of the Invention
p00011The invention relates to an electrochemical actuator as defined in claim 1. Other advantageous embodiments are cited in the dependent claims.
p00012The present invention relates to actuator systems constructed and arranged to be moved from a first orientation to a second orientation, comprising at least one electrochemical cell comprising a negative electrode and a positive electrode, in which one or both of the negative electrodes and positive is an actuator, and comprises a first portion and a second portion, and in which, with the charge and / or discharge, a species is sandwiched, uninterleaved, alloyed with oxidizes, reduces, or is galvanized with the first portion to a different degree than with the second portion, and undergoes a resulting dimensional change relative to the second portion, thereby imparting to the actuator a differential tension between the first and second portions, causing a displacement of at least a portion of the actuator, displacement of the actuator which performs mechanical work without the need to be coupled to a structure that performs said work.
p00013The present invention also relates to actuator systems constructed and arranged to be displaced from a first orientation to a second orientation, comprising at least one electrochemical cell comprising a negative electrode and a positive electrode, in which one
<dl><dt /><dd>or both of the negative and positive electrodes is an actuator, and comprises a first portion and a second portion, and in which, with the charge and / or discharge, a species is sandwiched, deinterleaved, or alloyed with the first portion in a different degree than with the second portion, and undergoes a resulting dimensional change in relation to the second portion, thereby imparting to the actuator a differential tension between the first and second portions, causing the displacement of at least a portion of the actuator, displacement of the actuator which performs mechanical work without the need to be coupled to a structure that performs said work. </dd></dl>
The present invention also relates to actuator systems constructed and arranged to be displaced from a first orientation to a second orientation, comprising at least one electrochemical cell comprising a negative electrode and a positive electrode, in which one
<dl><dt /><dd>or both of the negative and positive electrodes is an actuator, and comprises a first portion and a second portion, and in which with the oxidation and / or reduction of the first portion to a different degree than the second portion, and undergoes a change resulting dimensional in relation to the second portion, thereby imparting to the actuator a differential voltage between the first and second portions, causing a displacement of at least a portion of the actuator, actuator displacement which performs mechanical work without the need to be coupled to a structure that performs said work. </dd></dl>
The present invention also relates to actuator systems constructed and arranged to be displaced from a first orientation to a second orientation, comprising at least one electrochemical cell comprising a negative electrode and a positive electrode, in which one
<dl><dt /><dd>or both of the negative and positive electrodes is an actuator, and comprises a first portion and a second portion, and in which, with the charge and / or discharge, a species is electrochemically deposited in the first portion to a different degree than in the second portion, and undergoes a resulting dimensional change in relation to the second portion, thereby imparting to the actuator a differential tension between the first and second portions, causing a displacement of at least a portion of the actuator, displacement of the actuator which performs mechanical work without the need to be coupled to a structure that performs said work. </dd></dl>
The present invention also relates to actuator devices comprising at least one electrochemical cell comprising a negative electrode, a positive electrode, and a species that can be interleaved, deinterleaved, alloyed with, oxidized, reduced, or galvanized with a first portion of the electrochemical cell in a different degree than with a second portion of the electrochemical cell, thereby suffering the first and / or second portions a dimensional change with the discharge, causing the displacement of the actuator that performs mechanical work, in which the electrochemical cell is constructed and arranged to be charged at the factory, and is partially discharged after use,
<dl><dt /><dd>or it no longer loads after the first download. </dd></dl>
p00015The present invention also relates to infusion pumps comprising at least one electrochemical cell comprising a negative electrode, a positive electrode, and a kind of intercalation, in which the negative and / or positive electrode undergoes a dimensional change with the charge and / or discharge, in order to cause infusion of a fluid in a body.
p00016The present invention also relates to actuators constructed and arranged to be used in a physiological framework, the actuators comprising a first potion adjacent to a second portion, in which the first portion undergoes a dimensional change when exposed to a body fluid comprising a species, and in which the electrochemical intercalation resulting from the species in the first portion, the deintercalation of the species from the first portion, or the oxidation / reduction of the first portion as a result of contact with the species, imparts a dimensional change of the actuator.
p00017The present invention also relates to electrochemical actuators for administering a drug in a body, the electrochemical actuators comprising at least one negative electrode, at least one positive electrode, and one species, in which the electrochemical actuator is subjected to a voltage
p00018or applied current, whereby the application of the voltage or current, or its cessation, includes the intercalation of the species into at least one electrode of the electrochemical actuator, resulting in a volumetric or dimensional change of the electrochemical actuator, and in which the Volumetric or dimensional change results in the administration of a drug in a body.
p00019Brief Description of the Drawings
p00020FIG. 1 shows an example of an actuator system (a) without application of a voltage or current, and (b) with application of a voltage or current, according to an embodiment of the invention.
p00021FIG. 2 shows an example of an actuator system (a) without the application of a voltage or current, and (b) with the application of a voltage or current, to dispense a fluid in an adjacent fluid container, according to an embodiment of the invention .
p00022FIGS. 3A-C show an actuator system that has sufficient rigidity to affect the travel speed and the length of the actuator travel.
p00023FIG. 4 shows an example of an actuator system, according to an embodiment of the invention.
p00024FIG. 5 shows another example of an actuator system, according to an embodiment of the invention.
p00025FIG. 6 shows another example of an actuator system, according to an embodiment of the invention.
p00026FIG. 7 shows another example of an actuator system, according to an embodiment of the invention.
p00027FIG. 8A shows an actuator system comprising first and second portions that are formed of different materials.
p00028FIG. 8B shows an actuator system comprising first and second portions that are formed of different materials, after immersion in water.
p00029FIG. 9 shows an actuator system comprising a layer of Zn (a) in the form of Zn, and
p00030(b) with the conversion of Zn to Zn (OH) 2, resulting in actuator system performance.
p00031FIG. 10 shows another actuator system comprising a layer of Zn (a) in the form of Zn, and (b) with the conversion of Zn to Zn (OH) 2, resulting in the actuator system acting.
p00032FIG. 11 shows an actuator system comprising a lithium ion cell, in which the actuator (a) has zero voltage before exposure to an electrolyte, and (b) undergoes actuation after exposure to the electrolyte.
p00033FIG. 12 shows a lithium ion cell or a nickel metal hydride cell assembled in (a) the charged state, and (b) with spontaneous discharge after emergency in an electrolyte.
p00034FIG. 13 shows an actuator system comprising two different portions (a) before exposure to an electrolyte, and (b) with exposure to an electrolyte, in which the system undergoes bending or curling.
p00035FIG. 14 shows an actuator system comprising two different portions (a) before exposure to an electrolyte, and (b) with exposure to an electrolyte, in which the system undergoes flexion or opening of the structure.
p00036FIG. 15 shows an actuator system having a warped structure (a) before exposure to a species, and (b) with exposure to a species, in which the system undergoes action.
p00037FIG. 16 shows a schematic design for an energy-powered self-powered electrochemical pump.
p00038FIG. 17 shows a graph of the displacement curve versus time for an actuator that changes in a self-powered way, with amplification of the accumulated voltage.
p00039FIG. 18 shows a graph of the displacement curve for an electrochemical changing actuator controlled by a 20% duty cycle.
p00040FIG. 19 shows a galvanostatic discharge profile of a bimorphic electrochemical actuator that uses a 0.10 mm thick tin metal sheet attached to a copper metallic sheet.
p00041FIG. 20 shows a galvanostatic discharge profile of an electrochemical bimorphic cell that uses a 0.05 mm thick tin metal sheet attached to copper.
p00042Other aspects, embodiments and features of the invention will be apparent from the following detailed description when considered in conjunction with the accompanying drawings. The accompanying figures are schematic and are not intended to be drawn to scale. For the purpose of clarity, not all components are labeled in each figure, nor is each component of each embodiment of the invention shown when the illustration is not necessary, to allow those of ordinary skill in the art to understand the invention. All patent applications and patents incorporated herein by reference are incorporated by reference in their entirety. In case of conflict, the present specification, including the definitions, will prevail.
p00043Detailed description
p00044The present invention generally provides systems and devices that involve electrochemical performance.
p00045In some cases, the present invention provides systems (for example, actuator systems) that can comprise at least one component, in which the application of a voltage or current to the component can generate a volumetric or dimensional change of the component. In some cases, volumetric or dimensional change can produce mechanical work. In some embodiments, at least a portion of the system may be constructed and arranged to be moved from one orientation to another orientation. The system may also be associated with another structure, so that a volumetric or dimensional change of the system may affect the orientation, shape, size, volume, or other characteristic of the structure. Systems such as these can be useful in various applications, including pumps (for example, infusion pumps) and drug delivery devices, for example.
p00046In some embodiments, the system may comprise a species associated with one or more components (eg electrodes) during system operation. The species, such as an ion, may be able to interact with one or more portions of the device. Some embodiments of the invention may involve the interaction of a species with one or more electrodes of the device, generating a volumetric or dimensional change in the electrode. As used herein, a "volumetric or dimensional change" refers to the expansion, contraction, and / or other displacement of a system or portion of a system. The volumetric or dimensional change may comprise one or more amounts of expansion, contraction, elongation, shortening, twisting, bending, shearing, or other displacement in one or more dimensions. In some cases, the volumetric or dimensional change can be isotropic. In some cases, the volumetric or dimensional change may be anisotropic. Such changes can be used for mechanical work, that is, performance. Systems may undergo any range of volumetric or dimensional changes that may be suitable for a particular application. For example, an actuator system can be placed in contact with a fluid container, and it can be expanded and contracted so that the system serves as a pumping device for dispensing fluid from the fluid container.
p00047In some embodiments, the present invention provides an electrochemical actuator comprising at least one electrochemical cell that includes an anode, a cathode, and a species (eg, lithium ion), in which the electrochemical cell undergoes a volumetric or dimensional change to the Apply a voltage or current. In some embodiments, the electrochemical actuator also comprises a structure that includes at least a portion constructed or arranged to be moved from a first orientation to a second orientation, for example by volumetric or dimensional change of one or a plurality of electrochemical cells. As the portion of the structure moves, mechanical work occurs. As explained in more detail below, a variety of systems can be operated by volumetric or dimensional change of an electrochemical cell.
p00048As used herein, an actuator system "constructed and arranged to be displaced" refers to an actuator system that can alter the orientation of the system, that is, through the displacement (eg, actuation) of at least a portion of the system. , which affects the behavior of the system or structure associated with the system in its intended purpose. Those of normal skill in the art will understand the meaning of this expression. In an illustrative embodiment, an actuator system can be placed adjacent to a structure such as a fluid container or reservoir, in which the actuator system is constructed and arranged so that movement or other displacement of the system affects the position, shape , size, or other characteristic of the fluid container to pump or dispense fluid from the fluid container.
p00049Advantageously, the displacement of a system, or a portion of a system, from a first orientation to a second orientation can be achieved by a variety of methods, for example bending, curling, twisting, elongation, and contraction, which can be altered, for example, varying the material composition of the system, the configuration of one or more electrochemical cells of the system, the applied voltage or current, the duty cycle, or other operating parameters, as described more fully below. In cases where the system is associated with a structure, the displacement of the system can be altered, for example, by changing the placement of the electrochemical cell in relation to the structure to be displaced, the shape of the structure, any materials in relation to of operation between the cell and the structure, and / or the compositions of the component materials. In some cases, the displacement may comprise a linear displacement of a portion of the system. In some cases, the displacement may comprise the curling of a portion of the system. For example, the system may comprise a disk-shaped portion that may have a first flat orientation, and, with actuation, the disk-shaped portion may be moved, curled, to a second, non-planar, hemispherical orientation.
p00050Additionally, the degree of displacement of a structure, or a portion of a structure, can be customized with respect to the particular application. For example, in some embodiments, the electrochemical cells of the invention can cause displacement of a structure, or a portion of a structure, for example, greater than 5 degrees, greater than 10 degrees, greater than 20 degrees, greater than 30 degrees , or greater than 40 degrees. Depending on the particular application, in other embodiments, electrochemical cells may cause displacement, for example, greater than 1 cm, greater than 10 cm, greater than 20 cm, greater than 50 cm, or greater than 1 m.
p00051In some cases, the volumetric or dimensional displacement of an electrochemical cell can be used when loading or unloading it to perform a physical displacement of the system, a portion of the system, or an adjacent structure or otherwise associated with the system. The volumetric or dimensional displacement (for example, net volume change) can be positive, zero, or negative during loading and / or unloading. In some cases, the net change in volume can easily be computed from the volume changes that occur in each of the constituent materials using tabulated data for the molar volumes of the constituent materials of the cell as a function of its composition or state of charge, or it can be measured directly in the electrochemical cell.
p00052Several different structures can be operated by an electrochemical cell described here. In some embodiments, the invention provides actuator systems (eg electrochemical actuators) constructed and arranged to be moved from a first orientation to a second orientation, with loading or unloading. In some cases, the actuator system can be constructed and arranged to be altered from a first form to a second form, with loading or unloading. In some cases, the displacement produced by the actuator may have the same sign (for example, positive, negative) as the volumetric or dimensional change that occurs in the electrochemical cell. For example, a positive displacement (for example, increase in the linear dimension) may correspond to a positive net change in volume (for example, expansion) of the electrochemical cell itself, and a negative displacement (decrease in the linear dimension) It may correspond to a negative net change in volume (contraction) of the electrochemical cell itself. In some cases, the displacement produced by the actuator may not have the same sign as the volumetric or dimensional change that occurs in the electrochemical cell. For example, as described in the Examples, a positive displacement can be produced by an electrochemical cell that undergoes a negative net change in volume. That is, the displacement of the actuator can be decoupled from the volumetric or dimensional change of the electrochemical cell.
p00053The actuator system may include at least one electrochemical cell comprising a negative electrode and a positive electrode. The actuator system may also include, for example, more than or equal to 2, more than or equal to 4, more than or equal to 10, more than or equal to 20, or more than or equal to 50 electrochemical cells, which are They can operate in series or in parallel. In some embodiments, multiple electrochemical cells can be joined electrically in parallel, but they can be stacked in order to increase the overall displacement while maintaining a low overall device voltage. In some embodiments, the net change in volume of the electrochemical actuator is used to carry out a physical displacement that results in the pumping or dispensing of a fluid, or the administration of a fluid to a body, including, but not limited to , a fluid comprising a drug.
p00054In some embodiments, one or both of the negative and positive electrodes can be an actuator and can change the shape and / or can be moved from a first orientation to a second orientation, with the charge or discharge of the electrochemical cell. In some cases, the actuator system may comprise a first portion and a second portion, optionally in electrical communication with each other, in which the first portion and a second portion undergo a differential volumetric or dimensional change, or a differential displacement, with the load or download For example, the electrode or electrodes that undergo form change or displacement may comprise a first portion that imposes a mechanical restriction on a second portion that may facilitate the movement of the electrode or electrodes. In some embodiments, a first portion is in electrical communication with a second portion. In some embodiments, a first portion is not in electrical communication with a second portion.
p00055In some cases, a first portion and a second portion (for example, corresponding to positive and negative electrodes, respectively or vice versa, of the electrochemical cell) may be in the form of layers, which can be placed immediately adjacent to each other, or, In other embodiments, they may be separated from each other by other material. In some embodiments, the first and second portions are joined together. In some embodiments, the first and second portions are different regions of the same part of the system, in which one portion undergoes a volumetric or dimensional change, electrochemically induced, to a greater extent than the other.
p00056In some embodiments, with loading and / or unloading, a species (for example, an intercalation species, an electron, or a galvanizing species) is sandwiched, deinterleaved, alloyed with, oxidized, reduced, or galvanized with or in the first portion to a different degree (for example, to a degree, concentration, tension, volume, change of form, or other change, different) than the second portion. For example, the species can be intercalated, deintercalated, or alloyed with, oxidized, reduced, or galvanized substantially with the first portion, but not with the second portion, or with the second portion to a lesser extent than with the first portion. As a result of the interleaving, deintercalation, or alloy, oxidation, reduction, or differential galvanization of the first portion to a different degree than the second portion, the first portion may undergo a resulting dimensional change, such as an increase
p00057or decrease in volume, or a linear dimension, or a change in aspect ratio. Because the second portion is not interspersed, deinterleaved, or alloyed with, oxidizes, reduces, or galvanizes the species, or does so to a lesser extent than the first portion, the second portion may not undergo a substantial dimensional change, or It may not undergo the same dimensional change as the first portion. As a result, a differential tension (for example, an opposite tension) is provided between the first and second portions, which can cause a displacement (for example, internal flexure or flexion) of at least a portion of the actuator. The resulting displacement of the actuator can perform mechanical work without the need to be coupled to a structure that performs said work. In certain embodiments of the invention, actuation of an actuator may include expansion, contraction, bending, arching, curling, folding, winding, or other forms of travel from a first orientation to a second orientation.
p00058In some cases, the actuator system may itself be a structure amplifying the tension or de-amplifying the voltage. For example, the actuator system, or a portion thereof (for example, an electrode), can amplify any displacement that arises, for example, from a change in volume that occurs in the system, or a portion thereof. In some embodiments, the actuator system or device may amplify the displacement that arises due to a change in the volume of an electrode. The displacement of the actuator can be used to exert a force or to carry out a displacement of a structure adjacent to the actuator.
p00059For any of the actuator systems and devices (e.g. pumps) described herein, although the displacement of the actuator system, or a portion thereof, can be used to perform mechanical work without the need to be coupled to a structure that performs said work. In some cases, the actuator system may be coupled to a structure that performs mechanical work (for example, a structure that amplifies the tension, a structure that disables the tension). In some cases, the actuator system may not be coupled to a structure that performs mechanical work.
p00060In the embodiment illustrated in FIG. 1A shows an example of an actuator system. As shown in this illustrative embodiment, an actuator system 110 includes a negative electrode 112 in electrical communication with a positive electrode 114. The positive electrode 114 may include a first portion 116 and a second portion 118. In some embodiments, portions 116 and 118 are made of different materials. Portions 116 and 118 may also have different electrical potentials. For example, the portion 116 may comprise a material that can interleave, deintercalate, allocate with, oxidize, reduce, or galvanize a species to a different degree than the portion 118. The portion 118 may be formed of a material that does not interleave, deinterlace , or is alloyed with, oxidizes, reduces, or substantially galvanizes the species. In some cases, the portion 116 may be formed of a material comprising one or more of aluminum, antimony, bismuth, carbon, gallium, silicon, silver, tin, zinc, or other materials that can be expanded by collating or alloying with or form a compound with aluminum. In a particular embodiment, the portion 116 is formed of a material comprising aluminum, which can be expanded by intercalating it with lithium. The portion 118 may be formed of copper, since copper is not interspersed or substantially alloyed with aluminum. In some cases, the portion 118 may act as a positive electrode current collector, and may extend outside the electrochemical cell, for example to form a tongue or a current conductor. In some embodiments, portion 118 can be attached to a tongue or a current conductor that extends outside the cell. The negative electrode 112 may also include a current collector. The actuator system 110 may include a separator 122. The separator may be, for example, a porous separator film, such as a fiberglass cloth, or a porous polymer separator. Other types of separators, such as those used in the construction of lithium ion batteries, can also be used. The actuator may also include an electrolyte 124, which may be in the form of a liquid, solid, or a gel. The electrolyte may contain an electrochemically active species, such as that used to form the negative electrode. The actuator system 110 can be tightly closed in an enclosure 126, such as a polymer container.
p00061As illustrated in the embodiment shown in FIG. 1B, the electrochemical cell can have a voltage 132, so that, when a closed circuit is formed between the negative and positive electrodes, an electronic current can flow between the two electrodes through the external circuit. If the negative electrode 112 is a lithium metal electrode, and the electrolyte contains lithium ions, a current of lithium ions can flow internally from electrode 112 to electrode 114. Intercalation of the portion 116 with lithium can result in a dimensional change, such as an expansion of volume. In some cases, this volume expansion can reach at least 25%, at least 50%, at least 75%, at least 100%, at least 150%, at least 200%, at least 250%, or at least 300% , compared to the initial volume. High volume expansion can occur, for example, when portion 116 is saturated with lithium. As portion 116 increases in volume due to lithium interleaving, portion 118, to which portion 116 may be attached, may not substantially expand due to minimal intercalation or the absence of lithium interleaving. Thus, portion 116 provides a mechanical restriction. This differential tension between the two portions causes the positive electrode 114 to suffer a flexure or flexion. As a result of the dimensional change and displacement of the positive electrode, the actuator system 110 can be moved from a first orientation to a second orientation. This displacement can occur whether the volumetric or dimensional change (for example, net volume change) of the electrochemical cell, due to the loss of lithium metal from the negative electrode and the formation of compound intercalated with lithium or an alloy of Lithium in the positive electrode, it is positive, zero, or negative. In some cases, the displacement of the actuator can occur with a volumetric or dimensional change (for example, net change in volume) of the actuator system, or a portion thereof, which is positive. In some cases, the displacement of the actuator can occur with a volumetric or dimensional change (for example, net change in volume) of the actuator system, or portion thereof, which is zero. In some cases, the displacement of the actuator can occur with a volumetric or dimensional change (for example, net change in volume) of the actuator system, or portion thereof, which is negative.
p00062As used herein, "differential voltage" between two portions refers to the difference in response (eg, performance) of each individual portion by applying a voltage or current to the two portions. That is, a system as described herein may include a component comprising a first portion and a second associated portion (for example, may be in contact, may be fully connected to) the first portion, in which, under essentially identical conditions , the first portion may undergo a volumetric or dimensional change and the second portion does not undergo any volumetric or dimensional change, producing tension between the first and second portions. The differential tension can cause the component, or a portion thereof, to move from a first orientation to a second orientation. In some cases, the differential tension can be produced by interleaving, deintercalation, alloy, oxidation, reduction, or differential galvanization of a species with one or more portions of the actuator system.
p00063For example, interleaving, deintercalation, alloy, oxidation, reduction, or differential galvanization of portion 116 relative to portion 118 can be achieved through various means. (FIG. 1A) In one embodiment, as described above, portion 116 may be formed from a different material from portion 118, in which one of the materials intercalates, deinterleaves, alloys with, oxidizes, reduces, or substantially galvanizes a species , while the second portion interacts with the species to a lesser extent. In another embodiment, portion 116 and portion 118 may be formed of the same material. For example, portion 116 and portion 118 may be formed of the same material and may be substantially dense, or porous, such as a pressed or sintered powder or a foam structure. In some cases, to produce a differential voltage when the electrochemical cell operates, the portion 116 or 118 may be thick enough so that, during the operation of the electrochemical cell, a composition gradient may arise due to the limited ionic transport, producing a differential voltage In some embodiments, a portion or an area of a portion may preferably be exposed to the species relative to the second portion or area of the second portion. In other cases, the protection or masking of one portion in relation to the other portion may result in less or greater interleaving, deintercalation, or alloy with the masked or protected portion compared to the unmasked or protected portion. This can be achieved, for example, by a surface treatment or a deposited barrier layer, lamination with a barrier layer material, or by chemically or thermally treating the surface of the portion to be masked / protected to facilitate or inhibit interleaving, deintercalation, alloy , oxidation, reduction, or galvanization with the portion. The barrier layers may be formed of any suitable material, which may include polymers, metals, or ceramics. In some cases, the barrier layer can also serve another function in the electrochemical cell, such as being a current collector. In some embodiments, the barrier layer can be uniformly deposited on the surface. In other cases, the barrier layer may form a gradient in composition and / or dimension, so that only certain portions of the surface preferably facilitate or inhibit intercalation, deintercalation, alloy, oxidation, reduction, or galvanization of the surface. Linear, stage, exponential, and other gradients are possible. In some embodiments, a variation in porosity along portion 116 or 118, including the preparation of a dense surface layer, can be used to help create a gradient of ion concentration and differential stress. The invention also contemplates other methods of interaction of a species with a first portion in a different degree to induce a differential tension between the first and second portions. In some embodiments, the flexure or flexion of an electrode is used to exert a force or to carry out a displacement that achieves a useful function, as described in more detail below.
p00064In several embodiments described herein, the first and second portions may be described as formed of different materials, which results in different characteristics and properties. It should be understood that, for any of the embodiments described herein, the first portion and the second portion may also be formed of substantially the same material. In cases where the first portion and the second portion may be formed of the same material, the first and second portions may optionally have at least one characteristic that differs, such as dimension, thickness, porosity, or the like, which may produce interleaving, deintercalation, alloy, oxidation, reduction, or differential galvanization, resulting in a differential tension. For example, the first and second portions may comprise the same material but may have different porosities, resulting in a porosity gradient along the first and second portions. In some cases, the first portion may comprise a porous material (for example, compact powder, foam) having a first density, and the second portion may comprise the porous material having a second density, different from the first density.
p00065As described herein, some embodiments of the invention involve the interaction of a species with one or more electrodes. For example, the electrode or electrodes can be interspersed with the species. In some embodiments, during operation of the actuator or device system, an electrode can obtain a concentration that varies spatially from the species, resulting in a differential voltage, resulting in the displacement of at least a portion of the system or device. That is, the species can be intercalated, for example, in a portion of the electrode to a greater degree than in a second portion of the electrode, resulting in a differential voltage.
p00066The actuators of the invention, or their portions (for example, electrodes), especially those that include at least a first portion that can interleave, deintercalate, allocate with, oxidize, reduce, or galvanize a species to a different degree than a second portion , may have any suitable shape such as a sheet, sheet, strip, sheet or folded strip, beam, cup, rod, tube, cylinder, etc., as long as it can be moved from a first orientation to a second orientation, which can be used to achieve a desired function. In some cases, at least a portion of the actuator may be perforated, and / or may have multiple "legs" or "arms" or branches. In some cases, the positive and / or negative electrode is not flat. For example, the positive and / or negative electrode may be a plate or pellet, or other non-flat shape. In some embodiments, the positive and / or negative electrode can have any shape and can comprise at least one groove, in which the groove or grooves can facilitate and / or guide the movement of the actuator system, or a portion thereof. For example, an electrode may be grooved or stamped to facilitate, guide or direct the way in which the electrode moves from a first orientation to a second orientation. In some cases, the electrode can be folded along at least one groove with the actuation.
p00067The actuators of the invention can range in size from the nanometric scale to the micrometric scale, and to the macroscopic scale. For example, in some embodiments, the actuator system 110 may have at least one dimension less than or equal to 1 meter, less than or equal to 10 centimeters, less than or equal to 1 centimeter, less than or equal to 1 millimeter, less than or equal to 100 micrometers, less than or equal to 10 micrometers, less than or equal to 1 micrometer, less than or equal to 100 nanometers, or less than or equal to 10 nanometer.
p00068An electrode of an actuator can also range in size from the nanometric scale, to the micrometric scale, and to the macroscopic scale. For example, in some embodiments, electrode 114 may have at least one dimension less than or equal to 1 meter, less than or equal to 10 centimeters, less than or equal to 1 centimeter, less than or equal to 1 millimeter, less than or equal to 100 micrometers , less than or equal to 10 micrometers, less than or equal to 1 micrometer, less than or equal to 100 nanometers, or less than or equal to 10 nanometer.
p00069Actuators (including electrodes) that include a first portion that can be interleaved, deinterleaved, alloyed with, oxidized, reduced, or galvanized with a species to a different degree than a second portion may be formed of any suitable material in any suitable form that allow interaction with said species (for example, a dimensionally active material). In some embodiments, the first portion is formed of a porous material that changes the dimension with ion exchange. The change in dimension may be a relatively uniform expansion or contraction of volume, or it may be a mode of deformation of the flexure or bending or curling type resulting from the introduction of differential tension, as described herein. The porous material can be a compact pressed powder or a metallic foam or composite material of the dimensionally active material. The second portion may be formed of a non-dimensionally active material. The first and second portions may additionally comprise additives such as a binder or a conductive additive such as carbon or a metal. The dimensionally active material may comprise, for example, one or more of the following species: Al, Au, Ag, Ga, Si, Ge, Ti, Sn, Sb, Pb, Zn, carbon, graphite, hard carbon, mesoporous carbon, an oxide, an intercalation oxide, a stratified oxide, mineral clay, sulfide, stratified sulfide, TiS2, MoS2, and WS2. It should be understood that the actuators of the invention may also comprise other metals, compounds containing metals, inorganic materials, and the like.
p00070In some cases, the actuators of the invention may undergo a dimensional change provided by a porous electrode that changes dimension with ion exchange. In some cases, the porous electrode, with the charge or discharge, undergoes a change in dimension that includes buckling, bending,
<dl><dt /><dd>or curled up In some embodiments, the porous electrode may comprise a porosity gradient, in which a first portion of the porous electrode has a porosity that is different from the porosity of a second portion of the porous electrode. In some cases, the porous electrode further comprises a surface layer in contact with the porous electrode, in which the surface layer is sandwiched, deinterleaved, alloyed with, oxidized, reduced, or galvanized to a greater degree than the porous (underlying) electrode. . The surface layer may partially or substantially cover or encapsulate the outermost surface of the porous electrode, so that the surface layer may be principally and / or directly exposed to other components of the system. In some cases, the surface layer can be intercalated or alloyed to a greater extent than the underlying porous electrode. In some cases, the surface layer may have a density greater than the underlying porous electrode.</dd></dl>
In some cases, a species that can interleave, deintercalate, allocate with, oxidize, reduce,
<dl><dt /><dd>or galvanizing at least a portion of an actuator (for example, a portion of an electrode), may be in the form of an ion. Non-limiting examples of ions include a proton, hydroxide ion, sulfate ion, chlorate ion, phosphate ion, and a nitrate ion. In other cases, the species may comprise an alkali metal or an alkaline earth metal. In certain embodiments, the species is an electron, which can cause oxidation.</dd></dl>
<dl><dt /><dd>or reduction of at least a portion of a surface. In other embodiments, the species is a galvanizing species, which can be electrochemically deposited in the first portion to a different degree than in the second portion. In some cases, the species can be selected from the group consisting of a proton, alkaline ion, lithium, ionic complex, hydroxyl ion, carbonate ion, chlorate ion, sulfate ion, phosphate ion, other multiatomic ionic complexes, and the like. In some cases, the species is selected from the group consisting of a proton, alkaline ion, ionic complex, hydroxyl ion, carbonate ion, chlorate ion, sulfate ion, and phosphate ion. In some cases the species is a proton.</dd></dl>
p00071The species may initially be present in an electrochemical cell in the form of a solid, such as the material used to form the positive or negative active species of the electrodes. In other cases, the species may be in the form of a solid that is laminated to one of the electrodes, but is not a part of the active material of the electrode. In another embodiment, the species may be in the form of a separate solid ionic source, such as a solid electrolyte. In yet another embodiment, the species may be present in the form of a liquid or a gel, for example as an electrolyte, and may be present in the electrochemical cell before the first charge / discharge of the cell. In other embodiments, these species may be present in a substance outside the electrochemical cell. For example, the species may be present in the environment in which the actuator is used. In a particular embodiment, the actuator is designed to immerse it in a fluid containing a species that can intercalate, allocate with, oxidize, reduce, or galvanize a portion of an electrode of the electrochemical cell. For example, the fluid can be a body fluid, and the species can be an ionic species present in the body fluid.
p00072In some cases, a device of the invention may comprise an anode, cathode, and lithium ions as the species. By applying an electric field between the anode and the cathode, the device can be reversibly charged and unloaded. In some cases, when charged, lithium ions can be inserted into the anode so that the anode undergoes a volumetric or dimensional change relative to the cathode, which remains essentially unchanged in volume or dimension. Upon discharge, lithium ions can be transported from the anode to the cathode, so that lithium ions are inserted into the cathode. As a result, the anode can return to its volume / shape before loading, and the cathode can undergo a volumetric or dimensional change relative to the anode. In some cases, both the anode and the cathode, whether simultaneously or not simultaneously, can undergo a volumetric or dimensional change with the charge / discharge cycle. In some cases, only one of the anode and cathode can undergo a volumetric or dimensional change with the charge / discharge cycle.
p00073The actuators of the invention can be used in a variety of applications. For example, the actuators can be used in microfluidic devices, in which, for example, switching and control functions can be performed by means of valves by the actuator. In other cases, the actuator can be used as a pump to cause a fluid to flow into a channel or out of a hole, including a pump for the controlled delivery of a drug. In other embodiments, an actuator may be part of an external or implantable medical device. The species that can be interleaved, deinterleaved, oxidized, reduced, or galvanized with at least a portion of the actuator (for example, a portion of an electrode) may be part of the electrochemical cell in some embodiments (for example, in manufacturing before of use); however, in other embodiments it may be a constituent of the medium in which the actuator is used. The actuators can also be part of Microelectromechanical Systems (MEMS) devices, such as micro mirror assemblies in which directly accessible micro actuators are operated individually. In other cases, one or more actuators can be constructed and arranged to be deployed in a structure with the application of a current or voltage. Such structures can be useful as tents or frames, for example. In other cases, an actuator of the invention may be a component of a surgical tool or medical implant, which can be expanded or contracted electrically by an electrical input. A variety of applications are described below in more detail.
p00074In some embodiments, the actuators of the invention can be used to displace or deform a structure adjacent to the actuator. For example, as shown in the embodiment illustrated in FIG. 2A, the actuator system 150 includes the actuator 151 which serves as a pump for dispensing fluid 170 from a reservoir 172. The pump can dispense different volumes of fluids, for example greater than 0.01 ml, greater than 0.01 ml, greater than 1 ml, greater than 5 ml, greater than 10 ml, greater than 100 ml, greater than 1 l. Actuator 151 may operate similarly to actuator 110 described in FIG. 1. Briefly, a species can be interleaved, deinterleaved, alloyed, oxidized, reduced, or galvanized with a first portion 156 of electrode 154 in a non-uniform manner relative to portion 158, so that a differential tension is induced between First and second portions. The second portion may be a mechanical restriction, which causes flexion or flexion of electrode 154, and, consequently, flexure or flexion of actuator 151. The reservoir 172 adjacent to the actuator 151 may be formed of a deformable material such that the flexure of the actuator 151 causes an increase in the pressure within the reservoir, forcing fluid 170 to be dispensed from the reservoir, as shown in FIG. . 2B. In some embodiments, the rate of dispensing or infusion of fluid 170 from the reservoir can be controlled by the rate and / or degree of displacement (eg, travel length) of the actuator from a first position to a second position. The dispensing speed can be controlled so that it is constant or variable. The rate and / or degree of action can be controlled by parameters such as the amplitude and / or duration of the current or voltage applied (for example, during loading or unloading), concentration of the species to be inserted, uninterleaved, alloyed or galvanized with an electrode of the electrochemical cell, and the material dimensions and compositions of the materials used to form the electrochemical cell, such as the configuration and material compositions of the first and second portions of the actuator, which interact with the species in different grades.
p00075One or more electrochemical cells, optionally in combination with one or more components, can be arranged to achieve the displacement of a system, or a portion of a system. In some cases, electrochemical cells that have different actuation capabilities can be arranged on a surface in a pattern, in which each electrochemical cell is independently controlled. Other cell configurations, components, and / or devices may be used in the context of the invention, as described in, for example, US Patent Publication No. 2006/0102455, which is based on US Patent Application Series No. 11 /150.477, and International Publication No. WO 2005/124918, which is based on International Series Application No. PCT / US / 2005/020554.
p00076The actuators of the invention can be manufactured with different rigidity of the materials, to allow different ranges of actuation rate and travel length. For example, an actuator that has a large travel length may be formed of one or more materials that have a relatively low stiffness. In such an embodiment, a short pulse of current can cause a slow displacement of an actuator from a first orientation to a second orientation. On the contrary, an actuator formed by one or more stiffer materials can be displaced only when current is applied. In such an embodiment, the actuator can be moved from a first orientation to a second or third orientation with each increase in current applied, in some cases, regardless of the load. In some embodiments, the transfer of energy from the actuator to a mechanical system is maximized when the rigidity of the actuator and mechanical systems is on par. Consequently, the choice of actuator materials can be chosen based on the particular application and / or the desired mode of action.
p00077FIGS. 3A-C show an example of how the stiffness of an actuator can influence the travel rate and the travel length of the actuator. In the embodiment illustrated in FIG. 3A, the actuator 180 includes a first portion that can interleave, deintercalate, allocate with, oxidize, reduce,
p00078or galvanize a species to a different degree than a second portion. The end 181 of the actuator can be fixed in one position, with the actuator in a first position a. The actuator may be adjacent to a piston 190 and a reservoir 192 containing fluid 194. With interleaving, deinterleaving, alloy
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p00090tion, oxidation, reduction, or non-uniform galvanization of a species (for example, with the first portion with respect to the second portion of the actuator), the actuator 180 can be moved from position a to position c, as shown in the FIG. 3C. Actuator 180 may be formed of one or more materials that have a low stiffness to achieve a large "ac" travel length. This can be achieved, for example, by applying a short pulse of current to the actuator, so that the actuator moves, which can cause the displacement of the piston 190, to dispense the fluid from the reservoir. A short pulse of current can slowly push the fluid out of the reservoir until the actuator relaxes to its new equilibrium position c. On the contrary, FIG. 3B shows the actuator 182 formed by a material of high rigidity in a first orientation, in which one end of the actuator is in position b. By applying a current of magnitude and duration similar to that of actuator 180, actuator 182 can be moved from position b to position c, as shown in FIG. 3C. The travel length of the actuator 182, "bc", is shorter than the travel length of the actuator 180, "ac", due to the different stiffness of the materials used to form the actuators 180 and 182. In some embodiments, the actuators can be stacked, for example in parallel or in series, to increase the load or force applied to a structure.
p00091The following examples further illustrate different configurations and ways in which actuators of the invention can be implemented.
p00092In the embodiment illustrated in FIG. 4, the actuator system 200 includes the actuator 210 that includes a positive electrode 212, a negative electrode 214, and an electrolyte layer 216 that includes species 218 that can be interleaved, uninterleaved, alloyed with, oxidized, reduced or galvanized with the positive or negative electrode. The transport of the species through the electrolyte layer under the applied voltage 220 can be used to move the actuator 210 up or down in the directions of the arrows 222 and
p00093224 This displacement can result in the action, which, for example, can be used to open or close a valve, move a mirror, pump, fluid, etc. As explained above, the combinations of materials used to form the positive and negative electrodes may vary. For example, suitable materials may include the active materials in a lithium ion or nickel metal hydride battery. As illustrated in this embodiment, the actuator system 210 is fixed at one end to the substrate 228. The substrate can act as a mechanical constraint, so that the portion 230 of the actuator undergoes minimal displacement or no displacement. Because the portion 232 of the actuator is not fixed, this portion undergoes a displacement that results in bending.
p00094In another embodiment, the species that can be interleaved, alloyed with, oxidized, reduced or galvanized with a portion of an actuator can be positioned such that a portion of the actuator is preferably exposed to the species, while a different portion of the actuator is not is exposed, or exposed to the species to a lesser extent. For example, in the embodiment illustrated in FIG. 5, the actuator system 250 includes the actuator 252 comprising a portion 254 and a portion 256. Portion 256 may be exposed to species 260, which is submerged in a substance 262 (eg, an electrolyte) to a greater extent than portion 254. Portion 254 and substrate 264 may be conductive and may serve as positive electrodes. and negative Portion 256 can be isolated from substrate 264 by an insulator 266. By applying a potential difference between the substrate (or a remote counter electrode) and portion 254, species 260 can be interleaved, deinterleaved, alloyed with, oxidized, reduced, or galvanized portion 256 to a degree greater than portion 254. The type of interaction of portions 254 and / or 256 with species 260 will depend, for example, on the particular type of species, and on the materials used to form portions 254 and 256. This interaction may cause the actuator 252 to flex as a result of the differential tension between portions 254 and 256.
p00095Structures such as actuator systems 200 and 250 can be manufactured by a wide variety of methods, including MEMS manufacturing, various methods of deposition of thin film structures, thick film coating technology, electrode deposition methods, and assembly. and physical lamination. Other manufacturing methods may also be suitable, and are known to persons of ordinary skill in the art.
p00096As shown in the embodiment illustrated in FIG. 6, the actuator system 270 includes an electrode 272 in electrical communication with the actuator 276, which may be integrally connected (or non-integrally connected) to the substrate 274. The actuator 276 may be of uniform composition; however, portion 280 may be exposed to species 282 to a greater extent than portion 284 of the actuator. Different exposure (for example, different areas of exposure) to the species may cause intercalation, deintercalation, alloy, oxidation, reduction, or galvanization with portion 280 to a different degree than with portion 284. This may cause actuator actuation. , for example in the direction of arrows 222 and 224.
p00097In some embodiments, the actuators of the invention are constructed and arranged to be used in a physiological framework, such as in a body. For example, some embodiments of the invention
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p00109they provide electrochemical actuators for administering a drug in a body, comprising at least one negative electrode, at least one positive electrode, and a species as described herein, in which the electrochemical actuator can be subjected to an applied voltage or current, with what the application of the voltage or current, or its termination, includes the intercalation of the species in at least one electrode of the electrochemical actuator, resulting in a volumetric or dimensional change of the electrochemical actuator. In some cases, volumetric or dimensional change may be useful in administering a drug to a body, or a fluid comprising a drug in a body, for example via dispensing or infusion methods, and other methods, as described herein. .
p00110In some cases, the actuator is submerged in a body fluid (eg, blood, urine, sweat, etc.) that comprises a species that can be interspersed with a portion of the actuator electrode. With interleaving, the electrode can undergo a displacement from a first orientation to a second orientation. In other embodiments, the species can be uninterleaved from a portion of the electrode in the body by exposing it to body fluid. Or in other embodiments, the species can oxidize or reduce a portion of the electrode by exposing it to body fluid, which results in displacement. In other cases, the actuator can be used outside the body, for example the actuator may be exposed to a body fluid extracted from a body.
p00111FIG. 7 is an illustrative example of an actuator that can be used in a physiological framework. Actuator 290 includes a positive electrode 292, a negative electrode 294, and an insulator 296 located between the two electrodes. The actuator 290 may be immersed in the body fluid 298 comprising the species 299, which can be interleaved into or can be uninterleaved out of one electrode to a degree greater than the other electrode, for example with the application of a voltage or current. This can cause the actuator to move from a first orientation to a second orientation. Different modes of actuator travel can be achieved, depending on the mechanical design of the actuator. For example, the actuator may be in the form of a beam, accordion, stent, disc, or a multilayered stacked structure. Other shapes and designs of actuators can also be used to induce expansion, contraction, folding, twisting, bending, winding, etc., of the structure from a first orientation to a second orientation. In some embodiments, the actuator may be in the form of a medical implant or a component of an implant, such as a stent, a sensor, a prosthesis, and the like.
p00112In another embodiment of the invention, an actuator system includes at least one electrochemical cell comprising a negative electrode, a positive electrode, and a species that can be interleaved, deinterleaved, alloyed with, oxidized, reduced, or galvanized with a first portion of the electrochemical cell to a different degree than a second portion of the electrochemical cell. As a result of one of the previous interactions of the species with the first and / or second portion, the first and / or second portions may undergo a dimensional change with the discharge, causing the displacement of the actuator that performs mechanical work. In some embodiments, the electrochemical cell is constructed and arranged to be charged at the factory, and unloaded during use. In some embodiments, the electrochemical cell is constructed and arranged to be charged at the factory, and is partially discharged after use, or is no longer charged after the first discharge. The actuator system can be constructed and arranged to discharge spontaneously. In some cases, the actuator can be downloaded one or more times in different cases to cause various actions. With the discharge (for example, partial discharge, complete discharge), the actuator can be discarded. Such a configuration may be useful for portable devices such as certain pumps, sensors, implants, and medical devices.
p00113An embodiment of the invention includes an infusion pump to infuse a liquid into a body. The infusion pump includes at least one electrochemical cell comprising a negative electrode, a positive electrode, and a species, in which the negative and / or positive electrode undergoes a dimensional change with the charge and / or discharge, to cause the infusion of the fluid in the body. As an alternative, the infusion pump may not include a species in manufacturing, but, with exposure to a species during use, the infusion pump can perform the action and infuse a fluid. In some arrangements, the infusion pump is constructed and arranged to discharge spontaneously. Such a device is self-powered energetically, meaning that the electrochemical cell of the device is manufactured in the charged state. The device may include positive and negative electrode materials, selected so that the electrochemical cell expands or deforms upon discharge. For example, low cost materials, such as silicon and tin, can be used as expansion materials (for example, as much as 300%) when being lithiated.
p00114The pumping speed, including the magnitude of volume dispensed and the duration of the dispensing, can be determined by the rate of expansion or deformation of the cell, which in turn can be controlled by the discharge rate of the electrochemical cell. The discharge control can be carried out by various methods, such as varying the resistance of an external circuit through which the cell is discharged. External controls may include, for example, a resistor, which includes a thin metal or wire that also serves as a fuse. This can be used to allow controlled self-discharge of the electrochemical cell through the resistor or external circuit. In a particular embodiment, a variable resistor is implemented in the external circuit, including a solid state circuit, in order to control the discharge rate and the pumping speed. By varying the external resistance of the cell, the instantaneous discharge rate and the actuation rate can be controlled.
p00115In another embodiment, the work cycle of the device can be varied in order to control the extent or degree of displacement or pumping. In this embodiment, the external circuit through which the device is discharged or charged can be repeatedly switched between open and closed circuit, or "on and off". That is, the duty cycle can be controlled by opening and / or closing an external circuit associated with the actuator device. The frequency and duration of the on / off pulses can provide control of the total travel and travel speed. For example, if a device in external short-circuit conditions shows a complete discharge in a time t that results in a total voltage , the switching between open and closed circuit conditions so that the total time used in the closed circuit is t / 10 corresponds to a 10% duty cycle, the net tension being / 10. In embodiments where the duration of the closed circuit pulse is constant, the deformation rate can be controlled by varying the pulse frequency. The pulse rate and duration can also be varied independently to suit the nonlinearities inherent in the displacement curve versus response time of the device in order to achieve a desired displacement profile versus the actuator or pump time.
p00116In other embodiments, the download speed can be designed in the cell (for example, a self-discharge speed can be engineered). In a particular embodiment, the internal impedance of the cell is designed using methods known to those skilled in the art of electrochemical devices or batteries, in order to produce a desired discharge rate. In conditions of external short-circuit, or in those conditions in which the resistance between the external conductors of the cell is substantially lower than the internal impedance of the cell, the discharge speed, and therefore the actuation rate, is mainly determined by the internal impedance of the cell. For example, the cell can be designed for a certain maximum discharge rate and lower speeds introduced using the control methods described herein, or it can be designed to have a relatively high internal impedance, which provides a safe and low discharge rate even in accidental short circuit conditions.
p00117The rate and / or amount of deformation of the device (and the corresponding speed and / or amount of pumping of a pump controlled by such device) can be constructed in the device such that, for example, a disposable single-use device pumps at a predetermined and set speed and / or volume and time. Alternatively, or in addition, a device with a control can be constructed so that the speed and / or degree of discharge / pumping can be varied during the use of the device, or can be adjusted between one of several different settings before using the device. device. In some cases, when the device can be used, multiple times, speeds and / or amount of discharge / pumping can be varied between uses, during uses, etc. Those of ordinary skill in the art are quite capable of designing, by means of digital or analog circuitry, or a combination, systems in a device for any of these characteristics.
p00118Through these and / or other means, the pumping speed can be varied widely by controlling the discharge rate of the electrochemical cell. In some embodiments, the download speed can be controlled remotely, for example, without wires through the transmission of signals sent to a control circuit that controls the duty cycle or resistance of the external load. If desired, the pump can dispense different volumes of fluids, for example greater than 0.01 ml, greater than 0.1 ml, greater than 1 ml, greater than 5 ml, greater than 10 ml, or greater than 50 ml.
p00119The actuator applications of the invention in the form of a pump can be used for applications that include, but are not limited to, the subcutaneous delivery of drugs or fluids, intravenous, intrathecal and other usual methods of delivering drugs and fluids to the body. , perfume air fresheners or dispensers, and implantable drug delivery devices.
p00120For example, it is well known that when a bimetallic cell is immersed in an electrolyte, one of the bimetallic pair is the anode, and does not oxidize preferably, while the other preferentially oxidizes. An example is the anodic protection of iron and steel with zinc. In an illustrative embodiment, FIG. 8A shows a first portion 302 and a second portion 304, the first and second portions being formed by different materials. FIG. 8B shows the same structure after immersion in water. The structure now includes a layer 306. If the first portion comprises Fe, the second portion comprising Zn, with exposure to water, forms portion 306, which comprises Zn (OH) 2. The reaction in portion 302 is 2H + + 2e = H2 (g), and the reaction in portion 306 is Zn + 2 (OH-) = Zn (OH) 2 + 2e.
p00121As shown in FIGS. 9A-B, the actuator 310 includes a first portion 312 and a second portion 314. If the first portion is formed by Fe and the second portion 314 is formed by Zn in thin layers, with the conversion of Zn to Zn (OH) 2 , volumetric expansion during the formation of Zn (OH) 2 (for example, Zn + 2 (OH-) = Zn (OH) 2 + 2e) would result in spontaneous action, causing displacement in the form of flexion, as shown in FIG. 9B. This spontaneous action can be used in actuators of the invention to perform mechanical work.
p00122As shown in FIG. 10A-B, if the first portion 320 is formed by Zn and the second portion 322 is formed by Fe, with the conversion of Zn (for example, Zn + 2 (OH-) = Zn (OH) 2 + 2e), the Structure 318 will open, as shown in FIG. 10B This type of action would be useful for structures such as a stent, a disc that expands to relieve a compressive effort between vertebrae, or other structures. Similar types of action can be achieved using a species that simply swells by preferential binding absorption or a molecular species from a fluid.
p00123Those of ordinary skill in the art will be able to select other bimetallic pairs that would be suitable for use in the invention.
p00124In the body, it is desirable to avoid significant gas evolution. It is also desirable to have ductile but strong materials that undergo permanent plastic deformation, for certain applications. In some embodiments, it may be advantageous to use an actuator that spontaneously discharges when a positive and negative material is electrically short-circuited and immersed in an electrolyte that contains a species that can be interleaved, uninterleaved, alloyed with, oxidized, reduced, or galvanize with at least a portion of the actuator.
p00125FIGS. 11A-B show a lithium ion cell (for example, comprising a portion Li0.5CoO2, and comprising another portion LixTi5O12, in which x> 4) assembled in the state of charge, and which undergoes spontaneous discharge with the emergency in a electrolyte. (As an alternative to a lithium ion cell, the actuator can be a nickel metal hydride cell (for example, comprising a Ni3 + OOH portion, and comprising the other portion MHx, in which M is a metal), assembled in the state of charge and suffering spontaneous discharge with the emergence in an electrolyte). FIG. 11A shows the actuator at zero voltage before exposure to an electrolyte, and FIG. 11B shows the actuator after exposure to the electrolyte. With the discharge, a first portion of the actuator expands to a volume greater than a second portion of the actuator, thereby causing flexion (contraction) of the actuator. Thus, spontaneous discharge with exposure of the actuator to an electrolyte can cause the action.
p00126FIGS. 12A-B show a lithium ion cell or a nickel metal hydride cell assembled in the state of charge (FIG. 12A) and undergoes a spontaneous discharge (FIG. 12B) with the emergence in an electrolyte. The shape of the actuator causes it to expand with spontaneous discharge.
p00127Various types of materials can be used in the actuators of the invention. For example, metallic titanium can be used as an electrode material when the species is hydrogen, since metallic titanium is a very good means of hydrogen absorption. Other suitable means of hydrogen absorption include noble metals. Pt, Rh, Ir and Au are also strong and ductile metals that can be used as electrode materials. In a particular embodiment, a stent that opens spontaneously (or another actuator design) can be manufactured by joining, for example, a hydrated metal to a non-hydrated metal, so that, upon exposure to an electrolyte, the transfer hydrogen from one to another causes the actuator to move. This specific approach can also benefit from the introduction of a diffusion barrier between the two metals, as it is widely used in semiconductor device technology, to prevent the diffusion of hydrogen between the two metals causing the action before exposure to the electrolyte, as shown in FIGS. 13
p0012814. FIG 13 shows an actuator system comprising two different portions, each comprising a different material (for example, metal), and optionally a diffusion barrier located between each portion, (a) before exposure to an electrolyte and ( b) with exposure to an electrolyte, in which the system undergoes bending or curling. Similarly, FIG. 14 shows an actuator system comprising two different portions, each comprising a different material (for example, metal), and optionally a diffusion barrier located between each portion, (a) before exposure to an electrolyte and (b) with exposure to an electrolyte, in which the system undergoes flexion or opening of the structure. In some embodiments, iridium is attractive as a metal used to form at least a portion of the actuator, due to its biocompatibility.
p00129In another embodiment, the actuators of the invention may include hinged structures, for example as shown in FIGS. 15A-B. The actuator can include a first portion 342 that can preferably interleave, deintercalate, allocate with, oxidize, reduce, or galvanize a species, and a second portion 344 that does not intercala, deintercala, alloys with, oxidizes, reduces, or preferably galvanizes the species. In some cases, the second portion 346 and the third portion 348 are formed of the same material. With exposure of the actuator to a first species, the first portion can interleave, deintercalate, allocate with, oxidize, reduce, or galvanize a species to a different degree from that of the second and / or third portion, causing displacement (for example , expansion) of the actuator, as shown in FIG. 15B. Optionally, the second portion 346 and the third portion 348 are formed of different materials, and, with exposure to a second species, the actuator can be moved from a first orientation to a second orientation.
p00130The actuators of the invention include a first portion and a second portion, which, with loading and / or unloading, is sandwiched, deinterleaved, alloyed with, oxidized, reduced, or galvanized a species with the first portion in a Different degree than with the second portion, the first portion experiencing a resulting dimensional change relative to the second portion, can be used in a variety of frames. Accordingly, the actuators of the invention may have configurations, shapes, and / or designs other than those described above. Examples of such configurations, shapes and / or designs include those described in US Patent Nos. 6,545,384; 5,907,211; 5,954,079; 5,866,971; 5,671,905; and 5,747,915.
p00131The considerations for the design of low-voltage, long-life electrochemical actuators are now described. In some embodiments, the design of a long-life, low-voltage electrochemical actuator includes certain operating criteria. In one embodiment, a method is provided for operating an electrochemical cell comprising a negative electrode, a positive electrode, a non-aqueous electrolyte, and lithium as a species (for example, a kind of intercalation). The electrochemical cell can be operated so that the positive electrode has a medium equilibrium potential (or open circuit voltage (OCV)) with respect to the metallic lithium throughout the state of charge of its use that is less than about + 4V The negative electrode may have an average potential with respect to metallic lithium throughout the state of charge of its use that is greater than about + 0.2V. The electrochemical cell may be in operating relationship with a component that can be moved from a first orientation to a second orientation. The operation of the electrochemical cell can cause a volumetric or dimensional change of the electrochemical cell. By applying a voltage less than about 10V to the electrochemical cell, the component can be moved from the first orientation to the second orientation from the volumetric or dimensional change of the electrochemical cell.
p00132As described in more detail below, too high potential in the positive electrode may result in electrochemical corrosion of the current collector and / or active materials in the positive electrode. In some cases, the high potential can also cause degradation of non-aqueous electrolytes or salts, which can result in loss of electrolyte conductivity and / or undesirable side effects in the cell. As such, certain electrochemical cells of the invention can be operated to have a medium lithium potential throughout the state of charge of the cell less than about + 4V, less than about 3.5V, less than about + 3.0V or less than about 2.5V.
p00133As also described below, a medium equilibrium potential that is too low (for example, with respect to metallic lithium throughout the state of charge of its use) can cause negative effects such as electrochemical corrosion of the negative electrode current collector, or the deposition of metallic lithium. Consequently, electrochemical cells can be operated so that the negative electrode has an average equilibrium potential greater than about + 0.2V, greater than about + 0.5V, greater than about + 1.0V, or greater than about + 1.5V. Depending on the particular electrochemical cell, a maximum range and a minimum range of average equilibrium potential of the positive and negative electrodes, respectively, can be chosen. For example, in one embodiment, the positive electrode has an average equilibrium potential less than about + 3.5V, and the negative electrode has a medium equilibrium potential greater than about + 0.5V. In another embodiment, the positive electrode has a medium equilibrium potential less than about + 3.5V, and the negative electrode has a medium equilibrium potential greater than about + 1.0V. In yet another embodiment, the positive electrode has an average equilibrium potential less than about + 3.5V, and the negative electrode has a medium equilibrium potential greater than about + 1.5V. In yet another embodiment, the positive electrode has an average equilibrium potential less than about + 3.0V, and the negative electrode has a medium equilibrium potential greater than about + 0.5V. Of course, other ranges of medium equilibrium potential for the positive and negative electrodes can be chosen.
p00134In certain embodiments, the operation of an electrochemical cell may involve applying a voltage less than about 10V to the electrochemical cell and, from the volumetric or dimensional change of the electrochemical cell, displacing the component from a first orientation to a second orientation. As explained in more detail below, the applied voltage (i.e., the operating voltage) is generally low, in order to increase the life cycle of the electrochemical actuator. Consequently, the operation of an electrochemical cell may include applying a voltage less than about 10V, less than about 8V, less than about 7.5V, less than about 6V, less than about 5V, or less than about 4V However, it should be understood that, for certain periods that require high energy performance over short times, the applied voltages may be greater than the applied steady state voltage. Consequently, more than 95% of the operating life of an electrochemical cell can be operated with an applied voltage of less than about 10V, less than about 8V, less than about 7.5V, less than about 6V, less than about 5V, or less than about 4V. In other cases, more than 90%, more than 80%, more than 70%, more than 60%, or more than 50% of the operating life of the electrochemical cell can be operated at such voltages.
p00135The following considerations for the design of long-life, low-voltage electrochemical actuators are specifically described for the design of electrochemical lithium cells with non-aqueous electrolyte. However, it should be understood that the principles can also be applied to any electrochemical cell used as an actuator.
p00136For the motive force for the transport of a species, including an ionic species, in an electrochemical cell used as an actuator it can be the overpotential (during charging) or the subotential (during discharge), being the overpotential and the subotential, respectively, the magnitude of the voltage applied above and below the equilibrium or idle or open circuit (OCV) voltage of the cell in a particular state of charge. The OCV as a function of the state of charge can easily be determined by those of normal skill in the art if it is known in potential versus ax (concentration) of each compound, and if the cell parameters such as the ratio of cathodic material are known to anodic and the degree of irreversible loss of the ionic species during the cycle. For example, LiCoO2-graphite cells can have an OCV that varies continuously with the state of charge between about 3.9V and around 3V, while LiFePO4-graphite cells have an almost constant voltage of around 3, 3V throughout a wide state of charge.
p00137For a high rate of performance, it may be desirable to have a large overpotential during loading, and a large subotential during discharge. On the other hand, it is also recognized here that the range of potentials applied to an electrochemical cell can influence the behavior and life of the cell, especially during many charge / discharge cycles, for several reasons. At the high end of the operating voltage range, it is recognized that too high potential can cause electrochemical corrosion of the current collector (such as aluminum) or active materials in the positive electrode, or degradation of non-aqueous electrolytes or salts. This can result in the loss of electrolyte conductivity or undesirable side effects such as the formation of gas inside the cell. At the low end of the operating voltage, too low potential can cause electrochemical corrosion of the negative electrode current collector (such as copper) or the deposition of metallic lithium, the latter occurring if the potential in the negative electrode reaches that in the that the metallic lithium is stable. Thus, for a high rate of performance, as well as for stability and long life in a non-aqueous lithium electrochemical cell used for the performance, it may be desirable to have a relatively low OCV, so that a high overpotential can be applied. during charging without reaching the stability limits of the electrolytic system or the positive current collector. However, the low CPO should not be too low; otherwise, a high sub-potential, applied during discharge, can reach potentials to which the anodic current collectors (such as copper) dissolve, or this can cause the metallic lithium to galvanize. The selection of active materials for the positive and negative electrodes that meet these criteria is important, since it may be desirable to provide high energy and actuation power in electrochemical cells of the invention.
p00138In some embodiments, it is desirable to have a positive electrode material with both a high rate and a high voltage, and an OCV measured with respect to metallic lithium that is less than about 4V. In other embodiments, the OCV measured with respect to lithium is less than about 3.5V, less than about 3V, or less than about 2.5V. Non-limiting examples of such positive electrode materials include compounds for electrodes based on LiFePO4, TiS2, TaS2, and their alloys and compositionally modified forms. In some cases, electrochemical cells include negative electrode materials with a high power as well as an OCV over the range of composition used that is at least + 0.1V with respect to metallic lithium. In other cases, the OCV is at least + 0.5V or more. For example, graphite can be a suitable material when used with a positive electrode material so that the net tension is substantial. Another suitable material includes the spinel of LixTiO2, for example the starting composition Li4Ti5O12, which, with lithiation, has an almost constant potential of about 1.57V with respect to metallic lithium over a wide range of lithium compositions , and an almost zero volume change. Consequently, this may allow the change in volume at the positive electrode to be used for actuation. In some embodiments, electrochemical cells based on such combinations of positive and negative electrode materials have cell OCVs typically less than about 3.5V. Of course, it is possible to have a cell voltage that varies between positive and negative values as the cell is charged or discharged, while maintaining a positive electrode potential that is not too high during the conditions described above. high and a negative electrode potential that is not too low with respect to metallic lithium.
p00139When such a cell is used for electrochemical actuation, the applied superpower and subpower potential can result in a charge voltage that is above, and a discharge voltage that is below, of the OCV of the cell. However, generally, the absolute value of the operating voltage of the cell remains low. For example, the absolute value of the operating voltage may be less than about 10V, less than 7.5V, less than 5V, or less than about 3.5V. It should be noted that for a high power performance for a short time, the applied voltages can be pulsed in nature and can be safely significantly greater than the steady state voltage that would normally result in electrochemical damage to such cells. However, for the operation of electrochemical cells in the conditions in which the cell voltage is maintained, to obtain a long life, the applied voltage can result in a potential in the positive electrode that is less than about 5V, less than about 4.5V, or less than 4V, with respect to metallic lithium. This can be allowed through the use of positive electrode materials based on compounds such as LiFePO4, LiTiS2, and LiTaS2.
p00140The selection criteria for compounds with high mechanical energy density and high power electrochemical performance are now described. The theoretical density of mechanical energy of the acting compounds is given by the equation ½ E2, in which E is the elastic modulus, and is the voltage that can be induced in the particular operating conditions. Thus, high tension materials and high elastic modulus have the potential to provide greater energy density in electrochemical cells of the invention.
p00141With respect to electrochemical actuators, it is recognized here that the tension obtained is not necessarily linear with the concentration of the intercalating or alloying species in the electrochemical cell. For example, in a plot of the stress versus the x concentration of Li of the intercalation compound LixTiS2, the slope of the curve steeply increases at low concentrations of Li, as described in US Pat. Series No. 11 / 796,138, incorporated herein by reference. Consequently, it is desirable, when LixTiS2 is used as an electrochemical actuation compound, to operate over a range of x of about 0 to 0.4 if it is desirable to obtain the maximum mechanical energy for a given electrical energy used to make operate the actuator, and / or to obtain the highest mechanical power of the actuator. The latter is concluded from the consideration that the amount of interleaved species x is the product of the electric current and time, so that, for a particular operating current, faster performance is obtained for compounds with a higher voltage for a given value of x.
p00142It is also recognized that the mechanical power of electrochemical actuators may depend on the speed capacity (eg, loading or unloading speed) of the electrochemical cell. A high speed capacity can be obtained by selecting electrolytes of high ionic conductivity, and / or designing cells so that the ionic or electronic diffusion lengths are short. For a particle-based electrode, for example, a fine particle size may be desirable, in order to decrease the diffusion length and, consequently, the diffusion time.
p00143Therefore, the transport properties of the materials can also be an important selection criterion for designing electrochemical actuators. For example, the chemical diffusion coefficient of the ionic species responsible for the change in volume can be selected to be high. An embodiment of the invention identifies a "power factor" that can be used as a merit factor to compare different materials, giving the equation ½ E2D, in which D is the chemical diffusion coefficient of the ionic species in The material of interest. FIG. 4 compares the power factor of different materials against their specific density. It is pointed out that materials of high power factor and low specific density can, being all the same, provide greater specific power as an electrochemical actuator. For example, stratified dicalcogenides such as TiS2 and TaS2 may be particularly useful electrochemical actuating compounds according to these criteria.
p00144It has been recognized that the merit factors of interest in the field of action also include the power density, which is the available mechanical power per unit volume, and the specific power, which is the available mechanical power per unit mass. It is desirable to maximize the values of both in most performance applications. It should be noted that the power density of electrochemical actuators requires consideration of the characteristic diffusion length that ionic species are transported during operation of the electrochemical actuator. While the transport length includes the length between electrodes, through the porosity of the electrode, and through the separator, the actuation rate does not exceed the time required for diffusional transport in the material itself. Thus, both particle size (for a particle-based actuator) and the chemical diffusion coefficient are important factors. To compare materials on the same basis, assuming that the materials can be processed to have similar particle sizes, the power density can be defined as the quantity ½ (E2DLi / x2), and the specific power as ½ (E 2x2 / DLI), in which x is the particle dimension (for example, radius or diameter). FIG. 4 compares the power density of different materials against their specific density, and FIG. 6 compares the power density against the specific power of different materials. Based on this selection criteria, suitable materials for electrochemical actuators can be chosen. For example, stratified dicalcogenides such as TiS2 and TaS2 can be particularly useful electrochemical actuating compounds.
p00145In one embodiment, the electrochemical actuators of the invention use at least two (for example, a first and a second) electrochemical actuators that work in concert so that as one is charged (for example, in order to produce useful mechanical work) , the other is downloaded,
p00146or vice versa. For example, a system or device may comprise a first and a second electrochemical cell configured in an antagonistic arrangement with respect to each other, so that the discharge of the first cell results in the loading of the second cell, and the discharge of the Second cell results in the loading of the first cell. The article may also include a component constructed and arranged to be moved from a first orientation to a second orientation by loading and / or unloading at least one of the first and second electrochemical cells. Of course, a structure that includes electrochemical cells that are configured in an antagonistic arrangement relative to each other can include a plurality of such sets of electrochemical cells, for example more than 2, more than 5, more than 10, more than 20 or more of 50 pairs of electrochemical cells that are configured in an antagonistic arrangement. Such cells can be operated in series or in parallel in relation to each other. Although pairs of opposite actuators have been previously used in active structures (for the reason that most actuators work better in tension than in compression, or vice versa), there are additional benefits of such designs for use in the electrochemical actuators of the invention. . Electrochemical actuators store or release electrical energy while performing mechanical work, and if such electrical energy dissipates (for example, in the form of heat dissipating electrical energy through a resistor), the energy consumption of the actuator or Actuator system can be elevated. However, by moving the electrical energy between actuators so that as one is charged the other is discharged, the electrical energy is largely conserved. Another benefit of antagonistic electrochemical actuators, located so that each can exert a force on the other, is that the effort exerted on the actuators can be controlled by loading or unloading one or both of the opposite actuators. For example, this arrangement may allow pre-stress on actuators to be controlled to optimize actuation force, creep, and / or actuator compliance. Still another benefit is that the accuracy of the actuator placement is improved when opposite actuators can be loaded or unloaded independently.
p00147Typical electrochemical cells include an electrode (for example, an anode) that expands, while the other (for example, the cathode) contracts during charging, or vice versa during discharge, in order to reduce the amount of change in volume in the cell This can be advantageous for certain applications, since a low volume change can reduce, for example, the delamination of certain layers in the cell. However, in some embodiments of the invention, it is advantageous that both electrodes expand during charging or discharge, or that one electrode does not contract while the other expands. Advantageously, such configurations allow maximum energy to be used for actuation, instead of wasting it in counteracting the other electrode.
p00148Accordingly, another embodiment includes an electrochemical cell comprising an anode and a cathode that are constructed and arranged such that during a cycle in which one of the electrodes expands at least 1% by volume, the other electrode does not contract substantially . In other embodiments, one of the electrodes expands at least 0.5% by volume, at least 2% by volume, or at least 4% by volume, while the other electrode does not contract substantially. For example, as one of the anode or cathode expands, the other can expand, or it may not change volume. A component can be operatively related to such an electrochemical cell, and the component can be moved from a first orientation to a second orientation by loading and / or unloading the electrochemical cell. This simultaneous expansion of the anode and cathode, or the expansion of one electrode while the other does not contract, can be performed using appropriate materials for the anode and cathode.
p00149In some cases, an electrode can spontaneously discharge a species (for example, lithium), causing an expansion or contraction of the electrode and / or movement of one or more components of the device from a first orientation to a second orientation. Electrode materials showing spontaneous discharge are known in the art and can be advantageous in cases where a particular "suspension" state of the device is desired, for example in the case of an intentional or accidental short-circuit of the electrochemical cell.
p00150Suitable materials for use as electrodes include electroactive materials, such as metals, metal oxides, metal sulphides, metal nitrides, metal alloys, intermetallic compounds, other compounds containing metals, other inorganic materials (eg, carbon), and the like. In some cases, the electrodes may advantageously comprise materials that have a high elastic modulus. In some cases, the material may be able to undergo a change in volume or other dimensions with the interaction with a species, as described here. In some embodiments, the electrodes may comprise a material comprising a crystalline structure, such as a single crystal or a polycrystalline. In some embodiments, the electrodes may comprise an amorphous or messy material.
p00151In some cases, the material that forms the anode comprises one or more of aluminum, silver, gold, boron, bismuth, gallium, germanium, indium, lead, antimony, silicon, tin. In some embodiments, the material that forms the anode may comprise Li4Ti5O12 or an alloy or doped composition thereof. Examples of materials that can form the cathode include LiCoO2, LiFePO4, LiNiO2, LiMnO2, LiMn2O4, Li4Ti5O12, TiSi2, MoSi2, WSi2, TiS2, or TaS2, or any alloy or doped composition thereof. In some cases, the material that forms the cathode may comprise TiS2 or TaS2. In other embodiments, the material forming the cathode may comprise LiMPO4, in which M is one or more transition metals of the first row (eg, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu , or Zn), or any alloy or doped composition thereof. In some cases, the cathode comprises carbon, in which the carbon may be in the form of graphite, a fiberglass structure, a vitreous carbon structure, a highly oriented pyrolytic graphite, a disordered carbon structure, or a combination of the same. An electrochemical cell comprising such material compositions can be operated at a cathodic potential described above, for example less than + 4V with respect to the metallic lithium potential. The anodic potential can be selected from the potentials described above, for example greater than + 0.5V with respect to the metallic lithium potential.
p00152In some cases, the material that forms the electrode may comprise species dispersed in the material. For example, the electrodes may comprise an amount of a species so that the electrode can serve as a source of the species within the device. In some embodiments, a substrate or other support material may interact with a species to induce a volumetric or dimensional change. For example, a silicon wafer, or other metal or metal-containing substrate can be lithiated so that a volumetric or dimensional change occurs with the charge / discharge of the electrochemical cell.
p00153The materials for use in electrodes of the invention can be selected to show certain properties with interaction with a species (eg, lithiation and deslitiation). For example, the materials can be selected to show a certain type or amount of volumetric or dimensional change (eg, performance) when used in an electrochemical cell as described herein. Those of normal skill will be able to select such materials using simple selection tests. In some cases, the properties and / or behavior of a material may be known, and a person of ordinary skill in the art would be able to select materials to suit a particular application based, for example, on the amount of volumetric change desired. For example, it is known that reversible intercalation of lithium with phosphoolivins Li (Fe, Mn) PO4 produces volume changes of 7.4-10%, based on the Fe / Mn ratio, as described in A. Yamada et al .,
p00154J. Electrochem. Soc., 148, A224 (2001). In some cases, the materials can be identified by incorporating a material such as an electrode into an electrochemical cell and observing the behavior of the material with the loading and unloading of the cell.
p00155In some cases, the electrode materials can be selected based on the stability of a material that interacts with the species. For example, when lithium is the species, a material can be selected based on its ability to quickly and / or reversibly accept lithium ions (for example, to be lithiated) and / or donate lithium ions (for example, to be disinitiated) With loading / unloading. Also, the corresponding stress associated with the reversible interaction of the species with the material can be determined by knowing the rate of ionic transport in the material. Such determinations can be experimentally evaluated or theoretically made using tabulated or estimated values of properties such as ionic diffusion coefficients, ionic and electronic conductivities, and surface reaction velocity coefficients. Those of ordinary skill in the art will be able to use this information to select materials suitable for use as electrodes.
p00156The electrodes can be manufactured by methods known in the art. In one embodiment, the electrode materials can be molded from powder-based suspensions containing a polymeric binder and / or a conductive additive such as carbon. The suspension can be calendered (for example, laminated) under high pressure (for example, several tons per linear inch) to form densely compact layers having a desired percentage of active material volume.
p00157Materials suitable for use as an electrolyte include materials capable of functioning as a means for the storage and transport of ions, and, in some cases, as a separator between the anode and the cathode. Any liquid, solid, or gel material capable of storing and transporting ions can be used, as long as the material is electrochemically and chemically non-reactive with respect to the anode and cathode, and the material facilitates the transport of ions (e.g., ions lithium) between the anode and the cathode. The electrolyte can be electronically non-conductive to prevent the short circuit between the anode and the cathode.
p00158The electrolyte may comprise one or more ionic electrolytic salts to provide ionic conductivity, and one or more liquid electrolyte solvents, gel polymeric materials, or polymeric materials. In some cases, the electrolyte can be a non-aqueous electrolyte. Suitable non-aqueous electrolytes may include organic electrolytes that include liquid electrolytes, gel electrolytes, and solid electrolytes. Examples of non-aqueous electrolytes are described, for example, by Dominey in Lithium Batteries, New Materials, Developments and Perspectives, Chapter 4, p. 137-165, Elsevier, Amsterdam (1994), and Alamgir et al. in Lithium Batteries, New Materials, Developments and Perspectives, Chapter 3, p. 93-136, Elsevier, Amsterdam (1994). Examples of non-aqueous liquid electrolytic solvents include, but are not limited to, non-aqueous organic solvents, such as, for example, N-methylacetamide, acetonitrile, acetals, ketals, esters, carbonates, sulfones, sulphites, sulfolanes, aliphatic ethers, cyclic ethers. , glymes, polyethers, phosphate esters, siloxanes, dioxolanes, N-alkyl pyrrolidones, substituted derivatives thereof (eg halogenated derivatives thereof), and combinations thereof.
p00159In some embodiments, electrochemical cells may further comprise a barrier or separator material (eg, layer) located within the system or device, for example between the cathode and the anode. The separator can be a material that separates or isolates the anode and cathode from each other, preventing short-circuiting, and allowing the transport of ions between the anode and the cathode. Materials suitable for use as separating materials include materials that have a high elastic modulus and / or high stiffness (eg, stiffness), materials that are electronically insulating, and / or materials that have sufficient mechanical strength to withstand high pressure, weight , and / or voltage (for example, load) without loss of function. In some cases, the separator layer may be porous. Examples of separator materials include glass, ceramics, a silicate ceramic, cordierite, aluminum oxide, aluminosilicates, or other oxides or nitrides or mixed metal carbides that are electronically insulating. In some cases, the separator layer may comprise a polymeric material. The separator layers comprising, for example, elastomeric materials may be useful to allow shear movements between one or more components.
p00160In one embodiment, the porous separator material can be molded as a particulate or suspended layer on the surfaces of one or both electrodes before assembling the layers, using methods known to those of ordinary skill in the art for processing ceramic materials. or coating technology, such as spray deposition, scraper coating, screen printing, web coating, reverse coating with comma bar, or coating with wide groove nozzle.
p00161The devices of the invention may further comprise additional components to suit a particular application. For example, the devices of the invention may comprise a powder supply, a current collector, such as a current collector comprising a conductive material, outer packing layers, separator layers, and the like. The packing layer may comprise an electrochemically insulating material or other protective material.
p00162The system or devices can optionally be pretreated or processed before using them as an actuator. The pretreatment of the devices can enhance the mechanical behavior, stiffness, the density of actuation energy, the actuation voltage, the reversibility, and / or the life time of the devices, and / or can reduce creep deformation and tension hysteresis. In some cases, the devices, or one or more of their components, can be subjected to hydrostatic pressure and / or uniaxial effort to consolidate the materials and / or components of the device, and / or reduce the amount of free volume. In some embodiments, the applied pressure may be 68.9 N / mm2 (10,000 psi), 137.9 N / mm2
p00163(20,000 psi), 206.8 N / mm2 (30,000 psi), 310.3 N / mm2 (45,000 psi), or greater. It should be understood that any amount of pressure applied can be used to pre-treat a device, so that the internal failure of the device is avoided and / or the improvement of the behavior of the device can be achieved.
p00164The following examples are intended to illustrate certain embodiments of the present invention, but should not be construed as limiting and do not exemplify the full scope of the invention.
EXAMPLE 1
p00165Self-powered electrochemical pump
p00166In this predictive example, the actuators of the invention can be used as self-powered electrochemical pumps for insulin therapy .
p00167Clinical treatment of type 1 diabetics is usually done by insulin therapy, in which long-acting and short-acting insulin injections are used in combination to respond to periodic blood glucose measurements. Treatment may include therapy with an insulin infusion pump, including continuous subcutaneous insulin infusion (CSII), which dispenses rapid acting insulin from a microprocessor-controlled pump through a tiny catheter. Some existing pumps can continuously dispense fast-acting insulin and can provide incremental doses before or after meals. The infusion set is changed every three days, so that the effective number of injections is drastically reduced throughout the conventional daily multiple injections (MDI) regimen. The exclusive use of fast acting insulin produces a much improved predictive capacity in dosing since the insulin forms that act prolonged work forming a deposit under the skin. However, the rate of insulin release from such deposits can vary significantly depending on factors such as physical activity. Self-powered electrochemical pumps can solve the problems of reduced effective number of injections and variable insulin release rates.
p00168A self-powered electrochemical pump can be designed to deliver a 2.0 ml payload over a period of 72 hours. FIG. 16 shows a schematic design for the self-powered electrochemical pump 350. The negative electrode 355 provides a source of lithium, while the positive electrode 360 is the expanding element. The cell is electrochemically balanced so that the lithium available in the negative electrode can expand the positive electrode. The pump can be designed for a 300% volume expansion of the positive electrode, creating a longitudinal displacement, not different from a piston, which supplies force to an actuating plate that in turn applies pressure to a reservoir 365 that contains the solution of insulin The vertical displacement of the positive electrode can be determined by its aspect ratio of width / height (which is assumed here to be 2: 1) and the change in volume. The electrolyte can be a standard non-aqueous lithium battery electrolyte. The packaging may be a polymeric packaging similar to that currently used for rechargeable lithium-ion batteries.
p00169Advantageously, the release rate of the insulin solution can be controlled by choosing appropriate materials used to form the positive electrode. For example, for an electrochemical pump having a positive electrode material of relatively low stiffness, the positive electrode can slowly move to its new equilibrium position with discharge. This can result in a slow application of a force to the reservoir, thereby causing the slow infusion of insulin to the body.
p00170The pump can have a volume of 8.6 ml, which will allow a total device volume of <15 ml. The pump mass of 14.5 g should allow a total device mass of about 20 g. With the appropriate choice of materials and electrolyte, this pump design can deliver insulin for 72 hours at the required baseline speed. For the bolus rate, which corresponds to a cell discharge rate of approximately C / 5 (i.e., 5 h of discharge for the entire capacity of the cell), additional design modifications may be incorporated. Additionally and / or as an alternative, the pump may have similar specifications as those for existing continuous infusion pumps. For example, fast acting insulin, such as the Lilly Lispro® product, is packaged as solutions with a concentration of 100 units per ml. Typical basal insulin levels can be adjusted between 0.5 to 1.5 units per hour. A bolus dose for a meal may consist of 1 unit per 10 g of carbohydrate consumed, so that as many as 10 units for a meal may be desired. The pharmacodynamics of rapid acting insulin suggests that the dose be given for 15 minutes. Any greater amount and some differences of a subcutaneous injection of the same amount can be observed. Thus, the peak delivery rate is a volume of 0.1 ml in 15 minutes. A linear compression of a tank with a cross section of 6.5 cm2 requires a maximum travel speed of 0.015 cm in 15 minutes or 0.167 micrometers per second. The total daily payload of insulin solution should be approximately 50 units or 0.5 ml. Thus, a three-day supply requires a payload of 1.5 ml by volume.
EXAMPLE 2
p00171Electrochemical actuator
p00172In this predictive example, an electrochemical actuator comprises a bimorphic structure that includes a layer of dimensionally active lithium storage material bonded to a copper layer. The copper layer is not substantially alloyed or intercalated with lithium, although it is electrochemically stable to the electrochemical cell's operating potential. This bimorphic structure forms the positive electrode of the cell. The copper layer can also act as a positive electrode current collector, and it can extend out of the tightly sealed end cell to form a current tongue or conductor, or it can be attached to a tongue or current conductor that extends out of the cell. The negative electrode is a metallic lithium layer attached to or deposited on a copper layer that serves as the negative current collector. Between the two electrodes a porous separator film is placed, for example a fiberglass cloth or a porous polymer separator such as those used in the construction of lithium ion batteries. The stratified cell is infused with a non-aqueous lithium conductive liquid electrolyte, as is commonly used in the technology of primary or rechargeable lithium batteries, or non-aqueous electric double layer capacitors. Examples include a solvent comprising a 1: 1 by volume mixture of ethylene carbonate and diethylene carbonate, to which a 1M concentration of LiPF6 has been added as a conductive lithium salt, or acetonitrile as the solvent to which it has been added. the same salt LiPF6.
p00173The electrochemical actuator closes tightly in a polymeric packing. When assembled, the cell is in a charged state, the positive tin electrode having a chemical potential for lithium less than the negative metallic lithium electrode. By connecting the negative and positive current collectors so that electric current flows between the two electrodes, a flow of lithium ion current occurs internally from the lithium to the tin. Tin alloy with lithium results in a volume expansion that can reach almost 300% when tin is saturated with lithium. As the tin layer increases in volume due to the lithium alloy, the copper layer to which it is attached provides a mechanical restriction, and the bimorph undergoes displacement (for example, bending). In the negative electrode, the loss of lithium can also result in a small effort, but this effort is much less than that of the positive electrode, since lithium is very ductile near room temperature. In this way, the entire cell undergoes flexure due to the change of volume of the tin layer in the electrochemical actuator comprising the positive electrode. The flexure of the cell in turn applies a pressure to a drug reservoir, which is located adjacent to the actuator. The drug reservoir contains a fluid that comprises a drug and is enclosed by a deformable vessel such as a bladder. The pressure applied causes the drug to be dispensed from the reservoir.
EXAMPLE 3
p00175Flexura of the electrochemical bimorph
p00176In this predictive example, the bimorphic structure of EXAMPLE 2 is manufactured in the form of a semicircle or "U" shaped flexure, as shown in FIGS. 3A-C. One end of the flexure is anchored to a support or housing of the dispensing device, while the other end is free to move as the bimorph undergoes a flexure. With the discharge of the electrochemical cell, the flexure extends outward, and the free end of the flexure applies a force to a bladder containing drug, dispensing a drug through a hole or valve in the bladder.
EXAMPLE 4
p00178Actuator that changes in a self-powered way, with accumulated amplification
p00179In this Example, an electrochemical cell was manufactured and studied to determine its ability to act with the application of a voltage or current. A porous pellet was pressed from 325 mesh tin powder (99.8% [metal base], Alfa Aesar) on a 1.3 cm (½ inch) diameter matrix under 3.3 kN (750 lbf). The pellet weighed 0.625 g and was measured to be 0.89 mm thick. The pellet was welded to 15 micrometer thick copper metallic paper using a BiSnAg (Indium Corporation of America) solder and # 5RMA (Indium Corporation of America) flow by heating the assembly in an air oven at 180 ° C for 30 minutes. This electrode assembly was used as the positive electrode in the electrochemical cell, while, as a negative electrode, lithium metal paper (,80.8 mm thick, Aldrich) was used.
p00180Two layers of Celgard 2400 separator were used to separate the positive tin electrode and the negative lithium metal paper electrode. The lithium metallic paper electrode was attached to a current collector also made of 15 micrometer thick copper metallic paper. A liquid electrolyte consisting of 1.33 M LiPF6 dissolved in a mixed solvent of ethylene carbonate, propylene carbonate, dimethyl carbonate, and ethyl and methyl carbonate (4: 1: 3: 2 by volume) was used. The cell was tightly sealed in an envelope made of a polyethylene bagging material, using a thermal sealer. With the assembly, the open circuit voltage of the cell was 2.8-2.9V, showing that it was in the charged state. With the discharge, the cell voltage dropped rapidly to a relatively constant value of 0.5-0.4V, as is characteristic of the electrochemical cell of Sn-Li.
p00181The cell was discharged through a 1 ohm resistor that connected the positive and negative current collectors. The normal measured displacement to the plane of the tin disk and the lithium metal paper while the cell was discharged was measured using a Micro-Epsilon linear variable differential transformer (LVDT). The readings were measured using a National Instruments NI-USB 6009 data acquisition device with an interface with LabView (National Instruments). FIG. 17 It shows a graph of the displacement resulting from this experiment as a function of time.
p00182After an initial small compression caused by the creep of lithium and separator under the small applied force of the LVDT, the actuator extended 1.8 mm as it was discharged over a period of 11 hours. This absolute displacement exceeded the initial thickness of the Sn pellet by about a factor of two. Inspection of the actuator disassembled after the test showed that the discharge had occurred, eroding the lithium from the negative electrode and moving away with the tin pellet on one side. It was easily observed that the displacement of the actuator was due to the deformation of the cylindrical tin pellet in a "curled" shape, the convex surface being the side facing the separator and the lithium electrode. Thus, it was observed that the change in the shape of the tin pellet was due to the creation of a differential voltage across the pellet, looking at the side of the lithium electrode undergoing expansion. The mechanical load in the direction of normal movement to the plane of the pellet after deformation showed that a load of more than 1 kg could be supported without fracturing the deformed pellet. Thus, the actuator has a substantial stiffness, which would be useful for applications such as dispensing or pumping a bladder filled with fluid, as in drug delivery applications in which the fluid can be dispensed through one or more needles or microneedles By placing the actuator of this example close to such a bladder filled with fluid, and enclosing the assembly in a rigid container, a drug delivery device could be obtained.
p00183Such a drug delivery device would be suitable, for example, for an insulin supply for 3 days (72 h). Fast acting insulin, such as the Lilly Lispro® product, is generally packaged as solutions with a concentration of 100 units per ml. The total daily payload of insulin solution may be approximately 50 units or 0.5 ml. In this way, a pump with a three-day supply can provide a total volume of ,02.0 ml. For example, the actuator described in this Example produced a displacement of more than 1.5 mm, which, when acting on a 13 cm2 area reservoir, can easily obtain the desired volume of 2.0 ml. Typical basal insulin levels can be adjusted between 0.5 and 1.5 units per hour. A bolus dose for a meal may consist of 1 unit per 10 g of carbohydrate consumed, so that as many as 10 units for a meal may be desired. The rapid acting insulin pharmacodynamics suggests that the dose can be delivered for 15 minutes. In this way, the peak delivery rate can correspond to 5% of the total volume for 15 minutes. By taking a 1.5 mm offset to correspond to a complete supply of a 2 ml insulin payload, the actuator in this example can easily meet the bolus speed requirement. In order to slow down the speed to meet the baseline speed requirement, an increase in the resistance of the external load or control of the duty cycle can be implemented, as described below in Example 7.
p00184This Example may demonstrate the electrochemical actuator and the drug delivery device in certain embodiments of the invention, demonstrating electrochemical performance due to the creation of a differential voltage across an electrode. Consideration of the net change in volume of the actuator during the discharge of the cell showed that the displacement obtained was not correlated with the net change in volume, and was in fact a sign opposite to the net change in volume of the cell. Comparing the partial molar volume of lithium in various LixSn alloys with the molar volume of pure lithium, it was observed that pure lithium had a higher molar volume, and therefore the discharge of a cell in which lithium was the negative electrode resulted in a net decrease in volume. For example, Li2.5Sn, a compound of relatively low stoichiometry Li / Sn, had a molar volume of 38.73 cm3 mol-1. Since pure metallic Sn has a molar volume of 16.24 cm3 mol-1, the difference, 22.49 cm3 mol-1, of the compound was the volume occupied by 2.5 Li in Li2.5Sn. In comparison, the molar volume of pure Li was 13.10 cm3 mol-1, so that 2.5 moles of metallic Li would have a volume of 32.75 cm3. Therefore, the complete discharge of a cell to form Li2.5Sn on the side of the positive electrode would result in the transfer of 2.5 moles of lithium from the Li electrode to the Sn, resulting in a net decrease in volume Of the device. Similarly, the molar volume of Li in Li4.4Sn, a compound of relatively high stoichiometry, is 42.01 cm3 mol-1, whereby 4.4 moles of pure metallic Li have a volume of 57.62 cm3 mol -1. Again, the discharge of such a cell results in a net decrease in volume. The outward or positive displacement observed in the actuator of this example occurred despite the negative change in volume with the discharge. The flexural or "curling" type deformation mode of the actuator amplified the deformation due to differential tension across the pellet.
EXAMPLE 5
p00185Galvanic discharge of an electrochemical actuator
p00186In the following example, the galvanostatic discharge of an electrochemical cell was studied. An electrochemical cell was manufactured as described in Example 4, with conductive copper adhesive tape used as the contact between the porous tin pellet and the copper current collector, instead of a soldering iron. The cell was galvanically discharged (constant discharge current) using a Maccor 4300 battery tester (Maccor). The tin pellet weighed 0.628 g, and was measured to be 1.06 mm thick. The theoretical capacity of the pellet was 624 mAh, assuming that all the tin was lithiated to the compound Li4,4Sn. With the assembly, the open circuit voltage of the cell was 2.8-2.9V, showing that it was in the charged state. The cell was discharged at 0.88 mA up to 0.01V. The discharge capacity was 56.22 mAh, showing that the cell was discharged to only 9% of its theoretical capacity during the discharge time of 63.6 h. However, it was observed that the Sn pellet had been curled in the same manner and to approximately the same deformation as the actuator in the Example
p001871. This Example demonstrated the current limited control of an electrochemical actuator that can spontaneously discharge and act if the positive and negative conductors were closed in an external circuit.
EXAMPLE 6
p00188Bimorphic electrochemical actuators
p00189A bimorphic electrode was made by masking one side of a 50 micron thick copper metal paper and 40 mm x 5 mm area with Kapton adhesive tape, and dipping the molten tin metal paper to coat one side with a tin layer. It was hoped that, with the electrochemical lithiation of tin, the restriction provided by the copper metallic paper would result in bending or "curling" of the bimorphic structure, the lithium tin being the convex side. An electrochemical cell like those in Examples 4 and 5 was assembled using this bimorph as the positive electrode, assembled with the tin layer facing the separator and the negative electrode of lithium metal paper. With the assembly, the cell's open circuit voltage was 2.8-2.9V, showing that the cell was in the charged state. The cell was galvanically discharged to 0.01 V with a current of 0.089 mA. The discharge capacity was 7.7 mAh, representing about 50% of the discharge state for a tin layer thickness of about 10 micrometers and assuming a completely lithiated Li4.4Sn composition. After discharge, the cell was disassembled, and the tin-copper bimorphic electrode showed substantial flexion at all free edges of the polymorph, demonstrating a change in shape.
p00190In other experiments, samples of metallic tin metal paper of 0.05 mm (99.999% [base in metals], Alfa Aesar) and 0.10 mm (99.99% [base in metals], Alfa Aesar) thick each joined to 15 micrometer thick copper metallic paper, forming flat bimorphic electrodes of 20 mm x 5 mm area. The electrochemical cells were constructed using two layers of Celgard 2400 separator to separate the positive bimorphic tin / copper electrode and a negative electrode of 0.4 mm thick aluminum foil (Aldrich). For each cell, the aluminum foil electrode was attached to a current collector also made of 15 micrometer thick copper metallic paper, and a liquid electrolyte consisting of 1.33 M LiPF6 dissolved in a mixed solvent was used of ethylene carbonate, propylene carbonate, dimethyl carbonate, and ethyl and methyl carbonate (4: 1: 3: 2 by volume). Each cell was tightly sealed in an envelope made of polyethylene bagging material, using a thermal sealer.
p00191The cells were galvanically discharged using a Maccor 4300 battery tester (Maccor). The cell made using tin metal paper 0.10 mm thick was discharged at 0.4178 mA to 0.01V. The discharge capacity was 1.65 mAh (4% of the theoretical discharge capacity). In FIG. 19 The download profile for this device is displayed. With disassembly, it was observed that the bimorphic electrode is "curled" at all free edges, demonstrating a severe change in shape.
p00192The cell made using a 0.05 mm tin foil was discharged at 0.4076 mA until the discharge capacity was 1.65 mAh (4% of theoretical capacity). In FIG. 20 the download profile for this device is displayed. Similar to the 0.10 mm tin metallic paper bimorph, this device, with disassembly, also showed flexion at all free edges of the bimorph.
p00193These examples demonstrated various electrochemical bimorphic actuators of the invention. These results also show that it may not be necessary to completely discharge the electrochemical cells of the invention in order to obtain a significant change, but that the differential voltage resulting from only a discharge of a few percent of the theoretical capacity of the cell may be enough to achieve the desired performance.
EXAMPLE 7
p00194Control of the work cycle of an electrochemical actuator
p00195An electrochemical actuator of a similar design to that described in Example 1 was subjected to a discharge controlled by the duty cycle, in order to obtain a slow deformation rate. The duty cycle was controlled by an electronic relay (Radio Shack), which was turned off and on via power control from a Maccor 4300 battery tester (Maccor), connected in series with the external 1 ohm load resistor through the electrochemical cell terminals. The relay was closed while receiving power from the battery tester, and opened when the power was interrupted. A 20% duty cycle was configured, in which the current was turned on for 50 ms for a total period of 200 ms. FIG. 18 shows a graph of the displacement curve for the electrochemical changing actuator, controlled by a 20% duty cycle. The resulting displacement of the device, shown in FIG. 18, demonstrated actuator deformation at a low controlled speed. As described herein, an alternative method of obtaining a controlled low strain rate can be to discharge the actuator in FIG. 18 through an external load of greater resistance.
EXAMPLE 8
p00196Self-powered electrochemical actuator that has a higher motor voltage
p00197In some circumstances, a higher average discharge voltage may be desirable than that for the preceding examples using tin and metallic lithium, such as when a substantial motor voltage is needed, even in the presence of significant cell polarization. The antimony can be an electrode material that changes in a useful way for such applications, due to its relatively higher open circuit voltage versus metallic lithium (,950.95V). An electrochemical device was prepared as in Example 1, using a mesh antimony powder -325 (99.5% [metal base], Alpha Aesar) instead of the tin powder. Antimony powder was pressed at 2250 lbf in a ½ inch diameter die. The resulting pellet had 0.687 g and a thickness of 1.31 mm, which corresponds to a theoretical capacity of 454 mAh. The sample was galvanically discharged at a current of 3,025 mA to 0.01V. The discharge capacity was 49.98 mAh (11% theoretical capacity), and resulted in severe deformation of the antimony pellet.
p00198Although various embodiments of the present invention have been described and illustrated herein, those of ordinary skill in the art will readily devise a variety of other means and / or structures for carrying out the functions and / or obtaining the results and / or one or more. of the advantages described herein, and each such variation and / or modification is considered within the scope of the claims.
Contents8
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| US12097028B2 | Cited by | United States of America | Applicant |
| US10750987B2 | Cited by | United States of America | Applicant |
60 members in 17 offices
Priority claims1
| Document | Office | Kind | Date |
|---|---|---|---|
| 83341206 | United States of America | P |
Members60
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| US2009014320A1 | United States of America | A1 | |
| EP2049791A2 | European Patent Office (EPO) | A2 | |
| KR20090046863A | Republic of Korea | A | |
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| EP2366896A2 | European Patent Office (EPO) | A2 | |
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| US2013020906A1 | United States of America | A1 | |
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| CA2665996C | Canada | C |
Numbers
- Publication
- 2358951
- Application
- 7872583
Titles2
- Spanish
- ACTUADOR ELECTROQUIMICO.
- English
- ELECTROCHEMICAL ACTUATOR.
Classification
- IPC, 1
- F03G7 00