Semi-solid electrode cell having a porous current collector and methods of manufacture

Semi-solid electrode battery with porous current collector and manufacturing method thereof

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the priority and rights of U.S. Provisional Application Serial No. 61/531,927 filed on September 7, 2011 under the name of Battery Manufacturing Method, which is incorporated herein by reference in its entirety.

Background technique

[0003] The embodiments described herein relate generally to the preparation of electrode cells for electrochemical devices, and more particularly to systems and methods for using semi-solid electrode cells with porous current collectors in battery modules.

[0004] Conventional battery systems store electrochemical energy by separating an ion source and an ion sink under different ion electrochemical potentials. The difference in electrochemical potential generates a voltage difference between the positive electrode and the negative electrode, and if the electrode is connected through a conductive element, the voltage difference generates a current. In a conventional storage battery system, the negative electrode and the positive electrode are connected by a parallel configuration of two conductive elements. The external element exclusively conducts electrons, however, the internal element separated by the separator and the electrolyte exclusively conducts ions. The external and internal flowing streams supply ions and electrons at the same rate because the charge imbalance cannot be maintained between the negative electrode and the positive electrode. The generated current can be used to drive external devices. The rechargeable battery can be recharged by applying the reverse voltage difference of the drive current and the ion current in the opposite direction to the discharged battery. Therefore, the active material of a rechargeable battery needs the ability to accept and provide ions. The increased electrochemical potential creates a larger voltage difference between the cathode and anode of the battery, which increases the electrochemically stored energy per unit mass of the battery. For high-power storage batteries, the ion source and the ion pool are connected to the separator through an element having a large ionic conductivity, and the high-conductivity element is connected to the current collector.

[0005] Typical battery manufacturing involves a large number of complex and expensive processes performed continuously, each of which suffers from yield losses, incurs capital costs for equipment, and includes operating expenses for energy consumption and consumable materials. The process first involves preparing a separate anode and cathode mixture, which is usually a mixture of electrochemically active ion storage compounds, conductive additives, and polymer binders. The mixture is coated on the surface of a flexible metal foil, and then compressed under high pressure to increase density and control thickness. These compressed electrode/foil composites are then cut into a size and/or shape suitable for the specific form factor of the battery being manufactured. Usually the cut electrode composite material is co-wound or co-stacked with the inserted ion-conducting/electronic-insulating separator film to construct the battery winding body, namely the "rolled body" or "stacked body", and then packaged in a metal can , Flexible polymer bags, etc. A liquid electrolyte can be used to infiltrate the resulting battery, which needs to be introduced in a carefully controlled environment.

[0006] The stored energy or charge of the manufactured battery and the intrinsic charge of the active material (mAh/g), the volume of the electrode (cn?), the thickness, area and number of layers of the product, and the load of the active material in the electrode medium (For example, the number of grams of active material/the number of cubic centimeters of electrode medium) is related. Therefore, in order to enhance commercial attractiveness (such as increased energy density and reduced cost), it is usually necessary to increase the area charge of the electrode set with a given battery form factor (mAh/cm²), it depends on the electrode thickness and active material load. In addition, there is a need to improve the conductivity between the current collector and the electrode material. For example, it may be necessary to increase the surface area of the current collector that is physically and/or electrically connected to the semi-solid electrode material.

[0007] Therefore, there is a need for a semi-solid electrode with a porous current collector. There is also a need for methods for manufacturing semi-solid electrode batteries with porous current collectors.

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Summary of the invention

[0008] The devices, systems, and methods described herein relate to the manufacture and use of semi-solid electrode batteries with porous current collectors. In some embodiments, an electrochemical cell includes an anode, a semi-solid cathode, and a separator (such as an ion permeable membrane) disposed therebetween. The semi-solid cathode includes a porous current collector and a suspension of an active material and a conductive material arranged in a non-aqueous liquid electrolyte. The porous current collector is at least partially disposed in the suspension so that the suspension substantially encapsulates the porous current collector.

Description of the drawings

[0009] FIGS. 1A-1C are schematic diagrams of a porous current collector used in an electrochemical cell according to an embodiment.

[0010] FIGS. 2-6 are schematic diagrams of electrodes disposed on a porous current collector according to specific embodiments.

[0011] Figures 7A and 7B show a system for depositing a semi-solid electrode material on or at least partially within a porous current collector according to one embodiment.

[0012] FIGS. 8A and 8B show a system for depositing a semi-solid electrode material on or at least partially within a porous current collector according to one embodiment.

[0013] Figures 9A and 9B show a system for depositing a semi-solid electrode material on or at least partially within a porous current collector according to one embodiment.

[0014] FIGS. 10A-10C illustrate a method of manufacturing an electrode with a porous current collector according to one embodiment.

[0015] FIGS. 11A-11G illustrate a method of manufacturing an electrochemical cell with a porous current collector electrode according to one embodiment.

[0016] FIG. 12 is a schematic diagram of a plurality of electrodes forming at least a portion of an electrochemical cell according to an embodiment.

[0017] FIG. 13 is a schematic diagram of a plurality of electrodes forming at least a portion of an electrochemical cell according to an embodiment.

Detailed ways

[0018] The embodiments described herein relate generally to the preparation of electrodes for electrochemical devices, and more specifically to systems and methods for using semi-solid electrodes with porous current collectors in battery modules. In some embodiments, electrochemical devices (such as batteries) manufactured directly from semi-solid suspensions completely avoid the use of conventional adhesives and electrode casting steps. Some of the advantages of this method include, for example: (i) a simplified manufacturing process with less equipment (ie less capital intensive), (ii) the ability to manufacture electrodes with different thicknesses and shapes (for example, by changing the extrusion Mold slot size), (iii) thicker OlOOum) and higher area charge (mAh/cm²) The processing of the electrode, thereby reducing the volume, mass, and the cost contribution of inert components relative to the active material, and (iv) the elimination of binders, thereby reducing bending and increasing the ionic conductivity of the electrode. The international patent publication number WO2012/024499 named'Stationary, Fluid Redox Electrode and the international patent publication number WO2012/088442 named Semi-Solid Fled Battery and Method of Manufacture describe the battery structure using semi-solid suspension , The entire disclosure of which is incorporated herein by reference.

[0019] The electrochemically active material and the corresponding semi-solid suspension of which the electrochemically active material is a part undergo volume changes during charging and discharging. To the extent that the battery temperature changes, for example, by ambient temperature during operation or self-heating, the electrode also undergoes volume changes related to thermal expansion and contraction. For electrode designs in which the main contact between the electrode medium and the current collector is through the face area (such as a flat foil), the common performance decay mechanism is

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Floor. The use of porous current collectors mitigates this and related effects. In some embodiments, the porous current collector acts as a support for the semi-solid suspension, facilitating continuous (mechanical, electrical, thermal) contact between the semi-solid suspension and the current collector.

[0020] As used herein, the term "semi-solid" refers to a material that is a mixture of liquid and solid phases, such as particle suspensions, colloidal suspensions, emulsions, gels, or micelles.

[0021] As used herein, the term "fused ionic storage liquid" or "fused liquid" refers to a liquid that is not only a solvent as in the case of an aqueous flow cell catholyte or anolyte, but also It is a liquid with redox activity. Of course, it is also possible to dilute such a liquid form or mix it with another non-redox active liquid that is a diluent or solvent, including mixing with such a diluent to form a lower molten liquid phase including ionic storage liquids, Emulsion or micelle.

[0022] As used herein, the terms "about" and "approximately" generally include the stated value plus or minus 10%. For example, about 5 will include 4.5 to 5.5, about 10 will include 9 to 11, and about 100 will include 90 to 110.

[0023] As used herein, the terms "activated carbon network" and "networked carbon" refer to the overall qualitative state of the electrode. For example, an electrode with an activated carbon network (or networked carbon) allows the carbon particles in the electrode to assume a single particle morphology and structure relative to each other, which promotes electrical contact and conductivity between the particles. In contrast, the terms "unactivated carbon network" and "unnetworked carbon" relate to where carbon particles exist either as single particle islands or as multi-particle coalescence islands, which may not be sufficiently connected to provide sufficient Conductive.

[0024] In some embodiments, an electrochemical cell includes an anode, a semi-solid cathode, and an ion permeable membrane disposed therebetween. The semi-solid cathode includes a porous current collector and a suspension of active material and conductive material arranged in a non-aqueous liquid electrolyte. The porous current collector is at least partially disposed in the suspension so that the suspension substantially encapsulates the porous current collector.

[0025] In some embodiments, an electrochemical cell includes an anode cavity at least partially defined by an ion permeable membrane, a first porous current collector, and an anode semi-solid suspension. The first porous current collector is disposed in the anode cavity so that the first porous current collector substantially fills the anode cavity. The anode semi-solid suspension is arranged in the anode cavity and is at least partially embedded in the first porous current collector. The electrochemical cell also includes a cathode cavity at least partially defined by an ion permeable membrane, a second porous current collector, and a cathode semi-solid suspension. The second porous current collector is disposed in the cathode cavity so that the second porous current collector Basically fill the cathode cavity. The cathode semi-solid suspension is arranged in the cathode cavity and is at least partially embedded in the second porous current collector. The ion permeable membrane is arranged between the anode cavity and the cathode cavity.

[0026] In some embodiments, the electrode includes a porous electronically conductive substrate and a semi-solid electrode material that includes an active material and a conductive material in a non-aqueous liquid electrolyte. The semi-solid electrode material is embedded in a porous substrate.

[0027] In some embodiments, a method of manufacturing an electrochemical cell includes suspending transfer of an anode semi-solid into an anode cavity in which a first porous electronically conductive current collector is disposed. The method also includes transferring the cathode semi-solid suspension to a cathode cavity in which a second porous electronically conductive current collector is disposed. The method includes disposing an ion permeable membrane between the anode cavity and the cathode cavity and sealing the anode cavity and the cathode cavity.

[0028] In some embodiments, the method of forming an electrode includes transferring a semi-solid electrode material having a suspension of an active material and a conductive material in a non-aqueous liquid electrolyte to an electronically conductive substrate. The method includes reducing the temperature of the semi-solid electrode material below the freezing point of the non-aqueous liquid electrolyte.

[0029] The cathode and/or anode materials described herein may be flowable semi-solid or fused liquid compositions. The flowable anode semi-solid (also referred to herein as "anode electrolyte") and/or the flowable cathode semi-solid (also referred to herein as "catholyte") include electrochemically active reagents (anode pellets and/or Or cathode pellets) and optional electronic conductivity

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A suspension of particles (such as carbon). The cathode particles and conductive particles are jointly suspended in the electrolyte to produce a cathode electrolyte semi-solid. The anode particles and conductive particles are co-suspended in the electrolyte to produce an anode electrolyte semi-solid. The semi-solid can flow in response to an applied pressure difference, a gravitational field, or other applied acceleration field that exerts or generates a force on the semi-solid and optionally by means of mechanical vibration.

[0030] In some embodiments, the anode and/or cathode particles have an effective diameter of at least lwn. In some embodiments, the cathode and/or anode particles have an effective diameter of about 1 wn to about 10 wn. In other embodiments, the cathode and/or anode particles have an effective diameter of at least 10 wn or greater.

[0031] In some embodiments, in order to increase the bulk density of the particles and thus the energy density of the semi-solid suspension while still maintaining a flowable semi-solid, the ion storage compound particles have a polydisperse size distribution, wherein the total volume of The finest particles present at at least 5% by volume are at least 5 times smaller than the largest particles present at at least 5% by volume of the total volume. In some embodiments, in order to increase the bulk density of particles and therefore the energy density of the semi-solid suspension while maintaining a flowable semi-solid, the ion storage compound particles have a bidisperse size distribution (ie, the distribution of particle number versus particle size There are two maximum values in), where the difference in size between the two maximum values is at least 5 times.

[0032] In some embodiments, the size distribution of the ion storage compound particles in the semi-solid is polydisperse, and the particle packing fraction is at least 50% by volume. In some embodiments, the particle packing fraction is about 50% to 70% by volume. In other embodiments, the particle packing fraction is at least 70% by volume or greater.

[0033] In some embodiments, the particles have a morphology that is at least equiaxed and spherical in order to increase the fluidity of the semi-solid suspension and reduce its viscosity while achieving a high particle packing density. In some embodiments, the spherical particles are dense, and in other embodiments, the spherical particles are porous. In some embodiments, spherical particles are made by spray drying the particle suspension to obtain spherical agglomerates of smaller particles.

[0034] In some embodiments, the particles of the ion storage material used in the semi-solid suspension are large enough so that surface forces do not prevent them from achieving high tap density and dry and high packing when formulated into a semi-solid suspension density. In some embodiments, the particle size is at least lwn. In other embodiments, the particle size is about lwn to about 10pm. In other embodiments, the particle size is at least 10 wn or greater.

[0035] In some embodiments, by using dispersants and surfactants that are well known to those skilled in the ceramic processing and colloidal chemistry fields, high particle bulk density and flowability and low viscosity are simultaneously achieved. These additives can be, for example, organic molecules with a C6-C12 backbone, which are used to provide space force when adsorbed on the particles. Examples of such additives include stearic acid and the commercially available surfactant Triton-X-100.

[0036] In some embodiments, a redox mediator is used to improve charge transfer within a semi-solid suspension. In some embodiments, the redox mediator is based on Fe+ or V²\V³⁺Or V⁴+. In one embodiment, the redox mediator is ferrocene.

[0037] In some embodiments, redox ions such as those dissolved in conventional aqueous or non-aqueous mobile batteries can be used, but in such embodiments, by using ionic liquids as solvents, the anolyte and/or catholyte There is increased solubility for such ions. In some embodiments, the redox chemistry is Fe-Cr, redox, or zinc-halogen chemistry.

[0038] In some embodiments, the conductive particles may have a shape including a spherical shape, a thin layer, or a rod shape to optimize the solid packing fraction, increase the net electronic conductivity of the semi-solid, and improve the rheological behavior of the semi-solid. Low aspect ratio or substantially equiaxed particles tend to flow well, however, they tend to have a low bulk density.

[0039] In some embodiments, the particles have multiple sizes so that by placing the smaller particles in the larger particles

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To increase the stacking score. In particular, the particle size distribution may be bimodal, where the average particle size of the larger particle mode is at least 5 times larger than the average particle size of the smaller particle mode. The mixture of large particles and small particles improves the flow of materials during battery loading and increases the solid volume fraction and bulk density in the loaded battery.

[0040] In some embodiments, the properties of the suspension can be modified before and after injecting the semi-solid into the sub-assembly container of the unfilled battery in order to promote flow during loading and bulk density in the loaded battery .

[0041] In some embodiments, the particle suspension is initially stabilized by interparticle space forces caused by surfactant molecules. After the particle suspension is injected into the sub-assembly container of the unfilled battery, chemical or heat treatment can cause these surface molecules to decompose or evaporate and promote densification. In some embodiments, the spatial force of the suspension is changed intermittently during the injection.

[0042] For example, the particle suspension can initially be stabilized by the electrostatic double repulsion between the particles to reduce the viscosity. Repulsion reduces the attraction between particles and reduces coalescence. After the particle suspension is injected into the sub-assembly container of the unfilled battery, the surface of the particles can be further modified to reduce the inter-particle repulsion and thereby promote particle attraction and accumulation. For example, an ionic solution such as a salt solution can be added to the suspension to reduce repulsion and promote aggregation and densification, resulting in increased solid fraction loading after injection. In some embodiments, salt is added intermittently during the suspension injection to increase the density in the incremental layer.

[0043] In some embodiments, the battery compartment is loaded with a particle suspension stabilized by the repulsive forces between the particles caused by the electrostatic double layer or short-range steric forces due to added surfactants or dispersants. After loading, the particle suspension is aggregated and densified by increasing the salt concentration of the suspension. In some embodiments, the added salt is a salt for working ions of a battery (for example, a lithium salt for a lithium ion battery), and when added, the liquid phase becomes an ion conductive electrolyte. The liquid phase contains a solvent that is subsequently used as a solvent component of the electrolyte (for example, for a rechargeable lithium battery, it may be one or more alkyl carbonates, or one or more ionic liquids). As the salt concentration is increased, the electric double layer that causes repulsion between the particles "collapses", and the attractive interaction causes the particles to flocculate, aggregate, merge, or otherwise densify. This allows the electrodes of the battery to be formed from a suspension (although it has a low viscosity), for example by pouring, injecting or pumping into a chamber that forms a mesh electrode, and then the particles in the suspension are combined for improved conductivity , Higher bulk density and longer service life.

[0044] In some embodiments, the injectable and flowable semi-solid becomes non-flowable by "fixing." In some embodiments, the fixation is performed by the action of photopolymerization. In some embodiments, immobilization is performed by the action of electromagnetic radiation having a wavelength emitted by the sub-assembly of an unfilled battery. In some specific embodiments, one or more additives are added to the flowable semi-solid to promote the immobilization of the flowable semi-solid.

[0045] In some embodiments, the injectable and flowable semi-solid becomes non-flowable by "plasticizing." In some embodiments, the rheological properties of the injectable and flowable semi-solid are modified by adding diluents, thickeners, or plasticizers. In some specific embodiments, these agents promote processability and help maintain the homogeneity of the semi-solid composition under flow conditions and compartment filling operations. In some specific embodiments, one or more additives are added to the flowable semi-solid to adjust its flow properties to suit processing requirements.

[0046] Semi-solid composition

[0047] In some embodiments, the anolyte and catholyte semi-solids provide a means to produce substances that collectively function as ion storage/ion source, electron conductor, and ion conductor in a single medium that serves as a working electrode.

[0048] Any anolyte and/or catholyte semi-solid ion storage redox composition as described herein, when measured in moles per liter (molar concentration), can have at least a 10M concentration of redox species. In some implementation

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In the solution, any anolyte and/or catholyte semi-solid ion storage redox composition may have at least 12M, at least 15M, or at least 20M. The electrochemically active substance may be an ion storage material or any other compound or ion complex capable of undergoing Faraday reaction in order to store energy. The electroactive substance can also be a multiphase material including the above-mentioned redox active solid mixed with a non-redox active phase, including a solid-liquid suspension, or a liquid-liquid multiphase mixture (including a liquid having intimate mixing with a supporting liquid phase). Micelles or emulsions of ion storage materials). Systems that utilize various working ions may include aqueous systems, where F or OIΓ are working ions, non-aqueous systems, where Li +, N'or other alkali ions are working ions, and even alkaline earth working ions such as Ca? + and M/ + Or A13+. In each of these cases, a negative electrode storage material and a positive electrode storage material may be required, and the negative electrode stores the related working ions at a lower absolute potential than the positive electrode. The battery voltage can be approximately determined by the difference between the ion storage potentials of the two ion storage electrode materials.

[0049] Systems that use both positive and negative ion storage materials are particularly advantageous because there are no additional electrochemical by-products in the battery. Both the positive electrode and the negative electrode materials are insoluble in the flowing electrolyte and the electrolyte will not be contaminated by the products of the electrochemical composition that must be removed and regenerated. In addition, when a non-aqueous electrochemical composition is used, a system using positive and negative lithium ion storage materials is particularly advantageous.

[0050] In some embodiments, the semi-solid ion storage redox composition includes materials that are proven to work in conventional solid lithium ion batteries. In some embodiments, the positive semi-solid electroactive material includes a lithium positive electroactive material, and lithium cations shuttle between the negative electrode and the positive electrode, and are inserted into solid matrix particles suspended in a liquid electrolyte.

[0051] In some embodiments, at least one energy storage electrode includes a fused ion storage liquid of a redox active compound, which can be organic or inorganic, and includes, but is not limited to, lithium metal, sodium metal, lithium metal alloys, and Or fetters and indium alloys without dissolved lithium, molten transition metal chlorides, thionyl chloride, etc., or redox polymers and organics that are liquid under the operating conditions of the battery. It is also possible to dilute such a liquid form or mix it with another non-redox active liquid that is a diluent or solvent, including mixing with such a diluent to form a low-melting liquid phase. However, unlike conventional flow cell catholytes or anolytes, the redox active components will account for at least 10% by mass of the total mass of the flowable electrolyte. In other embodiments, the redox active component will account for about 10% to 25% by mass of the total mass of the flowable electrolyte. In other embodiments, the redox active component will constitute at least 25% by mass or more of the total mass of the flowable electrolyte.

[0052] In some embodiments, the redox active electrode material, whether used as a semi-solid as defined above or as a condensed liquid form, contains storage related materials at a potential useful for the positive or negative electrode of the battery. Organic redox compounds of working ions. Such organic redox active storage materials include "P" doped conductive polymers such as polyaniline or polyethylene-based materials, polyoxynitrides (polynitroxide) or organic radical electrodes (for example, H. Ni shide et al., Electrochim Acta, 50, 827-831, (2004), and Κ. Nakahara et al., Chem. Phys. Lett., 359, 351-354 (2002)), dial-based organics and oxygen carbocyclic compounds and esters, Including compounds such as Li2C₆06>Li₂C8H404 and Li2C6H4 (h (see, for example, M. Armand et al. Nature Materials, DOI: 10.1038/nmat2372) and organic sulfur compounds.

[0053] In some embodiments, electrically insulating organic redox compounds are used. In some cases, the redox compound is a condensed liquid phase, such as an electrically insulating liquid or a flowable polymer. In such cases, the redox active slurry may or may not include additional carrier liquid. Additives can be combined with fused phase liquid redox compounds to increase electronic conductivity. In some embodiments, by combining with electronically conductive materials such as solid inorganic conductive materials (including but not limited to metals, metal carbides, metal nitrides, metal oxides, and carbon allotropes including carbon black, graphitic carbon, carbon fiber , Carbon microfiber, vapor grown carbon fiber (VGCF), fullerene carbon including "buckyball", carbon nanotube (CNT), more

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Wall carbon nanotubes (MWNT), single-walled carbon nanotubes (SWNT), graphene sheets or aggregates of graphene sheets, and materials containing fullerene fragments) are mixed or blended to give such electricity Insulating organic redox compounds are electrochemically active.

[0054] In some embodiments, by combining with electronically conductive polymers (including but not limited to polyaniline or polyethylene-based conductive polymers or poly(3,4-ethylenedioxy thiophene) (PEDOT), Polypyrrole, polythiophene, poly(p-phenylene), poly(triphenylene), polyleather, polyru, polynaphtalene, polyonion, polysoran, polycarbene, tetrasulfide Fullvalene-substituted polystyrene, ferrocene-substituted polyethylene, carbaryl-substituted polyethylene, polyoxyphenazine, polyacene, poly(heteroacene)) are mixed or blended, The organic redox compound that imparts such electrical insulation has electronic activity. The conductive additive is formed in the conductive frame within the insulating liquid redox compound, which significantly improves the conductivity of the composition. In some embodiments, the conductive additive forms a percolation path to the current collector.

[0055] In some embodiments, the redox-active electrode material comprises a sol or gel, for example, a metal oxide sol or gel prepared by the hydrolysis of a metal alkoxide (commonly referred to as "sol-gel in other methods"). Glue processing"). The oxidized sail gel with composition V4y is one of such redox active sol-gel materials.

[0056] Other suitable positive active materials include solid compounds known to those skilled in the art, such as those used in NiMH (metal hydride) and cadmium (NiCd) batteries. Other positive electrode compounds used for Li storage also include those commonly referred to as CFx used in a fluorinated carbon storage battery, or metal fluoride compounds with approximate stoichiometry MF2 or MF3, where Μ contains Fe, Bi, Ni , Co, Ti, V. Examples include H. Li, P. Balaya and J. Maier, LiStorage via Heterogeneous Reaction in Selected Binary Metal Fluorides and Oxides, Journal of The Electrochemical Society, 151 [1 Ding A1878-A1885 (2004), M. Bervas, AN Mansour, W.-S. Woon, JFAl-Sharab, F. Badway, F. Cosandey, LCKlein and GGAmatucci, Investigation of the Lithiation and Delithiation Conversion Mechanisms in a Bismuth Fluoride Nanocomposites, J. Electrochem. Soc., 153, A799 (2006), and I. Plitz, F. Badway, J. Al -Sharab, A.DuPasquier,F.Cosandey and GGAmatucci, Structure and Electrochemistry of Carbon-Metal Fluoride Nanocomposites Fabricated by a Solid State Redox Conversion Reaction^，＞ , J. Electrochem. Soc., 152, A307 (2005).

[0057] As another example, fullerene carbon including single-walled carbon nanotubes (SWNT), multi-walled carbon nanotubes (MWNT), or metal or metal-like nanowires can be used as ion storage materials. An example is in CK Chan, H. Peng, G. Liu, Κ. Mcllwrath, XF Zhang, RA Huggins and Y. Cui, High-performance lithium battery anodes using silicon nanowires, Nature Nanotechnology, published online on December 16, 2007 ;doi:10.1038/nnano. The silicon nanowires used as high energy density storage materials in the 2007.411 report.

[0058] Exemplary electroactive materials for positive electrodes in lithium systems include the general family of ordered rock salt compounds LiM02, which include a-NaFe0₂Type of those (so-called "layered compounds"), or orthorhombic LiMn0₂Structure types, or their different crystal symmetry, atomic ordering, or partially substituted metal or oxygen derivatives. Μ includes at least one first-line transition metal, but may include non-transition metals, including but not limited to Al, Ca, Mg, or Zr. Examples of such compounds include LiCo02, Mg-doped LiCo02, LiNi02, Li (Ni, Co, Al).₂ (Called "NCA") and Li (Ni ,Mn,Co) 0₂ (Called "NMC"). Other groups of exemplary electroactive materials include those having a spinel structure, such as LiMn₂0₄And its derivatives, the so-called "layered-spinel nanocomposite", in which the structure includes nano-scale regions with ordered rock salt and spinel-ordered olivine LiMP.₄And their derivatives, where M contains Mn.Fe.Co or Ni, partially fluorinated compounds such as LiVPChF, other "polyanionic" compounds as described below, and sail oxides V4y including V2O5 and V60n

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One or more.

[0059] In one or more embodiments, the active material includes a transition metal polyanionic compound, such as described in US Patent No. 7,338,734. In one or more embodiments, the active material contains an alkali metal transition metal oxide or phosphate, and for example, the compound has the composition Ax(M'l - aMa) y(XD₄) Ζ, Ax (M'l - aMa) y (DXD₄) Z or Ax (M' -Ma) y (X2D7) ζ, and has a value such that X, plus y (la) multiplied by one or more form valences of Μ', plus ya multiplied by Μ The valence or valence of the form is equal to ζ times the valence of the XD4, X2D7 or DXD4 group; or the compound contains the composition (Al-aMa) _XM^Z_y (XDJ z, (Al-aMa) xM'y(DXD4) Z (A-aMa) xM'y(X2D7) z and has such a value such that (la) x plus the number ax multiplied by Μ The valence of one or more forms of plus the valence of one or more forms of y times M'is equal to the valence of Z times XD4, X2D7 or DXD4 group. In this compound, A is the alkali metal and hydrogen. At least one, Μ'is the first row of transition metals, Χ is at least one of phosphorus, sulfur, stele, button and hook, and Μ'' is RA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB , IIIB, IVB, VB and VIB group metals, D is at least one of oxygen, nitrogen, carbon or halogen. The positively electroactive material can be an olivine structure compound LiMP.₄, Where M is one or more of V, Cr, Mn, Fe, Co, and Ni, wherein the compound is optionally doped at Li, M, or 0-sites. The defect at the Li site is compensated by adding metal or metalloid, and the defect at the 0 site is compensated by adding halogen. In some embodiments, the positive active material includes a thermally stable transition metal-doped lithium transition metal phosphate, which has an olivine structure and has the formula (Lii-_xZ_x) MP0₄, Where M is one or more of V, Cr, Mn, Fe, Co and Ni, and Z is a non-alkali metal dopant, such as at least one or more of Ti, Zr, Nb, Al or Mg, And χ is 0.005-0.05 _o

[0060] In other embodiments, the lithium transition metal phosphate material has Lii-_x-zMi₊zP0₄The total composition of, wherein M contains at least one transition metal selected from the first row of Ti, V, Cr, Mn, Fe, Co and Ni, wherein χ is OT and ζ can be positive or negative. Μ includes Fe, and ζ is about 0.15 to -0.15. The material can exhibit a solid solution in the composition range of 0<x<0.15 at room temperature (22-25°C), or the material can exhibit a stable solid solution in the composition range of χ between 0 and at least about 0.05 , Or the material can exhibit a stable solid solution in the composition range of χ between 0 and at least about 0.07. In the lithium-poor region, for example, x20.8, or x20.9, or x20.95, the material can also exhibit a solid solution.

[0061] In some embodiments, the redox-active electrode material includes a metal salt that stores alkali ions by undergoing a substitution or conversion reaction. Examples of such compounds include metal oxides commonly used as negative electrodes in lithium storage batteries, such as Co0, Co304, Ni0, Cu0, Mn0, which undergo a substitution or conversion reaction when reacting with Li to form LizO and remain in a more stable state. A mixture of metal components in the oxide form of the prototype or in the metal form. Other examples include metal fluorides such as CuF2, FeF2, FeF3, BiF3, CoF2, and NiF2, which undergo substitution or conversion reactions to form LiF and reduced metal components. Such fluoride can be used as a positive electrode in a lithium storage battery. In other embodiments, the redox-active electrode material contains monofluorocarbon or its derivatives. In some embodiments, the material undergoing the displacement or conversion reaction is in the form of pellets having an average dimension of 100 nanometers or less. In some embodiments, the material undergoing the displacement or conversion reaction comprises a nanocomposite material of an active substance mixed with an inert matrix, which includes, but is not limited to, conductive and relatively tough compounds, such as carbon, or metal, or metal sulfide. FeS2 and FeF3 can also be used as inexpensive and electronically conductive active materials in non-aqueous or aqueous lithium systems.

[0062] In some embodiments, the working ion is selected from Li\Na\H\Mg²\Al³\Or Ca%

[0063] In some embodiments, the working ion is selected from Li* or NaS

[0064] In some embodiments, the flowable semi-solid ion storage redox composition includes a solid that includes an ion storage compound.

[0065] In some embodiments, the ion is a proton or a vat ion and the ion storage compound is included in sickle-cadmium

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Or those used in metal hydride batteries.

[0066] In some embodiments, the ion is lithium, and the ion storage compound is selected from metal fluorides, such as CuF₂, FeF₂, FeFs, BiFs, COF2 and NiF2.

[0067] In some embodiments, the ion is lithium and the ion storage compound is selected from metal oxides, such as Co0, Co304, Ni0, Cu0, Mn0.

[0068] In some embodiments, the ion is lithium and the ion storage compound includes a compound selected from the group having the formula Lii-_x-zMizP04 compound intercalation compound, wherein M includes at least one transition metal selected from the first row of Ti, V, Cr, Mn, Fe, Co and Ni, where χ is 0-1 and ζ can be positive or minus.

[0069] In some embodiments, the ion is lithium and the ion storage compound includes a compound selected from the group having the formula (Lii-_xZ_x) Intercalation compound of MPO4 compound, where M is one or more of V, Cr, Mn, Fe, Co and Ni, and Z is a non-alkali metal dopant, such as Ti, Zr, Nb, Al or Mg One or more of them, and χ is 0.005-0.05.

[0070] In some embodiments, the ion is lithium and the ion storage compound is selected from the group consisting of LiMP.₄An intercalation compound of the compound of, wherein M is one or more of V, Cr, Mn, Fe, Co, and Ni, wherein the compound is optionally doped at the Li, M, or 0 site.

[0071] In some embodiments, the ion is lithium and the ion storage compound includes a compound selected from the group consisting of Ax(M'l-aMa)y(XD₄) Z, Ax (M'l-aMa) y (DXD₄) Z or Ax (M'_aMa) y (X₂D₇) The intercalation compound of z, where X plus y (-a) multiplied by one or more of the valence of M', plus the valence or valence of ya multiplied by M , is equal to ζ multiplied by XD, X2D7 or The valence of the form of the DXW group; and A is at least one of alkali metal and hydrogen, M'is the first transition metal, X is at least one of phosphorus, sulfur, stele, button and hook, and M `` is any RA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB and VIB group metals, D is at least one of oxygen, nitrogen, carbon or halogen.

[0072] In some embodiments, the ion is lithium and the ion storage compound includes a compound selected from Ai-_aM\) _XM\ (XD₄) Z, (Al-aMa) xM'y(DXD4) Z and (A-aMa) xM'y(X2D7) z intercalation compound, where (1)X plus the number aX multiplied by Μ The valence of one or more forms of plus the valence of one or more forms of y times Mis equal to ζ times XD₄>X₂The valence in the form of D7 or DXW group, and A is at least one of alkali metal and hydrogen, M'is the transition metal of the first row, and X is at least one of phosphorus, sulfur, stele, button and hook, Μ It is any group metal of RA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB and VIB, and D is at least one of oxygen, nitrogen, carbon or halogen.

[0073] In some embodiments, the ion is lithium and the ion storage compound includes an intercalation compound selected from the ordered rock salt compound LiM02, which includes a-NaFeO₂Or orthorhombic LiMnO₂Those of the structure type, or their different crystal symmetry, atomic ordering, or partially substituted metal or oxygen derivatives, where M includes at least one first-row transition metal, but may include non-transition metals, including but not limited to Al, Ca, Mg or Zr.

[0074] In some embodiments, the flowable semi-solid ion storage redox composition includes a solid that includes amorphous carbon, abnormal carbon, graphitic carbon, or metal-coated or metal-modified carbon.

[0075] In some embodiments, the flowable semi-solid ion storage redox composition includes a solid that includes a metal or metal alloy or metalloid or metalloid alloy or silicon.

[0076] In some embodiments, the flowable semi-solid ion storage redox composition includes a solid including nanostructures including nanowires, nanorods, and nanotetrapod pyramids.

[0077] In some embodiments, the flowable semi-solid ion storage redox composition includes a solid that includes an organic redox compound.

[0078] In some embodiments, the positive electrode includes a flowable semi-solid ion storage redox composition comprising

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Including a solid selected from the ordered rock salt compound LiM02, the ordered rock salt compound LiM02 includes a-NaFeO₂Or those of orthorhombic LiMnOs structure types, or their different crystal symmetry, atomic order, or partially substituted metal or oxygen derivatives, where M includes at least one first-row transition metal, but may also include non-transition metals , Which includes but is not limited to Al, Ca, Mg or Zr, and the negative electrode includes a flowable semi-solid ion storage redox composition, which includes selected from amorphous carbon, abnormal carbon, graphitic carbon, or metal coated or Metal modified carbon solid.

[0079] In some embodiments, the positive electrode includes a flowable semi-solid ion storage redox composition, which includes a redox composition selected from the group consisting of Ax(M'l-aMa)y(XD₄) Ζ, Αχ (Μ '-Ma) y (DXDz and Αχ (Μ' l-aMa) y (X₂D₇) A solid of z, where X, plus y (1-a) multiplied by one or more of the valences of M', plus ya multiplied by Μ , is equal to ζ multiplied by XD.X2D7 or The valence in the form of the DXW group, and A is at least one of alkali metal and hydrogen, M'is the first row of transition metals, X is at least one of phosphorus, sulfur, stele, button and hook, and M is any RA, IIIA, IVA, VA, VIA, VIIA, VmA, IB, IIB, IIIB, IVB, VB and VIB group metals, D is at least one of oxygen, nitrogen, carbon or halogen, and the negative electrode includes a flowable The semi-solid ion storage redox composition includes a solid selected from amorphous carbon, abnormal carbon, graphitic carbon, or metal-coated or metal-modified carbon.

[0080] In some embodiments, the positive electrode includes a flowable semi-solid ion storage redox composition that includes a compound having a spinel structure.

[0081] In some embodiments, the positive electrode includes a flowable semi-solid ion storage redox composition, the composition including LiMn₂0₄Compounds and derivatives thereof; layered-spinel nanocomposites, wherein the structure includes nano-scale regions with ordered rock salt and spinel order; so-called with a potential of more than 4.3V relative to Li/Li* "Voltage spinel" includes but is not limited to LiNiO.5Mnl.5O4; Olivine LiMP0₄And their derivatives, where M includes Mn, Fe, Co or Ni, partially fluorinated compounds such as LiVPCkF, other "polyanionic" compounds, and sail oxides VxOy include one or more of V2O5 and V6011.

[0082] In some embodiments, the semi-solid flow battery is a lithium battery, and the negative electrode active compound includes graphite, graphite boron-carbon alloy, hard carbon black or abnormal carbon, lithium titanate spinel, or lithium Solid metals or metal alloys or metalloids or metalloid alloys that react to form intermetallic compounds, including metals Sn, Bi, Zn, Ag, and Al, and metalloid Si and Ge.

[0083] Exemplary electroactive materials for negative electrodes in the case of lithium working ions include graphite or non-graphitic carbon, amorphous carbon, or intermediate carbon microspheres; unlithiated metals or metal alloys, such as Ag, One or more metals of Al, Au, B, Ga, Ge, In, Sb, Sn, Si, or Zn, or lithiated metals or metal alloys, including such compounds as LiAl, Li9A14, Li3Al, LiZn , LiAg, LiioAg3, Li5B4, Li7B6, Lii2Si7, Li2iSi8, Lii3Si4, Li2iSi5, Li5Sn2, Lii3Sn5, Li7Sn2, Li22Sn5, Li2Sb, Li3Sb, LiBi, or LisBi, or lithiated or uncrystallized metal alloy composition.

[0084] In some embodiments, the negative electrode includes a semi-solid ion storage redox composition that includes graphite, graphite boron-carbon alloy, hard carbon black or abnormal carbon, lithium titanate spinel, or Solid metals or metal alloys or metalloids or metalloid alloys that react with lithium to form intermetallic compounds, including metals Sn, Bi, Zn, Ag, and Al, and metalloid Si and Ge.

[0085] The current collector is electronically conductive under the operating conditions of the battery and should be electrochemically inert. Typical current collectors for lithium batteries include sheets or meshes, or copper, aluminum or titanium for negative current collectors in the form of sheets or nets, or any structure in which the current collectors can be distributed in the electrolyte and allow fluid flow, and for positive collectors. Fluid aluminum. The selection of current collector materials is well known to those skilled in the art. In some embodiments, aluminum is used as the current collector for the positive electrode. In some embodiments

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Among them, copper is used as the current collector for the negative electrode. In other embodiments, aluminum is used as the current collector for the negative electrode.

[0086] In some embodiments, the negative electrode may be a conventional fixed electrode, while the positive electrode includes a semi-solid redox composition. In other embodiments, the positive electrode may be a conventional fixed electrode, while the negative electrode includes a semi-solid redox composition.

[0087] A current collector material that is stable under the operating potential of the positive electrode and the negative electrode of the flow battery can be selected. In non-aqueous lithium systems, the positive current collector can contain aluminum or be coated with⁺Aluminum is a conductive material that does not electrochemically dissolve under an operating potential of 2.5-5V. Such materials include Pt, Au, Ni, conductive metal oxides such as oxide sail, and carbon. The negative current collector may include copper or other metals that do not form alloys or intermetallic compounds with lithium, carbon, and a coating that includes such a material on another conductor.

[0088] In some embodiments, by combining anode or cathode particles with pellets of electronically conductive materials, such as solid inorganic conductive materials (including but not limited to metals, metal carbides, metal nitrides, metal oxides, and carbon). The plain body includes carbon black, graphitic carbon, carbon fiber, carbon microfiber, vapor-grown carbon fiber (VGCF), fullerene carbon including "buckyball", carbon nanotube (CNT), multi-walled carbon nanotube (MWNT), Single-walled carbon nanotubes (SWNT), graphene sheets or aggregates of graphene sheets, and materials containing fullerene fragments) are mixed or blended to improve the electrochemical function of the semi-solid redox battery. In some embodiments, by combining with electronically conductive polymers (including but not limited to polyaniline or polyvinyl conductive polymers, or poly(3, 4-Ethylene dioxy thiophene (PEDOT), polypyrrole, poly thiophene, poly (p-phenylene), poly (triphenylene), poly leather, poly medicine, poly Cai, poly onion , Polysulfuran, polycarbophene, tetrathiafulvalene-substituted polystyrene, ferrocene substituted polyethylene, carbophene substituted polyethylene, polypyrazine, polyacene, poly(hetero Acene)) is mixed or blended to impart electronic activity to such electronically insulating organic redox compounds. In some embodiments, the resulting cathode electrolyte or anode electrolyte mixture has an electronic conductivity of at least about 10 μS/cm. In other embodiments, the mixture has an electronic conductivity of about 10 μS/cm to 10W/cm. In other embodiments, the mixture has an electronic conductivity of at least about 10 μS/cm, or at least about 10 μS/cm, or at least about 10 μS/cm or greater.

[0089] In some embodiments, the anode or cathode particles may be provided with a partial or complete conductive coating.

[0090] In some embodiments, the semi-solid ion storage redox composition includes an ion storage solid coated with a conductive coating material. In certain specific embodiments, the conductive coating material has a higher electronic conductivity than solids. In certain specific embodiments, the solid is graphite and the conductive coating material is a metal, metal carbide, metal oxide, metal nitride, or carbon. In certain specific embodiments, the metal is copper.

[0091] In some embodiments, the solid of the semi-solid ion storage material is coated with a metal that is redox inert under the operating conditions of the redox energy storage device. In some embodiments, the solids of the semi-solid ion storage material are coated with copper to increase the conductivity of the storage material particles, increase the net conductivity of the semi-solid, and/or promote the charge between the energy storage particles and the conductive additives Transfer. In some embodiments, the storage material particles are coated with about 1.5% by weight of metallic copper. In some embodiments, the storage material particles are coated with about 3.0% by weight of metallic copper. In some embodiments, the storage material particles are coated with about 8.5% by weight of metallic copper. In some embodiments, the storage material particles are coated with about 10.0% by weight of metallic copper. In some embodiments, the storage material particles are coated with about 15.0% by weight of metallic copper. In some embodiments, the storage material particles are coated with about 20.0% by weight of metallic copper.

[0092] In some embodiments, the conductive coating is disposed on the anode or cathode particles by chemical deposition of conductive elements and subsequent drying and/or fumigation.

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[0093] In some embodiments, the conductive coating is disposed on the anode or cathode particles by electroplating (eg, in a fluidized bed).

[0094] In some embodiments, the conductive coating is disposed on the anode or cathode particles by co-sintering with a conductive compound and subsequent pulverization.

[0095] In some embodiments, the electrochemically active particles have a continuous intra-particle conductive material or embedded in a conductive matrix.

[0096] In some embodiments, the conductive coating and the conductive network within the pellets are prepared by multi-component spray drying of semi-solid anode/cathode particles and conductive material pellets.

[0097] In some embodiments, the conductive polymer is one of the component semi-solids and provides an electronically conductive element. In some embodiments, the conductive polymer is one or more of the following: polyethylene, polyaniline, polyphenylene, polypyrrole, poly(p-phenylene), poly(triphenylene), Poly.grass, poly medicine, polynaphtalene (polynaphtalene), poly onion, poly pyran, poly carbo Jie sitting, polyacene, poly (heteroacene). In some embodiments, the conductive polymer is a compound that reacts in situ to form a conductive polymer on the surface of the active material particles. In one embodiment, the compound is 2-hexyl thiophene, or 3-hexyl thiophene and is oxidized during battery charging to form a conductive polymer coating on the solid particles in the cathode semi-solid suspension. In other embodiments, the redox active material can be embedded in the conductive matrix. The redox active material can coat the external and internal interfaces in the flocculated or coalesced pellets of the conductive material. In other embodiments, the redox active material and the conductive material can be the two components of the composite material pellets. Without being bound by any theory or mode of operation, such coatings can stabilize redox active particles and can help prevent unwanted reactions with carrier fluids or electrolytes. Therefore, it can act as a synthetic solid-electrolyte interface (SEI) layer.

[0098] In some embodiments, an inexpensive iron compound such as pyrite (FeS2) is used as an ion storage compound that is inherently electronically conductive. In one embodiment, the stored ion is LiS

[0099] In some embodiments, a redox mediator is added to the semi-solid to improve the rate of charge transfer within the semi-solid electrode. In some embodiments, the redox mediator is ferrocene or a ferrocene-containing polymer. In some embodiments, the redox mediator is one or more of tetrathiafulvalene-substituted polystyrene, ferrocene-substituted polyethylene, and carbosulfide-substituted polyethylene.

[0100] In some embodiments, the surface conductivity or charge transfer resistance of the current collector used in the semi-solid storage battery is increased by coating the surface of the current collector with a conductive substance. Such a layer can also serve as a synthetic SEI layer. Non-limiting examples of conductive coating materials include carbon, metals, metal carbides, metal nitrides, metal oxides, or conductive polymers. In some embodiments, the conductive polymer includes, but is not limited to, polyaniline or polyethylene-based conductive polymer, or poly(3,4-ethylenedioxyphene) (PEDOT), polypyrrole, Polythiophene, poly(p-phenylene), poly(triphenylene), polyleather, polyru, polynaphtalene, poly onion, polysoran, polycarbaze, tetrathiafulvalene- Substituted polystyrene, ferrocene substituted polyethylene, carbosulfide substituted polyethylene, polyphenazine, polyacene, poly(heteroacene)). In some embodiments, the conductive polymer is a compound that reacts in situ to form a conductive polymer on the surface of the current collector. In one embodiment, the compound is 2-hexyl thiophene and is oxidized at a high potential to form a conductive polymer coating on the current collector. In some embodiments, the current collector is coated with a metal that is redox inert under the operating conditions of the redox energy storage device.

[0101] The semi-solid redox composition may include various additives to improve the performance of the redox battery. In this case, the semi-solid liquid phase will contain a solvent, in which electrolyte salts, binders, thickeners, or other additives added to improve stability, reduce gas formation, and improve SEI formation on the negative electrode particles Wait. The reality of such additives

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Examples include vinylene carbonate (VC), vinyl vinylene carbonate (VEC), fluoroethylene carbonate (FEC), or alkyl cinnamate to provide a stable passivation layer on the anode or in oxidation Provide a thin passivation layer on the cathode; Propylene sultone (PS), propylene sultone (PrS), or thioethylene carbonate as a gas barrier; as a gas release/safety/cathode polymerization agent combination Benzene (BP), cyclohexylbenzene, or partially hydrogenated terphenyl; or lithium bisoxalate borate as an anode passivator.

[0102] In some embodiments, the non-aqueous positive electrode and negative electrode semi-solid redox composition is prevented from absorbing impurity water by incorporating the water-absorbing compound into the active material suspension or into the storage tank or other pipeline of the system. And produce acid (for example HF in the case of LiPF6 salt). Optionally, the additive is a basic oxide that neutralizes the acid. Such compounds include, but are not limited to, silica gel, calcium sulfate (such as a product called dry gypsum), aluminum oxide, and aluminum hydroxide.

[0103] Example 1: Preparation of non-aqueous lithium titanate spinel anode semi-solid for battery filled with semi-solid using lithium metal oxide as electrode material:

[0104] Mix 0.7 g Li in a dry state by first using a TURBULA shaker-mixer₄Ti₅0i₂^0.44g of carbon black for 1 hour to prepare 8% by volume of lithium titanium oxide (Li) as a conductive additive in a non-aqueous liquid electrolyte consisting of LiPF6 in a mixture of alkyl carbonates at 84% by volume.₄Ti₅0i2) and 8% by volume of carbon black suspension. Then 2.5 ml of electrolyte was added and the mixture was sonicated for 1 hour.

[0105] Preparation of non-aqueous lithium cobalt oxide cathode semi-solid:

[0106] A suspension containing 12% by volume of lithium cobalt oxide (LiCo02), 8% by volume of carbon black, and the balance being an electrolyte composed of LiPF6 in a mixture of alkyl carbonates was prepared. A turbula mixture was used to mix 1.05 g of lithium cobalt oxide with 0.22 g of carbon for 1 hour. After that, electrolyte was added in an appropriate amount to constitute the balance of the semi-solid suspension, and the mixture was sonicated for 1 hour.

[0107] Some embodiments described herein relate to semi-solid suspensions having greater than about 45% by volume of active material. In addition, in some embodiments, a sufficient amount of conductive additives (such as carbon black) may be added to the slurry to improve the conductivity and electrochemical performance of the electrode. In addition, some of the embodiments described herein involve a repeatable, scalable, manufacturing-oriented formulation process.

[0108] In some embodiments, the electrochemically active semi-solid suspension may include about 20% to about 75% by volume of a cathode or anode ion storage component, and about 0.5% to about 25% by volume of a conductive additive component , And about 25% to about 70% by volume electrolyte.

[0109] In some embodiments, as described in more detail herein, the slurry components may be mixed in a batch process with specific spatial and/or temporal ordering of component addition (eg, with a batch mixer). In some embodiments, the slurry components may be mixed in a continuous process (eg, in an extruder) of component addition with a specific spatial and/or temporal order.

[0110] In some embodiments, the process conditions (temperature; shear rate or rate regime; component addition sequence, position and rate; mixing or residence time) can be selected and/or modified to control the electrical properties of the prepared slurry. , Rheology, and/or composition (e.g. uniformity) properties. In some embodiments, the speed of the mixing element (for example, the edge of the leaf of Che Kunzi) is from about 0.5 cm/s to about 50 cm/s_oIn some embodiments, the minimum gap between the fluids flowing in the mixing event (eg, the distance from the edge of the carcass blade to the wall of the mixer shell) is about 0.05 mm to about 5 mm. Therefore, the shear rate (speed scale divided by length scale) is therefore about 1 to about 10,000 per second (inverse second). In some embodiments, the shear rate may be less than 1/sec, and in other embodiments, the shear rate is greater than 10,000/sec.

[0111] For example, the process conditions can be selected to prepare a prepared slurry having a mixing index of at least about 0.80, at least about 0.90, at least about 0.95, or at least about 0.975. In some embodiments, the process conditions can be selected to produce a product having at least about 1CT'S/cm, at least about 1Cf'S/cm, at least about 1CT⁴S/cm, at least about lCT³S/cm, or at least about 10^_2S/cm of electronic conductivity

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The rate of modulation slurry. In some embodiments, the process conditions can be selected to produce an apparent viscosity of less than about 100,000 Pa-s, less than about 10,000 Pa-s, or less than about 1,000 Pa-s at an apparent shear rate of 1000 s at room temperature. The modulation slurry. In some embodiments, the process conditions can be selected to prepare a reconstituted slurry having two or more properties as described herein.

[0112] The mixing and forming of the slurry electrode usually includes: (i) raw material delivery and/or supply, (ii) mixing, (iii) mixed slurry delivery, (iv) distribution and/or extrusion, and (ν) forming. In some embodiments, multiple steps in the process can be performed at the same time and/or with the same piece of equipment. For example, an extruder can be used to mix and convey the slurry at the same time. Each step in the process can include one or more possible embodiments. For example, each step in the process can be performed manually or through any various process equipment. Each step may also include one or more sub-processes and optional inspection steps to monitor process quality.

[0113] The delivery and/or supply of raw materials may include: batch-based manual weighing of materials with natural supply (such as allowing the mixer to accept materials into the mixture without external force), through a piston mechanism or screw type "side filling" Use forced batch-based manual weighing of materials, use a natural-supply gravity screw solids feeder (for example, at a rate that the mixer can naturally accept materials), use a forced-feed gravity screw solids feeder (for example, with Piston mechanism or screw type "side-fill combined device sold by Brabender Industries Inc), and/or any other suitable conveying and/or feeding method and/or any suitable combination thereof.

[0114] In some embodiments, a Banburry® type batch mixer, the mixing section of a twin-screw extruder, a centrifugal planetary mixer, and/or a planetary mixer can be used to mix the slurry . In some embodiments, the slurry can be sampled and/or monitored after mixing to measure and/or evaluate uniformity, rheology, conductivity, viscosity, and/or density.

[0115] In some embodiments, such as after mixing, for example, a piston pump, a peristaltic pump, a gear/lobe pump, a screw pump, a single screw extruder, a delivery part of a twin screw extruder, and/or any Other suitable conveying devices are used to convey and/or pressurize the slurry. In some embodiments, during delivery and/or pressurization, the torque and/or power of the delivery device, the pressure, flow, and/or temperature at the exit of the delivery device can be measured, monitored, and/or controlled.

[0116] In some embodiments, the slurry may be dispensed and/or squeezed, such as after being transported and/or pressurized. For example, use a hanger die sheet extrusion die, a winter manifold sheet extrusion die, a contoured sheet extrusion die, any nozzle operable to apply a continuous flow of material to the substrate , Inject into a mold of appropriate size and shape (for example, filling a bag with material), and/or any other suitable dispensing device, which can dispense and/or squeeze the slurry.

[0117] In some embodiments, the slurry can form the final electrode after dispensing. For example, the slurry may be calendered, stamped, and/or pressed, subjected to vibration settling, and/or cut into discontinuous parts. Additionally, in some embodiments, unwanted portions of the material can be removed (eg, masked and cleaned) and optionally recycled into the slurry manufacturing process.

[0118] The systems, mixing equipment, processes, and methods described herein can be used to prepare semi-solid suspensions (such as slurries) suitable for electrochemical devices (such as batteries). The semi-solid suspension prepared by such a system and method is suitable for formulating slurry-based electrodes with specific properties such as rheology, conductivity and electrochemical properties. For example, some suitable mixing devices include batch mixers (such as c. W. Brabender or Banburry® type), continuous compounding equipment such as single-screw or twin-screw extruders equipped with valves (such as Leistritz, Haake), High-shear mixers such as blade type mixers, high-speed mixers, and/or rotating impellers. In some embodiments, the mixing device may be operable to control the flowability of the slurry by adjusting the temperature, and/or to control the uniformity of the slurry by modulating the chemical composition.

[0119] In embodiments where a batch mixer is used to mix the slurry, the slurry can be transferred from the batch mixer to another

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A piece of processing equipment, such as an extruder. In such an embodiment, the transfer method can be selected to minimize electrolyte loss, not significantly disrupt the slurry state, and/or not introduce other processing difficulties, such as entrainment of ambient gas. In embodiments where an extruder (such as a twin screw) is used to mix the slurry, mixing and material transport occur together, thus eliminating one process step.

[0120] In some embodiments, some electrolyte loss is tolerable and used as a control specification, and as the electrolyte volume fraction increases and/or the mixing index increases, the tolerable amount generally decreases. For example, at a mixing index of 0.8, the maximum electrolyte loss can be controlled to less than about 39%, to less than about 33%, or to less than about 27%. With a mixing index of 0.9, the maximum electrolyte loss can be controlled to less than about 5%, to less than about 4%, or to less than about 3%. At a mixing index higher than 0.9, the maximum electrolyte loss can be controlled to less than about 5%, to less than about 4%, or to less than about 3%. The component concentration can be calculated to determine and/or predict the tolerable loss, and it varies according to the specific component. In other embodiments, loss tolerance will be higher, while in other embodiments they will be limited.

[0121] In some embodiments, the composition and mixing process of the slurry can be selected to uniformly disperse the components of the slurry to achieve a permeable conductive network and a sufficiently high volume conductivity in the entire slurry, which is the same as described herein. The required electrochemical properties described in more detail are related to obtain a rheological state conducive to processing, which may include transfer, conveying (such as extrusion), distribution, division or cutting, and post-distribution molding (such as compression molding, rolling Pressing, calendering, etc.), or any combination thereof.

[0122] The devices, systems, and methods described below are examples of a semi-solid electrode battery with a porous current collector and an example of a method for manufacturing the electrode battery according to specific embodiments. Although specific embodiments are discussed, it should be understood that more than one embodiment may be combined to form, for example, a hybrid embodiment. The systems and methods described below can be applied to half cells (for example, anode cells or cathode cells), full cells (for example, and anode cells and cathode cells separated by ion permeable membranes), or modules (for example, multiple full cells). Any of the semi-solids (or parts thereof) described above can be used in any of the embodiments described below. Similarly, any of the mixing methods described above can be used in combination with any of the embodiments described below.

[0123] FIGS. 1A-1C are illustrations of a porous current collector 120 (also referred to herein as a "current collector") used in an electrochemical cell according to one embodiment. In some embodiments, as shown in FIG. 1A, the current collector 120 may be formed of a wire mesh. The wire mesh (also referred to as a mesh herein) can include any number of wires 121, which can be assembled into various structures using appropriate processes, such as regular patterns or structures prepared by weaving, weaving, knitting, etc., or by random A more random pattern or structure prepared by distributing the wires 121 and connecting them by welding, adhesive or other suitable techniques. In addition, the wire 121 containing the mesh may be any suitable material. For example, in some embodiments, the wire is a metal such as steel, aluminum, copper, titanium, or any other suitable metal. In other embodiments, the filaments may be conductive non-metallic materials, such as carbon nanofibers or any other suitable materials. In some embodiments, the filament 121 may include a coating. For example, the coating can be configured to reduce corrosion and enhance or reduce adhesion properties (for example, a hydrophilic or hydrophobic coating, respectively).

[0124] The opening 122 defined by the mesh can be any suitable shape. For example, in some embodiments, the opening 122 is polygonal (eg, square, rectangular, pentagonal, hexagonal, etc.). In some embodiments, the woven mesh may include selvedges configured to prevent fraying. As similarly described, the woven mesh may include an outer edge (ie, selvedge) configured to prevent the mesh fabric from loosening, fraying, separating, and/or otherwise failing at the edge.

[0125] In some embodiments, the porous current collector 120 may be an electronically conductive (e.g., metallic) open-cell foam plastic (e.g., a honeycomb structure composed of a solid metal containing a relatively large volume fraction of gas-filled pores ). The open pores (eg, pores) form an interconnected network that allows the semi-solid suspension to flow through the foam and substantially fill the pores, so that the "gas-filled pores" become filled with the semi-solid suspension during electrode manufacturing. The pore size of the filling gas can be changed

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(Eg volume) and/or the density of the honeycomb structure to change the porosity of the foam. For example, the "pillars" between the "vertexes" of the honeycomb structure can be lengthened to create larger pores, thereby increasing the porosity of the foam. Alternatively, the "thickness" or "diameter" of the pillars can be reduced to increase the size of the pores.

[0126] In some embodiments, the porous current collector 120 may have a regular pattern or structure prepared by weaving, knitting, knitting, etc., or by randomly distributing the wires 121 and connecting by welding, adhesive or other suitable techniques. They produce a more random pattern or structure of electronically conductive "nets." Similar to the foam described above, the mesh has an interconnected network of pores, which allows the semi-solid suspension to flow through the mesh and substantially fill the pores. It can be in any of a variety of ways, including, for example, changing the thickness or diameter of a single filament 121, changing the distance between adjacent filaments 121, changing the angle at which a single filament intersects (such as weaving angle), or changing the number or the number in the pattern. Silk to change the porosity of the mesh.

[0127] Regardless of whether the porous current collector 120 is "format", "net", or any other porous structure as defined herein, porosity can be defined as the volume fraction of pores (such as gas-filled, liquid-filled, or filled Semi-solid) divided by the total volume of the porous current collector 120 (for example, the sum of the volume fraction of pores and the volume fraction of solid materials (for example, honeycomb structure or silk)). Therefore, the porosity can be changed to optimize electronic conductivity, electrical resistance, structural properties, and/or any other electrical and physical properties. For example, in some embodiments, the current collector 120 may have a porosity of at least 66%. In some embodiments, the current collector 120 may have a porosity of at least 80%. In some embodiments, the current collector 120 may have a porosity of at least 90%.

[0128] In some embodiments, the porous current collector 120 may include a plurality of similar or dissimilar porous substrates. For example, the porous current collector 120 may include a stack of porous substrates of different sizes and/or porosities. In some embodiments, the porous substrate or a stack of porous substrates may be disposed on a solid metal foil or mechanically connected to it (for example, soldering, brazing, welding). In the other manner described, the porous current collector 120 does not have to have uniform porosity characteristics (for example, a functionally graded structure is possible).

[0129] The porous current collector 120 may be any suitable shape or size. For example, as shown in FIG. 1B, the current collector 120 may be substantially rectangular. In other embodiments, the size and shape of the current collector 120 may substantially correspond to the shape and size of the electrochemical cell cavity (eg, as described further herein, in an anode cell and/or a cathode cell). For example, in some embodiments, the current collector 120 may be polygonal (eg, square, pentagon, hexagon, etc.) or oval (eg, circle, ellipse, oblong, etc.). As shown in FIG. 1C, the thickness T of the current collector 120 may be any suitable size. For example, in some embodiments, the thickness T may substantially correspond to the depth of the electrochemical cell cavity. In some embodiments, the current collector 120 may be thick enough so that the desired conductivity is achieved as described below. In some embodiments, the current collector 120 may fold on itself to increase the thickness T. In some embodiments, the current collector 120 may have a thickness T of about 50 microns to about 5,000 microns. In some embodiments, the current collector 120 may have a thickness T of about 100 microns to about 3,000 microns. In some embodiments, the current collector 120 may have a thickness T of about 200 microns to about 2,500 microns. In some embodiments, a portion of the current collector can be folded and compressed to form an integrated electrode lead.

[0130] Although the current collector 120 described above is a wire mesh, in other embodiments, the current collector 120 may be any suitable porous substrate. For example, in some embodiments, the current collector 120 may be a mesh frame, mesh material, non-metal, conductive mesh, plate mesh, engineered micro-framework, conductive foam, or the like. In some embodiments, the mesh size, wire diameter, opening size, or any other suitable substrate characteristics of the current collector 120 can be configured to produce optimized electrical properties. For example, increasing the diameter of the wire 121 can increase the thickness of the current collector 120 and allow better conductivity when placed in contact with the electrode material. In some embodiments, the opening 122 defined by the current collector 120 (wire mesh or other porous substrate) may be large enough not to adversely affect the suspension of electrode material (eg, such that a non-uniform suspension may be produced).

CN 104040764 Β

[0131] In use, the current collector can be placed in contact with an electrode material (for example, a semi-solid anode slurry or a semi-solid cathode slurry) and the current collector and the electrode material can be collectively disposed in the electrochemical cell cavity. For example, as shown in FIG. 2, the electrode 205 is formed of an electrode material 250 provided on the porous current collector 220. The current collector 220 may define a frame 221 configured to support the electrode material 250 so that the electrode material 250 and the current collector 220 are in electrical communication. In other embodiments, for example, as shown in FIG. 3, the electrode 305 is formed by at least partially embedding the electrode material 350 (for example, a semi-solid electrode material) in the porous current collector 320. The current collector 320 may define a frame 321 that supports the electrode material 350 while allowing a portion of the electrode material 350 to occupy any pores in the frame 321 of the current collector 320. The electrode material 350 disposed in the pores defined by the frame 321 may increase the conductivity therebetween and the frame 321 may serve as a support for at least a part of the electrode material 350.

[0132] In some embodiments, the charge of the electrochemical cell may correspond to the thickness of the electrode material. To further expand, the charging capacity of the battery corresponds to the thickness of the electrode material and the number of electrochemical cells arranged in the battery container. Therefore, although the embodiment shown in FIGS. 2 and 3 is an example of a single-sided electrode (for example, an electrode material provided only on one side of the current collector), the charging capacity of an electrochemical battery and therefore use such an embodiment The battery (not shown in FIG. 2 or 3) may be limited by the thickness of a portion of the current collector (for example, current collector 220 and/or 320) that is not in contact with the electrode material (for example, electrode material 250 and/or 350). In the other way, since the current collector (or some other conductive element) is an inert component of the electrochemical cell, minimizing the volume fraction of the current collector and maximizing the volume fraction of the active electrode material improves the performance of the electrochemical cell. Total energy density.

[0133] FIG. 4 is a schematic diagram of an electrode 405 according to an embodiment. The electrode 405 includes an electrode material 450 that substantially encapsulates the porous current collector 420. The electrode material 450 may be, for example, any semi-solid electrode material described herein (for example, a semi-solid anode or a semi-solid cathode). The porous current collector 420 includes a frame 421 substantially similar to those described above with reference to FIGS. 1A-1C. In some embodiments, the electrode material 450 may be placed under pressure such that the electrode material 450 is forced to flow through any pores (eg, voids, openings, gaps, pores, etc.) defined by the porous current collector 420. In other embodiments, the porous current collector 420 may be disposed in a bath of the electrode material 450 such that the electrode material 450 flows through the pores of the porous current collector 420 (for example, by wicking) and substantially encapsulates the current collector 420.

[0134] In some embodiments, the electrode material 450 may flow into the pores of the porous current collector 420 at approximately ambient temperature. In other embodiments, the electrode material 450 may be heated to promote the flow of the electrode material 450 into the pores of the porous current collector 420. In some embodiments, once the electrode material 450 has substantially encapsulated the porous current collector 420, the temperature can be lowered (e.g., to or below the freezing point of the electrode material 450) so that the electrode material 450 can be cured (e.g., hardened or hardened). ).

[0135] In this way, the conductivity between the electrode material 450 and the current collector 420 can be increased by increasing the surface area of the electrode material 450 in contact with the current collector 420. In addition, since the electrode material 450 substantially encapsulates the porous current collector 420, the charging amount relative to the thickness of the electrode can be increased. As shown in FIG. 4, the end of the current collector 420 may not be substantially enclosed. In this way, the current collector 420 may be connected to or include a tab configured as an electrical lead that is not substantially encapsulated by the electrode material 450. Alternatively, only one end (not shown) of the current collector 420 may be substantially not enclosed. Therefore, when the electrode 405 is disposed in the electrochemical cell cavity and a separator (ion permeable membrane) is disposed around the electrode 405, the tab may extend from the cavity to form an electrical lead for the electrochemical cell.

[0136] Although it is shown in FIG. 4 that the electrode 405 includes an electrode material 450 having a thickness substantially similar to that of the porous current collector 420, in other embodiments, the thickness need not be similar. For example, FIG. 5 is a schematic diagram of an electrode 505 according to an embodiment. As described above with reference to FIG. 4, the electrode 505 includes an electrode material 550 that substantially encapsulates the porous current collector 520. As shown in FIG. 5, the electrode material 550 may have a thickness greater than that of the porous current collector 520.

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[0137] Although it is shown in FIG. 5 that the electrode 505 includes a porous current collector 520 that includes an end that is not substantially encapsulated, in other embodiments, the electrode material may be configured to substantially encapsulate The end of the current collector. For example, FIG. 6 is a schematic diagram of an electrode 605 according to an embodiment. The electrode 605 includes an electrode material 650 that substantially encapsulates the porous current collector 620. More specifically, the electrode material 650 substantially encapsulates both ends of the porous current collector 620. As shown in FIG. 6, the porous current collector 620 includes a tab 623 configured to extend from the end of the porous current collector 620 so that the tab 623 is not substantially enclosed. In this way, the tab 623 can be configured to form electrical leads.

[0138] As described herein, in some embodiments, the current collectors 120, 220, 320, 420, 520, 620 may have about 50 microns to about 5,000 microns, about 100 microns to about 3,000 microns, or about 200 microns to about A thickness T of 2,500 microns. In some embodiments, the finished electrodes 205, 305, 405, 505, 605 may have a thickness substantially equal to the thickness T of the current collector 120, 220, 320, 420, 520, 620. In some embodiments, the finished electrode 205, 305, 405, 505, 605 may have a thickness greater than the thickness T of the current collector 120, 220, 320, 420, 520, 620. For example, as shown in FIGS. 5 and 6, the electrode materials 550, 650 extend beyond the thickness of the current collector 520, 620, so that the thickness of the completed electrode 505, 605 is greater than the thickness of the current collector 520, 620. In some embodiments, the thickness of the current collector is greater than about 20%, 25%, 30%, 35%, 40%, 50%, 55%, 60%, 65%, 70%, 75% of the thickness of the finished electrode , 80%, 85%, 90% or 95%. In some embodiments, the thickness of the current collector is substantially equal to the thickness of the finished electrode. In the other way, when the thickness of the completed electrode is substantially equal to or greater than the thickness of the current collector, the completed electrode can be considered to be a "double-sided" electrode.

[0139] Referring now to FIGS. 7A and 7B, a system 701 for manufacturing electrodes according to one embodiment is shown. The system 701 includes a porous current collector 720, a semi-solid electrode material 750 (also referred to herein as "electrode material"), and a distribution device 760. The semi-solid electrode material 750 can be any of those described in detail herein. The porous current collector 720 (also referred to herein as the "current collector") can be, for example, any porous material sheet described herein that is stored in the drum 725. The current collector 720 may be deployed from the drum 725 in a manual or automated process, so that the flat portion 726 of the current collector 720 extends from the drum 725. For example, a mechanical clamp (not shown) may clamp the end of the current collector 720 and pull the current collector 720 in one direction to unfold the drum 725. In some embodiments, the current collector 720 may travel on a conveyor system.

[0140] The distribution device 760 includes a storage tank 763 and a plurality of nozzles 761. The storage tank 763 is configured to contain a part of the electrode material 750. In this way, a portion of the electrode material 750 can flow through the nozzle 761 in response to the applied pressure. In some embodiments, the applied pressure may be a gravitational field applied on the electrode material 750. In other embodiments, the applied pressure can be provided by any suitable pump or the like. In some embodiments, the nozzle 761 can distribute sufficient force to a portion of the electrode material 750 so that the electrode 750 substantially fills the pores (eg, voids, openings, gaps, holes, etc.) of the current collector 720. In this way, the electrode material 750 may substantially encapsulate the current collector 720. In some embodiments, the system 701 may include any suitable device configured to facilitate the flow of electrode material 750 (eg, a device for applying agitation, vibration, sonication, etc.).

[0141] Although not shown in FIGS. 7A and 7B, the system 701 may include any suitable device configured to perform post-processing steps on the formed electrode. For example, in some embodiments, the system 701 may include a device configured to substantially cool the formed electrode. In such an embodiment, the device can cool the formed electrode to or below the freezing point of the electrode material 750, allowing the electrode material to solidify or harden. In some embodiments, the system 701 may include a configuration configured to cut the formed electrode (eg, the current collector 720 encapsulated by the electrode material 750) to any suitable size so that the formed electrode can be disposed in an electrochemical cell. In some embodiments, the system 701 may include any other suitable post-processing steps, such as calendering. In some embodiments, the system 701 may include a device (not shown) for connecting lugs (eg, electrical leads) and electrodes. For example, in some embodiments, it can be welded, crimped or otherwise fixed and connected electronically.

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Wire and electrode. In some embodiments, the system 701 may include a second dispensing device (not shown) configured to dispense the electrode material 750 on the opposite side of the current collector 720 and substantially encapsulate the current collector 720.

[0142] Referring now to FIGS. 8A and 8B, a system 801 for manufacturing electrodes according to one embodiment is shown. The system 801 includes a porous current collector 820, a semi-solid electrode material 850 (also referred to as "electrode material" herein), a distribution device 860, and a drum 870. The semi-solid electrode material 850 may be any of those described in detail herein. The porous current collector 820 (also referred to herein as the "current collector") can be, for example, any porous material sheet described herein that is stored in the drum 825. The current collector 820 may be deployed from the drum 825 in a manual or automated process so that the flat portion 826 of the current collector 820 extends from the drum 825 (as described above with reference to FIGS. 7A and 7B).

[0143] The distribution device 860 includes a storage tank 863 that defines a distribution tank 862. The storage tank 863 is configured to contain a part of the electrode material 850. In this manner, a portion of the electrode material 850 may flow through the groove 862 in response to the applied pressure (as described above with reference to FIGS. 7A and 7B). In some embodiments, the system 801 may include any suitable device configured to facilitate the flow of the electrode material 850 (eg, a device for applying agitation, vibration, sonication, etc.). In this way, the electrode material 850 may be deposited on the current collector 820. As shown in FIG. 8B, the roller 870 may be configured to join the electrode material 850 and the current collector 820 to apply a compressive force so that the electrode material 850 fills the pores of the current collector 820 and substantially encloses the current collector 820. Although not shown in FIGS. 8A and 8B, the system 801 may include any post-processing steps included in the system 701 including the second dispensing device described with reference to FIGS. 7A and 7B.

[0144] Referring now to FIGS. 9A and 9B, a system 901 for manufacturing electrodes according to an embodiment of the present invention is shown. The system 901 includes a porous current collector 920, a semi-solid electrode material 950 (also referred to herein as an "electrode material"), a storage tank 963, and a control device 975. The semi-solid electrode material 950 may be any of those described in detail herein and is provided in the storage tank 963. The porous current collector 920 (also referred to herein as the "current collector") may be, for example, any porous material sheet described herein that is stored in the drum 925. The current collector 920 may be deployed from the drum 925 in a manual or automated process, so that a portion 926 of the current collector 920 extends from the drum 925. More specifically, a part of the current collector 920 passes through the storage tank 963 so that the part 926 of the current collector 920 is disposed in the electrode material 950. In this way, the electrode material 950 may substantially encapsulate and impregnate the current collector 920. Although not shown in Figures 9A and 9B, the system 901 may include any suitable device configured to facilitate encapsulation of the current collector 920 (such as any of those described above).

[0145] As shown in FIG. 9B, the system 901 may include a control device 975 configured to remove excess material from the current collector 920. For example, the current collector 920 can pass through the storage tank 963 so that the electrode material 950 substantially encapsulates the current collector 920 and a scraper (such as the control device 975) can engage the electrode material 950 and/or the current collector 920 to remove excess from the current collector 920 Electrode material 950. Although not shown in FIGS. 9A and 9B, the system 901 may include any post-processing steps included in the system 701 described with reference to FIGS. 7A and 7B.

[0146] FIGS. 10A-10C are schematic diagrams of a system 1001 for manufacturing electrodes according to an embodiment. The system 1001 includes a porous current collector 1020, a semi-solid electrode material 1050 (also referred to herein as "electrode material"), and a mold 1080. The mold 1080 includes a first plate 1081 and a second plate 1085. The first plate 1081 defines a recess 1082 and a notch 1083, each of which is configured to receive a portion of the porous current collector 1020. Although the recess 1082 is shown to be substantially rectangular in FIGS. 10A and 10B, the first sheet 1081 may define a recess having any suitable shape. For example, in some embodiments, the recess 1082 may be substantially concave, convex, triangular, pyramidal, or any other suitable shape. The second plate 1085 is a substantially flat plate and can be configured to move relative to the first plate 1081 as described further herein.

[0147] The porous current collector 1020 can be any porous current collector described herein. In this way, the porous current collector 1020 includes a frame 1021, which can serve as a support for at least a portion of the electrode material 1050, as described further herein.

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frame. The porous current collector 1020 also includes a lug 1023 configured to be disposed in the notch 1083 of the first plate 1081. As shown in FIG. 10A, as further described herein, a porous current collector 1020 may be disposed in the recess 1082 and the notch 1083 of the first plate 1081 and configured to receive at least a portion of the electrode material 1050.

[0148] The electrode material 1050 can be substantially similar to any electrode material described herein. In addition, the electrode material 1050 may include an anode active material (that is, the electrode material 1050 is an anode material) or a cathode active material (that is, the electrode material is a cathode material). As shown in FIG. 10A, the required amount of electrode material 1050 is configured to be disposed between the porous current collector 1020 and the second plate 1085. In some embodiments, the electrode material 1050 may be actively transferred to the mold 1080 (eg, the gap between the second sheet 1085 and the porous current collector 1020). In other embodiments, the electrode material 1050 can be extruded so that the electrode material 1050 defines the desired shape, and can be fed into the mold 1080 (eg, continuously or modularly). In other embodiments, the electrode material 1050 may be disposed in a foldable container, for example, and may be delivered to the mold 1080 modularly.

[0149] A required amount of electrode material 1050 is provided between the second plate 1085 and the porous current collector 1020, as shown by the arrow AA in FIG. 10B, so that the second plate 1085 can move relative to the first plate 1081. In this way, the second plate 1085 exerts a force on the electrode material 1050± to move the electrode material 1050 relative to the porous current collector 1020. The pressure applied on the electrode material 1050 causes the electrode material 1050 to flow within the pores (eg, voids, openings, gaps, etc.) defined by the frame 1021 of the porous current collector 1020. Therefore, as shown in FIGS. 10B and 10C, the electrode material 1050 substantially encapsulates the porous current collector 1020. The tab 1023 provided in the notch 1083 can remain substantially unencapsulated by the electrode material 1050, and can therefore serve as an electrical lead for the electrochemical cell in which the formed electrode is provided.

[0150] Although it is shown in FIGS. 10A and 10B that the electrode material 1050 is moved relative to the porous current collector 1020, in some embodiments, the electrode material 1050 may be disposed in the recess 1082 of the lower plate 1081 and the current collector 1020 may be provided. Move with respect to the electrode material 1050. Similarly, the upper plate 1085 can be placed in contact with the current collector 1020 to move the current collector 1020 relative to the electrode material 1050.

[0151] In some embodiments, the system 1001 may include device(s) configured to facilitate the flow of electrode material 1050. For example, in some embodiments, the system 1001 may include a device configured to apply vibration, ultrasonic treatment, or agitation to the first sheet 1081, the second sheet 1085, the porous current collector 1020, and/or the electrode material 1050. In some embodiments, the electrode material 1050 can be heated to promote flow. In such an embodiment, the system 1001 may include a device configured to provide heat to the first sheet 1081, the second sheet 1085, the porous current collector 1020, and/or the electrode material 1050.

[0152] In some embodiments, the system 1001 may include a device configured to reduce the temperature of the electrode material 1050 (eg, to a freezing point or below). For example, the electrode material 1050 substantially encapsulates the porous current collector 1020. In some embodiments, the temperature of the electrode material 1050 can be lowered so that the electrode material 1050 solidifies (eg, hardens around the porous current collector 1020). In some embodiments, the first plate 1081 may be cooled so that when the electrode material 1050 is forced to contact the first plate 1081 by the movement of the second plate 1085, the thermal energy is transferred away from the electrode material 1050, thereby reducing the thickness of the electrode material 1050. The temperature is lowered below the freezing point to facilitate the processing of the formed electrode material 1050. The frozen electrode material 1050 can then be used manually (for example by hand) or mechanically (for example by conveyor, robot, etc.) to manufacture an electrochemical cell. The electrode material 1050 can then be returned to the ambient temperature before use.

[0153] Although the porous current collector 1020 is associated with the electrode material before "freezing" of the electrode material as described above, in some embodiments, any suitable method may be used to form the electrode material 1050, which may include substantially cooling The electrode material 1050 (for example, to a freezing point or below) to facilitate the processing of the formed electrode material 1050. For example, the required amount of liquid or semi-solid electrode material 1050 can be set in the mold (for example, between the first plate 1081 and the second plate 1085)

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The recess 1082) ο can transfer thermal energy away from the electrode material 1050, thereby reducing the temperature of the electrode material 1050 below the freezing point to solidify the electrode material 1050. Then, the solid electrode material 1050 can be manually (for example, by hand) or mechanically (for example, by a conveyor, a manipulator, etc.) placed on a current collector (porous or conventional foil), and then assembled into an electrochemical cell. The electrode material 1050 can then be returned to the ambient temperature before use.

[0154] FIGS. 11A-11G are schematic diagrams showing a method 1102 of a system for manufacturing an electrochemical cell according to an embodiment. The system includes a substrate 1110A (for example, configured to form an electrode battery once manufactured), a porous current collector 1120, a semi-solid electrode material 1150 (also referred to herein as an "electrode material"), and a mold 1180. As shown in FIG. 11A, the mold 1180 includes a first plate 1181 and a second plate 1185. As described further herein, the first sheet 1181 defines a recess 1182 configured to receive a portion of the substrate 1110A, the porous current collector 1120, and the electrode material 1150. Although the recess 1182 is shown to be substantially rectangular in FIG. 11A, the first plate 1181 may define a recess having any suitable shape. For example, in some embodiments, the recesses may be substantially concave, convex, triangular, pyramidal, or any other suitable shape. The second sheet 1185 is a substantially flat sheet, and as described further herein, it can be configured to move relative to the first sheet 1181.

[0155] The substrate 1110A may be any suitable battery material. For example, in some embodiments, the substrate 1110A is a laminated substrate (composition is similar to known laminated substrates). In some embodiments, the substrate 1110A is substantially flat, and may be moldable (eg, plastically deformable in response to an applied force) (see, for example, FIG. 11B). In some embodiments, the substrate 1110A may define a cavity or groove (not shown) before being manufactured, which cavity or groove may receive a portion of the porous current collector 1120 and the electrode material 1150 as described further herein.

[0156] The electrode material 1150 can be substantially similar to any electrode material described herein. In addition, the electrode material 1150 may include an anode active material (that is, the electrode material 1150 is an anode material) or a cathode active material (that is, the electrode material is a cathode material). The porous current collector 1120 can be any porous current collector described herein. In this way, the porous current collector 1120 includes a frame (not shown in FIGS. 11A-11G), which can serve as a support for at least a portion of the electrode material 1150, as described further herein. As described further herein, the porous current collector 1120 also includes tabs 1123 configured to extend beyond the substrate and serve as electrical leads.

[0157] As shown in FIG. 11C, a porous current collector 1120 may be disposed on the substrate 1110A and a required amount of electrode material 1150 may be disposed between the porous current collector 1120 and the second plate 1185. In some embodiments, the electrode material 1150 may be actively transferred to the mold 1180 (eg, the gap between the second sheet 1185 and the porous current collector 1120). In other embodiments, the electrode material 1150 can be extruded so that the electrode material 1150 defines a desired shape, and it can be fed into the mold 1180 (eg, continuously or modularly). In other embodiments, the electrode material 1150 can be placed in a foldable container, for example, and can be delivered to the mold 1180 modularly.

[0158] A required amount of electrode material 1150 is provided between the second plate 1185 and the porous current collector 1120, as shown by the arrow BB in FIG. 11C, so that the second plate 1185 can move relative to the first plate 1181. In this way, the second plate 1185 exerts a force on the electrode material 1150± to move the electrode material 1150 relative to the porous current collector 1120. The pressure applied on the electrode material 1150± causes the electrode material 1150 to flow in the pores (eg, voids, openings, gaps, etc.) defined by the frame of the porous current collector 1120. In addition, a part of this force is transferred to the base material 1110A, so that the base material 1110A is deformed to substantially fill the groove 1182 of the first plate 1081. In this manner, the substrate 1110A can be deformed to fill the groove 1182, thereby defining a substrate cavity in which the porous current collector 1120 and the electrode material 1150 are disposed.

[0159] As shown in FIG. 11D, when the electrode material 1150 and the porous current collector 1120 are disposed in a cavity (not shown) defined by the substrate 1110A, the electrode material 1150 may substantially encapsulate the porous current collector 1120. The lug 1123 can be configured from

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The cavity extends beyond the edge of the substrate 1110A and can be kept substantially unencapsulated by the electrode material 1150. The system may also include any suitable device configured to promote the flow of electrode material 1150, such as those described above.

[0160] Accompanying the substrate 1110A defines a cavity (not shown) and the current collector 1120 and the electrode material 1150 are disposed therein, and a separator 1190 (for example, an ion permeable membrane) is disposed around the cavity to surround the electrode material 1150 and the porous collector. The fluid 1120 (the separator does not surround the tab 1123), thereby forming an electrode battery (see, for example, FIG. 11E). The electrode battery may be an anode battery 1110, for example. The method 1101 also includes forming a second electrode cell, such as a cathode cell 1130 in a similar manner as described. As shown in FIG. 11F, the cathode battery 1130 may be disposed adjacent to the anode battery 1110 and the system may include a device configured to apply heat to a portion of the anode battery 1110 and a portion of the cathode battery 1130. In this way, substrate materials (for example, substrate 1110A) can be joined together (for example, by chemical bonding generated by the application of heat). Therefore, as shown in FIG. 11G, the connection of the anode cell 1110 and the cathode cell 1130 forms an electrochemical cell 1100 (for example, a battery cell).

[0161] FIG. 12 is an illustration of at least a portion of an electrochemical cell 1200 according to an embodiment. As described further below, this portion of the electrochemical cell 1200 includes a set of anodes 1210 and a set of cathodes 1230 arranged in an alternating arrangement and separated by a set of separators 1290. The anode 1210 and the cathode 1230 may be substantially similar to any of those described herein. Further expanded, each of the anode 1210 and the cathode 1230 includes a porous current collector 1220 that is substantially encapsulated by an electrode material 1250 (for example, an anode material and a cathode material, respectively). This portion of the electrochemical cell 1200 also includes a set of anode electrical leads and a set of cathode electrical leads that are in physical and electrical contact with the anode 1210 and the cathode 1230, respectively. In addition, each anode lead may be physically and electronically connected together (for example, by ultrasonic welding), so that each anode lead forms a single anode electrical lead 1223. Similarly, each cathode lead can be physically and electronically connected to form a single cathode electrical lead 1233. In this way, the anode lead 1223 and the cathode lead 1233 may be electrically connected with the anode terminal (not shown) and the cathode terminal (not shown) to form, for example, a storage battery.

[0162] The separator 1290 may be, for example, an ion permeable membrane. As shown in FIG. 12, each of the separators 1290 is configured to extend substantially beyond the surfaces of the anode 1210 and the cathode 1230, thereby reducing the possibility of electrical shorts originating from the anode 1210 contacting the cathode 1230. Although it is shown in FIG. 12 that the separator 1290 is separately disposed between a pair of adjacent anode and cathode, in other embodiments, the separator may be substantially continuous, such that a single separator separates each anode and cathode pair. . In other embodiments, one or more anodes 1210 and/or one or more cathodes 1230 may be disposed in, for example, a separator bag (not shown). Similarly stated, a single separator can substantially encapsulate the anode or the cathode. In such an embodiment, the separator pocket may correspondingly define an opening or port configured to receive an anode lead or a cathode lead.

[0163] Although it is shown in FIG. 12 that the current collector 1220 is encapsulated by the electrode material 1250 and connected to the electrical leads 1223 and 1233, in some embodiments, the storage battery may include a current collector that has substantially no electrode material. Encapsulated integrated electrical leads. For example, FIG. 13 is an illustration of at least a portion of an electrochemical cell 1300 according to an embodiment. This part of the electrochemical cell 1300 includes a set of anodes 1310 and a set of cathodes 1330 arranged in an alternating arrangement and separated by a separator 1390 (for example, an ion permeable membrane). As shown in FIG. 13, the separator 1390 may be substantially continuous, such that a single separator separates each adjacent pair of anode 1310 and cathode 1330. In other embodiments, the separator 1390 may be of any suitable configuration, such as those described above with reference to FIG. 12.

[0164] The anode 1310 and the cathode 1330 may be substantially similar to any of those described herein. Further expanded, each of the anode 1310 and the cathode 1330 includes a porous current collector 1320 that is substantially encapsulated by an electrode material 1350 (for example, an anode material and a cathode material, respectively). The anode cell 1310 and the cathode cell 1330 can also be configured to include integrated electrical leads 1323 and 1333, respectively. The anode electrical lead 1323 and the cathode electrical lead 1333 may, for example, be portions of the current collector 1320 configured to extend beyond the electrode material 1350 (eg, substantially unencapsulated). In this way, the anode lead 1323 and the cathode lead 1333 can be

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The anode terminal (not shown) and the cathode terminal (not shown) are electrically connected to form, for example, a storage battery.

[0165] Although it is shown in FIG. 13 that the anode 1310 and the cathode 1330 constitute the electrodes separately, in other embodiments, the anode and the cathode may be connected to a sheet or foil (for example, a bipolar that is also referred to as an "electrode pair" for simplicity). structure). In such an embodiment, a plurality of electrode pairs may be arranged in a stacked structure in which a separator is provided between each adjacent electrode pair.

[0166] Although various embodiments have been described above, it should be understood that they are presented only by way of example and not limitation. For example, although the embodiments herein describe electrochemical devices such as lithium ion batteries, the systems, methods, and principles described herein are applicable to all devices that contain electrochemically active media. Said another way, including at least one active material (source or pool of carriers), conductive additives and ion conductive medium (electrolyte) any electrode and/or device, such as batteries, capacitors, electric double layer capacitors (Such as super capacitors), pseudo capacitors, etc. are all within the scope of the present disclosure. In addition, this embodiment can be used for non-aqueous and/or water-containing electrolyte battery chemistry.

[0167] When the methods and steps described above indicate that certain events occur in a certain order, those of ordinary skill in the art who obtain the benefits of the present disclosure will recognize that the order of certain steps can be changed, and such changes are based on the present invention. Invented variants. In addition, if possible, certain steps can be performed simultaneously in a parallel process, as well as in the order described above. In addition, some steps may be partially completed and/or omitted before proceeding to subsequent steps.

[0168] Although various embodiments have been specifically shown and described, various changes in form and details can be made. For example, although various embodiments are described as having specific features and/or component combinations, other embodiments having any feature and/or any combination or sub-combination of components from any embodiment described herein are also possible. The specific structure of each component can also be changed.

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