Lithium ion battery

0001This application claims priority under 35 USC § 119 (e) and is filed on September 2, 2011, US Provisional Patent Application No. 61 / 530,545, and on June 1, 2012. Claim the interests of 35 USC 61 / 654,184 filed, each of which is incorporated herein by reference in its entirety for all purposes.

0002The present invention relates to the field of lithium ion batteries. In particular, the present invention relates to a lithium ion battery containing a spinel positive electrode and a non-aqueous electrolyte.

0003Lithium-ion batteries are being strongly promoted in hybrid electric vehicle (HEV) and plug-in hybrid electric vehicle (PHEV) applications. 4V spinel type LiMn₂O₄Positive electrode and 3.4V olivine type LiFePO₄Both positive electrodes are of great interest in this regard due to the low cost of Mn and Fe and their environmental friendliness. In addition, these positive electrodes provide higher rate capacity and higher safety than layered oxide positive electrodes. But LiMn₂O₄Positive electrode and LiFePO₄The positive electrode has a limited energy density due to its low capacitance or low operating voltage. One way to improve energy and output density is to increase the operating voltage. In this regard, the 5V spinel positive electrode LiMn_1.5Ni_0.5O₄Has a nearly flat operating voltage close to V, and Ni^2+/3+And Ni^3+/4+There is great interest because of the permissible capacity obtained by the action of redox pairs.

0004But LiMn_1.5Ni_0.5O₄The positive electrode may be characterized by suboptimal cycle characteristics in conventional carbonate electrolytes, which is a large lattice during the cycle with the formation of three cubic phases with large differences in lattice constants during the charge-discharge process. It may be due to distortion. Another cause for suboptimal cycle performance is Li_xNi_1-xO impurities and the corrosion reaction between the positive electrode surface and the carbonate electrolyte at a high operating voltage of about 5 V can be mentioned.

0005To improve cycle performance as discussed in Patent Document 1; and Non-Patent Document 1, LiMn_1.5Ni_0.5O₄Partial substitution of Mn and Ni in Li, Al, Mg, Ti, Cr, Fe, Co, Cu, Zn, and Mo has been pursued. Improvements in cycle performance can be achieved with conventional carbonate electrolytes at room temperature by partial cation substitution, while high temperature cycle performance is associated with the instability inherent in conventional carbonate electrolytes and the decomposition reactions promoted at high temperatures. Therefore, the problem still remains.

0006In Patent Document 2, the formula CH₃COOCH₂CH_3-xF_xDecomposition in the range of +1.0 to 3.0V based on the chain fluorinated carboxylic acid ester represented by (where x is 2 or 3) and the equilibrium potential between metallic lithium and lithium ions. Non-aqueous electrolytes used in secondary batteries containing film-forming compounds are described. This electrolyte has been used in various embodiments in secondary batteries provided with a lithium-transition metal oxide positive electrode with a charge cutoff voltage of 4.2 V.

<p num="0007"><patcit num="1"><text>U.S. Pat. No. 6,337,158 (Nakajima)</text></patcit><patcit num="2"><text>U.S. Patent Application Publication No. 2010/0035162 (Chiga)</text></patcit></p>

<p num="0008"><nplcit num="1"><text>Liu et al, J.Phys.Chem.C 13: 15073-15079,2009</text></nplcit></p>

<p num="0009"> Despite the aforementioned efforts in the art, there is still a need for lithium-ion batteries that operate at high voltages (ie, up to about 5V) and exhibit improved cycle performance at high temperatures.</p>

<p num="0010"> In one embodiment, it is a lithium-ion battery: (a) With housing; (b) Negative electrode and positive electrode that are arranged in the housing and are in conductive contact with each other, and the positive electrode is a manganese positive electrode containing a lithium-containing manganese composite oxide having a spinel structure as an active material, and lithium-containing manganese composite oxidation The thing is a formula Li_zMn_1.5Ni_xM_yO_4-d(In the formula, M is at least one metal selected from the group consisting of Al, Cr, Fe, Ga, Zn, Co, Nb, Mo, Ti, Zr, Mg, V, and Cu, 0.38 x &lt;0.5, 0 &lt;y 0.12, 0 d 0.3, and 0.00 &lt;z 1.1, where z varies with the emission and uptake of lithium ions and electrons during charging and discharging) Represented by, with negative and positive; (c) A non-aqueous electrolyte composition that is located in the housing and provides an ionic conductive passage between the negative and positive electrodes, at least one electrolyte salt, and at least one fluorinated acyclic carboxylic acid. With a non-aqueous electrolyte composition containing an acid ester and / or at least one fluorinated acyclic carbonate; (d) Porous separator between negative electrode and positive electrode, Lithium-ion batteries are provided.</p><p num="0011"> In another embodiment, it is a lithium-ion battery: (a) With housing; (b) Negative electrode and positive electrode that are arranged in the housing and are in conductive contact with each other, and the positive electrode is a manganese positive electrode containing a lithium-containing manganese composite oxide having a spinel structure as an active material, and lithium-containing manganese composite oxidation The thing is a formula Li_zNi_xM_yMn_2-xyO_4-d (Equation IB) (In the equation, z is 0.03 to 1.0; z varies with the emission and uptake of lithium ions and electrons during charging and discharging; x is 0.3 to 0.6; M is Cr, Fe, Co, Includes one or more of Li, Al, Ga, Nb, Mo, Ti, Zr, Mg, Zn, V, and Cu; y is 0.01-0.18 and d is 0-0.3) Represented by, with negative and positive; (c) A non-aqueous electrolyte composition that is located in the housing and provides an ionic conductive passage between the negative and positive electrodes, at least one electrolyte salt, and at least one fluorinated acyclic carboxylic acid. With a non-aqueous electrolyte composition containing an acid ester and / or at least one fluorinated acyclic carbonate; (d) Porous separator between negative electrode and positive electrode, A lithium ion battery comprising the above is provided in the present invention.</p><p num="0012"> In yet another embodiment, it is a lithium-ion battery: (a) With housing; (b) Negative electrode and positive electrode that are arranged in the housing and are in conductive contact with each other, and the positive electrode is a manganese positive electrode containing a lithium-containing manganese composite oxide having a spinel structure as an active material, and lithium-containing manganese composite oxidation The thing is a formula LiMn_1.5Ni_xM_yO₄(In the equation, M is at least one metal selected from the group consisting of Al, Cr, Fe, Ga, and Zn, with 0.4 x &lt;0.5 and 0 &lt;y 0.1). Represented by, with negative and positive; (c) A non-aqueous electrolyte composition that is located in the housing and provides an ionic conductive passage between the negative and positive electrodes, at least one electrolyte salt, and at least one fluorinated acyclic carboxylic acid. With a non-aqueous electrolyte composition containing an acid ester and / or at least one fluorinated acyclic carbonate; (d) Porous separator between negative electrode and positive electrode, A lithium ion battery comprising the above is provided in the present invention.</p><p num="0013"> In yet another embodiment, the fluorinated acyclic carboxylic acid ester has the following structural formula: R¹--- C (O) O --- R²(In the formula, R¹Is CH₃, CH₂CH₃, CH₂CH₂CH₃, CH (CH₃)₂, CF₃CF₂H, CFH₂, CF₂R³, CFHR³, And CH₂R^fSelected from the group consisting of R²CH independently₃, CH₂CH₃, CH₂CH₂CH₃, CH (CH₃)₂, And CH₂R^fSelected from the group consisting of R³May be replaced with at least one fluorine C₁~ C₃Alkyl group, R^fIs a C substituted with at least one fluorine₁~ C₃Alkyl group and R¹Or R²At least one of contains at least one fluorine, R¹Is CF₂If H, then R²Is CH₃is not it) Can be represented by and / or The fluorinated acyclic carbonate has the following structural formula: R⁴--- OC (O) O --- R⁵(In the formula, R⁴And R⁵Independently, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH (CH₃)₂, And CH₂R^fSelected from the group consisting of R^fIs a C substituted with at least one fluorine₁~ C₃Alkyl group and R⁴Or R⁵At least one of them contains at least one fluorine) Can be represented by; and</p><p num="0014"> In yet another embodiment of the invention, an electronically powered or assited device comprising a lithium ion battery as described above is disclosed.</p>

0015<figref num="1">The experimental results in Example 1 are shown in graph form.</figref><figref num="2">The experimental results in Example 2 are shown in graph form.</figref><figref num="3">The experimental results in Example 3 are shown in graph form.</figref><figref num="4">The experimental results in Example 4 are shown in graph form.</figref><figref num="5">The experimental results in Example 5 are shown in graph form.</figref><figref num="6">The experimental results in Example 6 are shown in graph form.</figref><figref num="7a">The experimental results in Example 7 are shown in graph form.</figref><figref num="7b">The experimental results in Example 7 are shown in graph form.</figref><figref num="7c">The experimental results in Example 7 are shown in graph form.</figref><figref num="8">The experimental results in Example 8 are shown in graph form.</figref><figref num="9">The experimental results in Example 9 are shown in graph form.</figref><figref num="10">The experimental results in Example 10 are shown in graph form.</figref><figref num="11">The experimental results in Example 11 are shown in graph form.</figref>

0016A lithium ion battery, which is a type of storage battery in which lithium ions move from the negative electrode to the positive electrode during discharging and lithium ions move from the positive electrode to the negative electrode during charging, is disclosed in the present specification. Lithium-ion batteries disclosed herein have a non-aqueous electrolyte composition that provides an ionic conductive passage between the housing and the negative and positive electrodes that are located within the housing and are in conductive contact with each other. Includes objects and a porous separator between the negative and positive electrodes. The lithium-ion batteries disclosed herein can operate at high voltages using the positive electrodes of the invention (ie, up to about 5 V relative to the Li | Li + reference electrode), so this type of battery may optionally be. Sometimes referred to as a "high voltage" lithium-ion battery. This shows improved cycle performance at high temperatures compared to other conventional lithium-ion batteries.

0017The lithium ion battery described herein includes a positive electrode that is an electrode of an electrochemical cell that undergoes reduction during discharge. In galvanic cells such as batteries, the positive electrode is a more positively charged electrode. The positive electrode of the lithium ion battery of the present invention is a manganese positive electrode containing a lithium-containing manganese composite oxide having a spinel structure as a positive electrode active material. The lithium-containing manganese composite oxide in the positive electrode used in the present invention is of the formula. Li_zMn_1.5Ni_xM_yO_4-d (Equation IA) (In the formula, M is at least one metal selected from the group consisting of Al, Cr, Fe, Ga, Zn, Co, Nb, Mo, Ti, Zr, Mg, V, and Cu, 0.38 x &lt;0.5, 0 &lt;y 0.12, 0 d 0.3, 0.00 &lt;z 1.1, where z varies with the emission and uptake of lithium ions and electrons during charging and discharging) It is represented by.

0018In one embodiment, M in the above formula is Fe; in another embodiment, M in the above formula is Ga; in another embodiment, M in the above formula is Fe and Ga.

0019In various embodiments of the invention, the values of x and y are: x = 0.38 / y = 0.32, x = 0.39 / y = 0.1l1, x = 0.40 / y = 0.1, x = 0.41 / y. = 0.09, x = 0.42 / y = 0.08, x = 0.43 / y = 0.07, x = 0.44 / y = 0.06, x = 0.45 / y = 0.05, x = 0.46 / y = 0.04, x = 0.47 / y = 0.03 , X = 0.48 / y = 0.02, x = 0.49 / y = 0.01.

0020In one embodiment, z has a value represented by 0.03 z 1.1. In another embodiment, z has a value represented by 0.03 z 1.0.

0021In one embodiment, M in the above formula is at least one metal selected from the group consisting of Al, Cr, Fe, Ga, and Zn, 0.4 x &lt;0.5, and 0 &lt;y 0.1. , Z = 1, and d = 0.

0022The above-mentioned lithium positive electrode material is considered to be stabilized by the presence of the M component in the compound. As described in US Pat. No. 7,303,840, the manganese positive electrode stabilized by other systems may also contain a spinel-layered composite containing a manganese-containing spinel component and a lithium-rich layered structure. it can.

0023In another embodiment, the lithium-containing manganese composite oxide in the positive electrode used in the present invention is of the formula. Li_zNi_xM_yMn_2-xyO_4-d (Equation IB) (In the equation, z is 0.03 to 1.0; z varies with the emission and uptake of lithium ions and electrons during charging and discharging; x is 0.3 to 0.6; M is Cr, Fe, Co, Includes one or more of Li, Al, Ga, Nb, Mo, Ti, Zr, Mg, Zn, V, and Cu; y is 0.01-0.18 and d is 0-0.3) Contains oxides of. In one embodiment, in the above equation, x is 0.38 to 0.48, y is 0.03 to 0.12, and d is 0 to 0.1. In one embodiment, in the formal, M is one or more of Li, Cr, Fe, Co, and Ga.

0024The positive electrode active material described and used herein is prepared using methods such as the hydroxide precursor method described by Liu et al. (J. Phys. Chem. C13: 15073-15079, 2009). can do. In that method, KOH is added to precipitate the hydroxide precursor from a solution containing the desired amount of manganese, nickel, and acetate of other metals. As described in detail in the examples herein, the resulting precipitate is oven dried and then the desired amount of LiOH · H.₂Bake in oxygen at about 800 to about 950 ° C for 3 to 24 hours with 0. Alternatively, the positive electrode active material can be prepared using a solid phase reaction method or a sol-gel method as described in US Pat. No. 5,738,957 (Amine).

0025The positive electrode containing the positive electrode active material includes, for example, an effective amount of the positive electrode active material (for example, about 70% by weight to about 97% by weight), a polymer binder such as vinylidene polydifluoride, and N-methylpyrrolidone as a conductive carbon. It can be prepared by a method of mixing in a suitable solvent of the above to form a paste, then coating it on a current collector such as an aluminum foil and drying it to form a positive electrode.

0026The lithium-ion battery of the present invention further includes a negative electrode, which is an electrode of an electrochemical cell in which oxidation occurs during discharge. In galvanic cells such as batteries, the negative electrode is a more negatively charged electrode. The negative electrode contains a negative electrode active material, which may be any material capable of storing and releasing lithium ions. Examples of suitable negative electrode active materials are lithium alloys such as lithium-aluminum alloys, lithium-lead alloys, lithium-silicon alloys, lithium-tin alloys; carbon materials such as graphite and mesocarbon microbeads (MCMB); black phosphorus. , MnP₄, And CoP₃Phosphorus-containing materials such as; SnO₂, SnO, and TiO₂Metal oxides such as; as well as Li₄Ti₅O₁₂And LiTi₂O₄Lithium titanate, such as, but is not limited to these. In one embodiment, the negative electrode active material is lithium titanate or graphite.

0027The negative electrode can be made by a method similar to that described above for the positive electrode, for example, dissolved or dispersed in a binder organic solvent such as a vinyl fluoride copolymer or water, and then mixed with a conductive active material and pasted. To get. This paste is coated on a metal foil, preferably aluminum or copper foil, used as a current collector. Drying of the paste is preferably carried out using heat, thereby binding the active material to the current collector. Suitable negative electrode active materials and negative electrodes are commercially available from companies such as NEI Inc. (Somerset NJ) and Farasis Energy Inc. (Hayward CA).

0028The lithium-ion battery of the present invention further contains a non-aqueous electrolyte composition, which is a chemical composition suitable for use as an electrolyte in a lithium-ion battery. The electrolyte composition usually contains at least one non-aqueous solvent and at least one electrolyte salt. The electrolyte salt is an ionic salt that is at least partially soluble in the solvent of the non-aqueous electrolyte composition and at least partially dissolved in the solvent of the non-aqueous electrolyte composition to become an ion and a conductive electrolyte. Form the composition. The conductive electrolyte composition causes the positive and negative electrodes to make ionic conductive contact with each other, thereby liberating ions, especially lithium ions, and moving between the negative and the positive, thereby the electrolyte between the negative and the positive. Charges are conducted through the composition.

0029The solvent in the non-aqueous electrolyte composition of the lithium ion battery of the present invention can contain at least one fluorinated acyclic carboxylic acid ester and / or at least one fluorinated acyclic carbonate. The fluorinated acyclic carboxylic acid ester suitable for use as a solvent in the present invention has the following structural formula: R¹--- C (O) O --- R² (Equation IIA) (In the formula, R¹Is CH₃, CH₂CH₃, CH₂CH₂CH₃, CH (CH₃)₂, CF₃, CF₂H, CFH₂, CF₂R³, CFHR³, And CH₂R^fSelected from the group consisting of R²Independently, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH (CH₃)₂, And CH₂R^fSelected from the group consisting of R³May be replaced with at least one fluorine C₁~ C₃Alkyl group, R^fIs a C substituted with at least one fluorine₁~ C₃Alkyl group and R¹Or R²At least one of contains at least one fluorine, R¹Is CF₂If H, then R²Is CH₃is not it) Can be represented by.

0030In some embodiments, R¹Is CH₃, CH₂CH₃, CH₂CH₂CH₃, CH (CH₃)₂, CF₃, CFHR³, And CH₂R^fSelected from the group consisting of R²CH independently₃, CH₂CH₃, CH₂CH₂CH₃, CH (CH₃)₂, And CH₂R^fSelected from the group consisting of R³May be replaced with at least one fluorine C₁~ C₃Alkyl group, R^fIs a C substituted with at least one fluorine₁~ C₃Alkyl group and R¹Or R²At least one of them contains at least one fluorine.

0031In some embodiments, R¹Is CH₃, CH₂CH₃, CH₂CH₂CH₃, CH (CH₃)₂, And CH₂R^fSelected from the group consisting of R²Independently, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH (CH₃)₂, CH₂R^fSelected from the group consisting of R^fIs a C substituted with at least one fluorine₁~ C₃Alkyl group and R¹Or R²At least one of them contains at least one fluorine.

0032In yet another embodiment, the fluorine-containing carboxylic acid ester suitable for use in the present invention has the formula: R⁸--C (O) O--R⁹ (Equation IIB) (In the formula, R⁸And R⁹Represents an alkyl group independently, R⁸And R⁹The total number of carbon atoms in is 2-7, R⁸And / or R⁹It has been replaced with at least two hydrogen fluorines in R⁸And R⁹Are all FCH₂Does not contain groups and FCH groups) Can be represented by.

0033In certain embodiments, the fluorinated acyclic carboxylic acid ester is: CH₃C (O) OCH₂CF₂H (2,2,-difluoroethyl acetate, CAS No.1550-44-3), CH₃C (O) OCH₂CF₃(2,2,2-trifluoroethyl acetate, CAS No.406-95-1), and CH₃C (O) OCH₂CF₂CF₂H (2,2,3,3-tetrafluoropropyl acetate, CAS No.681-58-3) Selected from one or more members of the group consisting of.

0034In one particular embodiment, the fluorinated acyclic carboxylic acid ester solvent is CH₃C (O) OCH₂CF₂H.

0035The fluorinated acyclic carbonate suitable for use as a solvent in the present invention has the following structural formula: R⁴--- OC (O) O --- R⁵ (Equation III) (In the formula, R⁴And R⁵Independently, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH (CH₃)₂, And CH₂R^fSelected from the group consisting of R^fIs C₁~ C₃Alkyl group and R⁴Or R⁵At least one of them contains at least one fluorine) Can be represented by.

0036In certain embodiments, the fluorinated acyclic carbonate solvent is: CH₃OC (O) OCH₂CF₂H (Methyl 2,2-Difluoroethyl Carbonate, CAS No.916678-13-2), CH₃OC (O) OCH₂CF₃(Methyl 2,2,2-trifluoroethyl carbonate, CAS No. 156783-95-8), and CH₃OC (O) OCH₂CF₂CF₂H (Methyl 2,2,3,3-Tetrafluoropropyl carbonate, CAS No.156783-98-1) Selected from one or more members of the group consisting of.

0037In one particular embodiment, the fluorinated acyclic carbonate solvent is CH₃OC (O) OCH₂CF₃Is.

0038Mixtures of two or more of these fluorinated acyclic carboxylic acid esters and / or fluorinated acyclic carbonate solvents can also be used.

0039Fluorinated acyclic carboxylic acid esters and fluorinated acyclic carbonates suitable for use in the present invention can be prepared using well-known methods. For example, acetyl chloride can be reacted with 2,2-difluoroethanol (with or without a basic catalyst) to form 2,2-difluoroethyl acetate. In addition, 2,2-difluoroethyl acetate and 2,2-difluoroethyl propionate can be prepared using the methods described by Wiesenhofer et al. (Pamphlet 2009/040367 A1, Example 5). .. Similarly, methyl chloroformate can be reacted with 2,2-difluoroethanol to form methyl 2,2-difluoroethyl carbonate. Alternatively, some of these fluorinated solvents are Matrix Scientific (Columbia). It can be purchased from companies such as SC). For best results, it is desirable to purify the fluorinated acyclic carboxylic acid ester and the fluorinated acyclic carbonate to a purity level of at least about 99.9%, especially at least about 99.99%. These fluorinated solvents can be purified using a distillation method such as vacuum distillation or rotary band distillation.

0040The non-aqueous electrolyte composition in the lithium ion battery of the present invention is a solvent containing at least one fluorinated acyclic carboxylic acid ester and / or fluorinated acyclic carbonate and at least one co-solvent. It can also contain a mixture. Examples of suitable co-solvents include, but are not limited to, ethylene carbonate, propylene carbonate, fluoroethylene carbonate, tetramethylene sulfone, and ethyl methyl sulfone. For best results, it is desirable to use battery grade co-solvents or to have a purity level of at least about 99.9%, especially at least about 99.99%. In one embodiment, the co-solvent is ethylene carbonate. In another embodiment, the fluorinated acyclic carboxylic acid ester is CH₃CO₂CH₂CF₂It is H and the co-solvent is ethylene carbonate or fluorinated ethylene carbonate.

0041The above-mentioned fluorinated acyclic carboxylic acid ester and / or fluorinated acyclic carbonate, and co-solvent depend on the properties desired for the electrolyte composition in order to form the solvent mixture used in the electrolyte composition. And can be mixed in various ratios. In one embodiment, the fluorinated acyclic carboxylic acid ester and / or the fluorinated acyclic carbonate comprises from about 40% to about 90% by weight of the solvent mixture. In another embodiment, the fluorinated acyclic carboxylic acid ester and / or the fluorinated acyclic carbonate comprises from about 50% to about 80% by weight of the solvent mixture. In another embodiment, the fluorinated acyclic carboxylic acid ester and / or the fluorinated acyclic carbonate comprises from about 60% to about 80% by weight of the solvent mixture. In another embodiment, the fluorinated acyclic carboxylic acid ester and / or the fluorinated acyclic carbonate comprises from about 65% to about 75% by weight of the solvent mixture. In another embodiment, the fluorinated acyclic carboxylic acid ester and / or the fluorinated acyclic carbonate constitutes about 70% by weight of the solvent mixture.

0042In another embodiment, the non-aqueous electrolyte composition is a fluorinated acyclic carboxylic acid ester CH.₃CO₂CH₂CF₂Contains a solvent mixture containing H and ethylene carbonate, CH₃CO₂CH₂CF₂H constitutes from about 50% to about 80% by weight of the solvent mixture. In another embodiment, the non-aqueous electrolyte composition is a fluorinated acyclic carboxylic acid ester CH.₃CO₂CH₂CF₂Contains a solvent mixture of H and ethylene carbonate, CH₃CO₂CH₂CF₂H constitutes from about 65% to about 75% by weight of the solvent mixture.

0043The non-aqueous electrolyte composition in the lithium ion battery of the present invention also contains at least one electrolyte salt. Suitable electrolyte salts include Lithium hexafluorophosphate, LiPF₃(CF₂CF₃)₃, Bis (trifluoromethanesulfonyl) imide lithium, Bis (perfluoroethanesulfonyl) imidelithium, (Fluorosulfonyl) (Nonafluorobutanesulfonyl) Imid Lithium, Bis (fluorosulfonyl) imide lithium, Lithium tetrafluoroborate, Lithium perchlorate, Lithium hexafluoroarsenate, Lithium trifluoromethanesulfonate, Tris (trifluoromethanesulfonyl) methidolithium, Lithium bis (oxalate) oxalate, Lithium difluoro (oxalate) oxalate, Li₂B₁₂F_12-xH_x(In the formula, x is 0-8), and Lithium fluoride and B (OC₆F₅)₃Mixtures with anionic receptors such as However, the present invention is not limited to these.

0044Mixtures of two or more of these or equivalent electrolyte salts can also be used. In one embodiment, the electrolyte salt is lithium hexafluorophosphate. The electrolyte salt can be present in the non-aqueous electrolyte composition in an amount of about 0.2 to about 2.0 M, particularly about 0.3 to about 1.5 M, especially about 0.5 to about 1.2 M.

0045The non-aqueous electrolyte composition in the lithium ion battery of the present invention can also contain at least one additive that is believed to contribute to the formation of a thin film on one or both electrodes. Suitable such additives include Fluoroethylene carbonate (sometimes referred to herein as 4-fluoro-1,3-dioxolane-2-one, CAS No. 114435-02-8) and its halogenation, C.₁~ C₃, And halogenated C₁~ C₃Derivative, Ethylene sulfate, and its halogenated, C₁~ C₃, And halogenated C₁~ C₃Derivative, Vinyl ethylene carbonate, and its halogenation, C₁~ C₃, And halogenated C₁~ C₃Derivative, Vinylene carbonate, and its halogenated, C₁~ C₃, And halogenated C₁~ C₃Derivative, Maleic anhydride, and its halogenated, C₁~ C₃, And halogenated C₁~ C₃Derivatives, as well Vinyl acetate However, the present invention is not limited to these.

0046In one embodiment, the preferred additive is fluoroethylene carbonate.

0047These additives are generally commercially available; for example, fluoroethylene carbonate is available from companies such as China LangChem INC. (Shanghai, China) and MTI Corp. (Richmond, CA). It is desirable to purify these additives to a purity level of at least about 99.0%, especially at least about 99.9%. Purification can be carried out using a well-known method as described above. When using this type of additive, the amount is generally about 0.01% to about 5% by weight, especially about 0.1% to about 2% by weight, especially about 0.5% to about 1.5% by weight of the total electrolyte composition. Exists in.

0048The lithium ion battery of the present invention also has a porous separator between the negative electrode and the positive electrode. The porous separator functions to prevent a short circuit between the negative electrode and the positive electrode. Porous separators usually consist of single or multiple sheets of microporous polymers such as polyethylene, polypropylene, polyamide, or polyimide, or a combination thereof. The pore size of the porous separator is large enough to allow ion transport and provide ionic conductive contact between the negative and positive electrodes, but direct contact between the negative and positive electrodes, or particle permeation, Alternatively, it is small enough to prevent dendrites that can form on the negative and positive electrodes. An example of a porous separator suitable for use in the present invention is U.S. Patent Application No. 12 / 963,927 published as U.S. Patent Application Publication No. 2012/0149852 A1 (filed December 9, 2010). Disclosed in its entirety and incorporated by reference in its entirety as part of this specification for all purposes.

0049The housing of the lithium-ion battery of the present invention may be any suitable container that houses the above-mentioned components of the lithium-ion battery. Such containers can be manufactured in the form of small or large cylinders, prismatic cases, or pouches.

0050The lithium-ion batteries of the present invention are used for grid storage or various electronic means such as transportation means (self-propelled vehicles, automobiles, trucks, buses, or airplanes), computers, communication devices, cameras, radios, or conductive tools. It can be used as a power source for output or auxiliary equipment.

<p num="0051"> The behavior and effects of certain embodiments of the invention herein will become more apparent from the series of examples described below. The embodiments on which these examples are based are merely representative, and the selection of these embodiments for describing the present invention herein is a material, component not described in the examples. , Reactants, conditions, techniques, configurations, and designs do not indicate that they are not suitable for use in the present invention, and the subject matter not described in the examples is the appended claims and their equivalents. It does not indicate that it is excluded from. By comparing the results obtained from the examples with the results obtained from a particular test designed to serve as a controlled experiment and to provide a basis for comparison as different types of solvents are used. The importance of the examples can be better understood.</p><p num="0052"> The meanings of the abbreviations used in the examples are as follows: "g" means gram, "mg" means milligram, "μg" means microgram, "L" means liter , "ML" means milliliter, "mol" means mol, "mmol" means mmol, "M" means molar concentration, "% by weight" means weight percent However, "Hz" means hertz, "mS" means milliliters, "mA" means milliliters, "mAh / g" means milliliters / gram, and "V" means volt. Meaning, "xC" means a constant current capable of fully charging / discharging the positive electrode in 1 / x hours, "SOC" means the charged state, and "SEI" is formed on the surface of the electrode material. "KPa" means kilopascals, "rpm" means rotations / minute, and "psi" means pounds / square inch.</p><p num="0053">LiMn_1.5Ni_0.42Fe_0.08O₄Preparation of positive electrode active material Iron-doped LiMn by the hydroxide precursor method described by Liu et al. (J. Phys. Chem. C 113, 15073-15079, 2009)._1.5Ni_0.5O₄Was synthesized. With this method, 7.352 g of Mn (CH)₃COO)₂ 4H₂O, 2.090g Ni (CH₃COO)₂ 4H₂O, and 0.278 g of Fe (CH)₃COO)₂The hydroxide precursor was precipitated from this solution by dropping 200 mL of a 3.0 M KOH solution into a 100 mL solution containing. The resulting precipitate was collected by filtration, washed thoroughly with deionized water and then dried in the oven to give 3.591 g of transition metal hydroxide.</p><p num="0054"> 0.804g of LiOH · H containing the transition metal hydroxide₂O was mixed with O at a heating / cooling rate of 1 ° C / min at 900 ° C in air for 12 hours. Obtained LiMn_1.5Ni_0.42Fe_0.08O₄Is free of impurities as measured by X-ray powder diffraction._1.5Ni_0.5O₄Showed the same cubic spinel structure as.</p><p num="0055">LiMn_1.5Ni_0.42Fe_0.08O₄Fabrication of positive electrode LiMn produced as described above_1.5Ni_0.42Fe_0.08O₄(2.08g) Positive electrode active material, 0.26g Denka black (acetylene black, obtained from DENKA Corp., Japan), 2.16g polydifluoroethylene (PVDF) solution (12% by weight in N-methylpyrrolidone (NMP)) , Kureha America Inc., New York, NY, KFL # 1120), and an additional 2.93 g of NMP mixed first using a planetary centrifuge mixer (Shinky ARE-310, Shinky, Japan) at 2,000 rpm. Then, it was mixed using a shearing mixer (IKA (registered trademark) Works, Wilmington, NC) to form a uniform slurry. The slurry was coated on aluminum foil using a doctor blade gate and dried in a convection oven at 100 ° C. for 10-15 minutes. The resulting electrodes were calendared at ambient temperature between steel rolls with a diameter of 102 mm with a nip force of 370 kg. The electrodes were further dried in a vacuum oven at 90 ° C. at -25 inch Hg (-85 kPa) for 6 hours.</p><p num="0056">Preparation of non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate 2,2-Difluoroethyl acetate obtained from Matrix Scientific (Columbia, SC) is purified twice by rotary band distillation to a purity of 99.99% as measured by gas chromatography using a flame ionization detector. did. Purified 2,2-difluoroethyl acetate (7.32 g) and 3.10 g of ethylene carbonate (99% anhydrous, Sigma-Aldrich, Milwaukee, WI) were mixed with each other. To 9.0 mL of the resulting solution, 1.35 g of lithium hexafluorophosphate (99.99% battery grade, Sigma-Aldrich) was added and the mixture was shaken for a few minutes until all the solids were dissolved.</p><p num="0057">Preparation of non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate and fluoroethylene carbonate additive 4-Fluoro-1,3-dioxolan-2-one obtained from China LangChem INC (Shanghai, China) was purified by vacuum distillation. Purified 4-fluoro-1,3-dioxolane-2-one (0.053 g) was added to 5.30 g of the above non-aqueous electrolyte composition and the mixture was shaken for a few minutes.</p><p num="0058">Methyl 2,2,2-trifluoroethyl carbonate (CH)₃OC (O) OCH₂CF₃) Synthesis In a dry box, chloroformate (232.0 g, Sigma-Aldrich), 2,2,2-trifluoroethanol (202.0 g, Sigma-Aldrich) and pyridine (194.0 g, anhydrous, anhydrous, at 0-15 ° C. Sigma-Aldrich) and dichloromethane (1.5L, anhydrous, EMD) Added to solution with Chemicals, Gibbstown, NJ. The mixture was stirred at room temperature for the weekend. Taking a sample for NMR analysis showed that the conversion of 2,2,2-trifluoroethanol was 100%. The mixture was filtered. The recovered solid was washed with dichloromethane and the combined organic liquid filtrate was washed 5 times with 50 mL of 5% HCl. Pyridine was detected when a sample for NMR analysis was taken. No pyridine was then detected by NMR after washing the organic liquid filtrate with 25 mL of 5% HCl four more times. The organic liquid filtrate was washed with brine (50 mL). Dichloromethane was removed from the organic liquid filtrate by rotary evaporation. The resulting crude product (273 g) was dried on a molecular sieve and then purified twice by rotary band distillation column distillation. A pure material (101.6 g) was obtained, which was used in the electrolyte composition.</p><p num="0059">Preparation of non-aqueous electrolyte compositions containing methyl 2,2,2-trifluoroethyl carbonate, ethylene carbonate, and fluoroethylene carbonate additives Methyl 2,2,2-trifluoroethyl carbonate (10.0 g) was dried on 4A molecular sieves (1.0 g) for the weekend and then further dried overnight on 4A molecular sieves (1.0 g). The dried methyl 2,2,2-trifluoroethyl carbonate was then filtered through a PTFE (polytetrafluroethylene) filter plate using a syringe. The dried and filtered methyl 2,2,2-trifluoroethyl carbonate (2.80 g) was mixed with ethylene carbonate (Novolyte, 1.20 g) and the resulting solvent mixture was shaken until all solids were dissolved. .. LiPF in 2 mL GC vial (oven dried)₆(0.076 g, Novolyte, Cleveland OH) was added, followed by 1.0 mL of the above solvent mixture. The net weight of the resulting mixture was 1.36 g. The mixture was shaken until all solids were dissolved. To the above mixture was added 4-fluoro-1,3-dioxolane-2-one (14 mg, LongChem, Shanghai, China, purified by vacuum distillation). The obtained non-aqueous electrolyte composition was shaken and stored in a dry box.</p><p num="0060">Preparation of Non-Aqueous Electrolyte Compositions Containing 2,2,2-Trifluoroethyl Acetate, Ethylene Carbonate, and Fluoroethylene Carbonate Additives 2,2,2-Trifluoroethyl acetate (CH) obtained from SynQuest Laboratories (Alachua FL)₃C (O) OCH₂CF₃) Was purified twice by rotary band distillation column distillation, and purified to a purity of 99.9% as measured by gas chromatography using a flame ionization detector. The purified 2,2,2-trifluoroethyl acetate (10.0 g) was dried over a weekend on a 4A molecular sieve (1.0 g) and further dried overnight on a 4A molecular sieve (1.0 g). The purified and dried 2,2,2-trifluoroethyl acetate was then filtered through a PTFE filter plate using a syringe. The filtered material (2.80 g) was mixed with ethylene carbonate (Novolyte, 1.20 g) and the resulting solvent mixture was shaken until all solids were dissolved. LiPF in 2 mL GC vial (oven dried)₆(0.076 g, Novolyte, Cleveland OH) was added, followed by 1.0 mL of the above solvent mixture. The net weight of the resulting mixture was 1.38 g. The mixture was shaken until all solids were dissolved. To this mixture was added 4-fluoro-1,3-dioxolane-2-one (14 mg, LongChem, Shanghai, China, purified by vacuum distillation). The obtained non-aqueous electrolyte composition was shaken and stored in a dry box.</p><p num="0061">Methyl 2,2-difluoroethyl carbonate (CH)₃OC (O) OCH₂CF₂Synthesis of H) Purified by 2,2-difluoroethanol (113.9.0 g, Matrix Scientific, Columbia SC, rotary band distillation column distillation) in an oven-dried 2 L 3-neck flask fitted with an overhead stirrer and cooled in a water bath under nitrogen protection. Fluoroformate (136.1 g, Sigma-Aldrich) in a solution of pyridine (113.9 g, anhydrous, Sigma-Aldrich) and dichloromethane (0.80 L, anhydrous, EMD Chemicals, Gibbstown NJ) with a syringe pump. Add slowly over 3 hours. The resulting mixture was stirred at room temperature overnight. When a sample for NMR analysis was taken, it was found that 2,2-difluoroethanol was not detected. The mixture was filtered and the filtrate was washed with 100 mL of 10% HCl followed by two more washes with 50 mL of 10% HCl. Taking a sample for NMR analysis revealed that pyridine was not detected. Then add 50 mL of 5% Na to the filtrate.₂CO₃The solution was then washed with 100 mL of brine. The organic layer is anhydrous DDL₄It was dried on (50 g) for 2 hours and then on a molecular sieve (4A, 50 g) overnight. Dichloromethane was removed by rotary evaporation of the dried solution. The obtained crude product (208 g) was purified by rotary band distillation column distillation. A pure product (101.7 g) was obtained and used in the electrolyte composition.</p><p num="0062">Preparation of non-aqueous electrolyte compositions containing methyl 2,2-difluoroethyl carbonate, ethylene carbonate, and fluoroethylene carbonate additives Methyl 2,2-difluoroethyl carbonate (10.0 g) was dried overnight on a 4A molecular sieve (1.0 g) and then further dried overnight on a 4A molecular sieve (1.0 g). Dry methyl 2,2-difluoroethyl carbonate was then filtered through a PTFE filter plate using a syringe. The filtered material (2.80 g) was mixed with ethylene carbonate (Novolyte, 1.20 g) and the resulting solvent mixture was shaken until all solids were dissolved. LiPF in 2 mL GC vial (oven dried)₆(0.228 g, Novolyte) was added, followed by 1.5 mL of the above solvent mixture. The net weight of the resulting mixture was 2.19 g. The mixture was shaken until all solids were dissolved. To 1.0 g of this mixture was added 4-fluoro-1,3-dioxolane-2-one (10 mg, LongChem, Shanghai, China, purified by vacuum distillation). The obtained non-aqueous electrolyte composition was shaken and stored in a dry box.</p><p num="0063">Preparation of non-aqueous electrolyte composition containing methyl 2,2-difluoroacetate, ethylene carbonate, and fluoroethylene carbonate additives Methyl 2,2-difluoroacetate (HCF) obtained from SynQuest₂C (O) OCH₃) Was purified twice by rotary band distillation column distillation, and purified to a purity of 99.9% as measured by gas chromatography using a flame ionization detector. Purified methyl 2,2-difluoroacetate (10.0 g) was dried overnight on a 4A molecular sieve (1.0 g) and then further dried overnight on a 4A molecular sieve (1.0 g). The purified and dried methyl 2,2-difluoroacetate was then filtered through a PTFE filter plate using a syringe. The filtered material (2.80 g) was mixed with ethylene carbonate (Novolyte, 1.20 g) and the resulting solvent mixture was shaken until all solids were dissolved. LiPF in 2 mL GC vial (oven dried)₆(0.228 g, Novolyte) was added, followed by 1.5 mL of the above solvent mixture. The net weight of the resulting mixture was 2.15 g. The mixture was shaken until all solids were dissolved. To 1.0 g of the mixture was added 4-fluoro-1,3-dioxolane-2-one (10 mg, LongChem, Shanghai, China, purified by vacuum distillation). The obtained non-aqueous electrolyte composition was shaken and stored in a dry box.</p><p num="0064">Acetic acid 2,2,3,3-tetrafluoropropyl (CH)₃C (O) OCH₂CF₂CF₂Synthesis of H) Acetyl chloride (132.0 g, 97%, SynQuest) in an oven-dried 0.5 L round-bottomed flask equipped with magnetic agitation and cooled in an ice-water bath under nitrogen protection. 94.2 g (Sigma-Aldrich) was added slowly with a syringe pump over 3 hours. A 10% NaOH solution trap was connected to the flask through a tube to capture the generated HCl gas (a funnel was used to prevent the NaOH solution from returning to the system by suction). The mixture was stirred at room temperature overnight. When a sample for NMR analysis was taken, 2,2,3,3-tetrafluoropropanol was detected. Acetyl chloride (0.6 g) was added to the mixture and the mixture was stirred at room temperature for 2 hours. NMR analysis showed the absence of 2,2,3,3-tetrafluoropropanol. 25 mL of the mixture 10% Na₂CO₃Washed 5 times with, then with 25 mL of water, followed by 25 mL of brine. The resulting mixture is anhydrous DDL₄It was dried overnight on (20 g) and then twice on a 5 g 4A molecular sieve. The obtained crude product was purified by rotary band distillation column distillation. A pure material (82.7 g) was obtained and used in the electrolyte composition.</p><p num="0065">Preparation of non-aqueous electrolyte composition containing 2,2,3,3-tetrafluoropropyl acetic acid, and ethylene carbonate 2,2,3,3-tetrafluoropropyl acetate (10.0 g) was dried overnight on a 4 A molecular sieve (1.0 g) and then filtered through a PTFE filter plate using a syringe. The dried and filtered material (2.80 g) was mixed with ethylene carbonate (Novolyte, 1.20 g) and the resulting solvent mixture was shaken until all solids were dissolved. LiPF in 2 mL GC vial (oven dried)₆(0.076 g, Novolyte, Cleveland OH) was added, followed by 1.0 mL of the above solvent mixture. The net weight of the resulting mixture was 1.42 g. The mixture was shaken until all solids were dissolved. The obtained non-aqueous electrolyte composition was filtered through a PTFE filter plate using a syringe and stored in a dry box.</p><p num="0066">Methyl 2,2,3,3-tetrafluoropropyl carbonate (CH)₃OC (O) OCH₂CF₂CF₂Synthesis of H) 2,2,3,3-tetrafluoropropanol (132.0 g, 97%, SynQuest) and pyridine (132.0 g, 97%, SynQuest) in an oven-dried 2 L 3-neck flask equipped with an overhead stirrer and cooled in a water bath under nitrogen protection. Chloroformate (113.4 g, Sigma-Aldrich) was slowly added to a solution of 94.9 g, anhydrous, Sigma-Aldrich) and dichloromethane (0.80 L, anhydrous, EMD Chemicals) over 3 hours with a syringe pump. The resulting mixture was stirred at room temperature overnight. When a sample for NMR analysis was taken, it was found that 2,2,3,3-tetrafluoropropanol was not detected. The mixture was filtered and the resulting filtrate was washed with 100 mL of 10% HCl followed by 50 mL of 10% HCl twice. NMR analysis revealed that pyridine was detected. The mixture was washed with 50 mL of 10% HCl and NMR analysis revealed that no pyridine was detected. 50 mL of the mixture 5% Na₂CO₃Washed with 100 mL brine. The organic layer is anhydrous DDL₄It was dried on (50 g) for 2 hours and then on a molecular sieve (4A, 50 g) overnight. The dried organic layer was rotationally evaporated to remove dichloromethane. The obtained crude product was purified by rotary band distillation column distillation. A pure material (96.0 g) was obtained and used in the electrolyte composition.</p><p num="0067">Preparation of non-aqueous electrolyte composition containing methyl 2,2,3,3-tetrafluoropropyl carbonate, and ethylene carbonate Methyl 2,2,3,3-tetrafluoropropyl carbonate (10.0 g) was dried overnight on a 4A molecular sieve (1.0 g). The dried methyl 2,2,3,3-tetrafluoropropyl carbonate was then filtered through a PTFE filter plate using a syringe. The dried and filtered material (2.80 g) was mixed with ethylene carbonate (Novolyte, 1.20 g) and the resulting solvent mixture was shaken until all solids were dissolved. LiPF in 2 mL GC vial (oven dried)₆(0.076 g, Novolyte, Cleveland OH) was added, followed by 1.0 mL of the above solvent mixture. The net weight of the resulting mixture was 1.43 g. The mixture was shaken until all solids were dissolved. The obtained non-aqueous electrolyte composition was filtered through a PTFE filter plate using a syringe and stored in a dry box.</p><p num="0068">LiMn_1.5Ni_0.42Fe_0.08O₄/ Li Semi-battery manufacturing LiMn prepared as described above_1.5Ni_0.42Fe_0.08O₄A positive electrode, a Celgard® separator 2325 (Celgard, LLC.Charlotte, NC), a lithium foil negative electrode (0.75 mm thick), and a few drops of the non-aqueous electrolyte composition of interest in a 2032 stainless steel coin cell can ( LiMn sandwiched between Hosen Co., Ltd., Japan)_1.5Ni_0.42Fe_0.08O₄Formed a / Li half-cell.</p><p num="0069">LiMn_1.5Ni_0.42Fe_0.08O₄/ Li₄Ti₅O₁₂Full cell manufacturing LiMn prepared as described above_1.5Ni_0.42Fe_0.08O₄Positive electrode, Celgard® separator 2325 (Celgard, LLC.Charlotte, NC), Li₄Ti₅O₁₂LiMn with the negative electrode (Farasis Energy Inc., Hayward, California) and a few drops of the target non-aqueous electrolyte composition sandwiched in a 2032 stainless steel coin-type battery can._1.5Ni_0.42Fe_0.08O₄/ Li₄Ti₅O₁₂A full cell was formed.</p><p num="0070">Example 1 LiMn having a non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate_1.5Ni_0.42Fe_0.08O₄Room temperature cycle performance of / Li half-cell Using the non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate prepared as described above, LiMn as described above._1.5Ni_0.42Fe_0.08O₄A / Li half-cell was made. This LiMn_1.5Ni_0.42Fe_0.08O₄The / Li half-cell cycle was performed between 3.5 and 4.95 V at a rate of 0.2 C at 25 ° C. The cycle performance data is shown in Fig. 1. As can be seen from the figure, LiMn shakes the non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate._1.5Ni_0.42Fe_0.08O₄The / Li half-cell had a capacity retention of 96% at 100 cycles at room temperature.</p><p num="0071">Example 2 LiMn with a non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate and fluoroethylene carbonate_1.5Ni_0.42Fe_0.08O₄Room temperature cycle performance of / Li half-cell Using a non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate and a fluoroethylene carbonate additive prepared as described above, LiMn as described above._1.5Ni_0.42Fe_0.08O₄A / Li half-cell was made. This LiMn_1.5Ni_0.42Fe_0.08O₄The / Li half-cell cycle was performed between 3.5 and 4.95 V at a rate of 0.2 C at 25 ° C.</p><p num="0072"> The cycle performance data is shown in Fig. 2. As can be seen from the figure, LiMn having a non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate and a fluoroethylene carbonate additive._1.5Ni_0.42Fe_0.08O₄The / Li half-cell had a capacity retention of 98% at 80 cycles at room temperature.</p><p num="0073">Example 3 (Comparison example) LiMn with standard EC / EMC electrolyte_1.5Ni_0.42Fe_0.08O₄Room temperature cycle performance of / Li half-cell 1M LiPF containing ethyl carbonate (EC) / ethyl methyl carbonate (EMC) in a volume ratio of 30:70₆Using a standard electrolyte containing (Novolyte, Cleveland, OH), LiMn as described above_1.5Ni_0.42Fe_0.08O₄A / Li half-cell was made. This half-cell cycle was performed at a rate of 0.2 C between 3.5 and 4.95 V at 25 ° C.</p><p num="0074"> The cycle performance data is shown in Fig. 3. As you can see, LiMn with standard EC / EMC electrolyte_1.5Ni_0.42Fe_0.08O₄The / Li half-cell had a capacity retention of 98% at 100 cycles at room temperature.</p><p num="0075">Example 4 LiMn having a non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate_1.5Ni_0.42Fe_0.08O₄/ Li high temperature cycle performance of half cell Using a non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate, LiMn as described above._1.5Ni_0.42Fe_0.08O₄A / Li half-cell was made. This LiMn_1.5Ni_0.42Fe_0.08O₄The / Li half-cell cycle was performed between 3.5 and 4.95 V at a rate of 0.5 C at 55 ° C.</p><p num="0076"> The cycle performance data is shown in Fig. 4. As can be seen from the figure, LiMn having a non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate_1.5Ni_0.42Fe_0.08O₄The / Li half-cell had a capacity retention of 97% at 100 cycles at 55 ° C.</p><p num="0077">Example 5 LiMn with a non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate and fluoroethylene carbonate_1.5Ni_0.42Fe_0.08O₄/ Li high temperature cycle performance of half cell Using a non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate and a fluoroethylene carbonate additive, LiMn as described above._1.5Ni_0.42Fe_0.08O₄/ L An i-half-cell was manufactured. This LiMn_1.5Ni_0.42Fe_0.08O₄The / Li half-cell cycle was performed between 3.5 and 4.95 V at a rate of 0.5 C at 55 ° C.</p><p num="0078"> The cycle performance data is shown in Fig. 5. As can be seen from the figure, LiMn having a non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate and a fluoroethylene carbonate additive._1.5Ni_0.42Fe_0.08O₄The / Li half-cell had a capacity retention of 99% at 100 cycles at 55 ° C.</p><p num="0079">Example 6 (Comparison example) LiMn with standard EC / EMC electrolyte_1.5Ni_0.42Fe_0.08O₄/ Li high temperature cycle performance of half cell Using standard EC / EMC electrolytes, LiMn as described above_1.5Ni_0.42Fe_0.08O₄A / Li half-cell was made. This LiMn_1.5Ni_0.42Fe_0.08O₄The / Li half-cell cycle was performed between 3.5 and 4.95 V at a rate of 0.5 C at 55 ° C.</p><p num="0080"> The cycle performance data is shown in Fig. 6. As you can see, LiMn with standard EC / EMC electrolyte_1.5Ni_0.42Fe_0.08O₄The / Li halfcell had a capacity retention of only 39% at 100 cycles at 55 ° C.</p><p num="0081">Example 7 LiMn with various electrolytes_1.5Ni_0.42Fe_0.08O₄/ Li Semi-cell Electrochemical Impedance Spectroscopy LiMn with various electrolytes (see Table 1)_1.5Ni_0.42Fe_0.08O₄Electrochemical impedance spectroscopy (EIS) studies of the / Li halfcell were performed at 100% SOC (ie fully charged) after 100 cycles at 55 ° C. Frequency is 10⁵Hz ~ 10^-3It was in the Hz range. The magnitude of the AC voltage was 10 mV.</p><p num="0082"> The obtained EIS spectra are shown in FIGS. 7a (half-cell of Example 1), 7b (half-cell of Example 2), and 7c (half-cell of Comparative Example 3), and the results are summarized in Table 1. .. As can be seen from the data in the table, the SEI resistance (Rs) and charge transfer resistance (Rct) are half-cells having a non-aqueous electrolyte composition containing 2,2-difluoroethyl acid (half-cell of Example 1). And a half-cell having a non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate and a fluoroethylene carbonate additive (half-cell of Example 2) is a half-cell having a standard EC / EMC electrolyte (Example 3 (Example 3). It was much smaller than the half-cell) of the comparative example). These results indicate that the non-aqueous electrolyte composition containing the fluorinated component suppresses the growth of SEI and the surface charge transfer rate at high temperature (55 ° C) is significantly improved.</p><p num="0083"><tables num="1"><img id="000002" he="68" wi="153" file="JP6178317B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0084">Example 8 LiMn with a non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate and fluoroethylene carbonate_1.5Ni_0.42Fe_0.08O₄/ Li₄Ti₅O₁₂Full cell high temperature cycle performance Using a non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate and a fluoroethylene carbonate additive, LiMn as described above._1.5Ni_0.42Fe_0.08O₄/ Li₄Ti₅O₁₂A full cell was prepared. This LiMn_1.5Ni_0.42Fe_0.08O₄/ Li₄Ti₅O₁₂A full cell cycle was performed at 55 ° C. at a rate of 0.5C between 1.95 and 3.4V.</p><p num="0085"> The cycle performance is shown in Fig. 8. As you can see from the figure, this LiMn_1.5Ni_0.42Fe_0.08O₄/ Li₄Ti₅O₁₂Full cells had a capacity retention of 94.8% at 100 cycles at 55 ° C.</p><p num="0086">Example 9 (Comparison example) LiMn with standard EC / EMC electrolyte_1.5Ni_0.5O₄/ Li₄Ti₅O₁₂Full cell high temperature cycle performance Using standard ethyl carbonate (EC) / ethyl methyl carbonate (EMC) electrolytes, LiMn as described above_1.5Ni_0.5O₄/ Li₄Ti₅O₁₂A full cell was prepared. This LiMn_1.5Ni_0.5O₄/ Li₄Ti₅O₁₂A full cell cycle was performed at 55 ° C. at a rate of 0.5C between 1.95 and 3.4V.</p><p num="0087"> The cycle performance is shown in Fig. 9. As you can see from the figure, LiMn with a standard electrolyte_1.5Ni_0.5O₄/ Li₄Ti₅O₁₂Full cells were measured to retain only 61.9% capacity at 100 cycles at 55 ° C.</p><p num="0088">Example 10 CH₃OCO₂CH₂CF₂LiMn with a non-aqueous electrolyte composition containing H: EC (70:30) and fluoroethylene carbonate_1.5Ni_0.42Fe_0.08O₄/ Li high temperature cycle performance of half cell CH₃OCO₂CH₂CF₂Using a non-aqueous electrolyte composition containing H: EC (70:30) and fluoroethylene carbonate additive (1%), LiMn as described above._1.5Ni_0.42Fe_0.08O₄A / Li half-cell was made. This LiMn_1.5Ni_0.42Fe_0.08O₄The / Li half-cell cycle was performed between 3.5 and 4.95 V at 60 mA / g at 55 ° C.</p><p num="0089"> The cycle performance data is shown in Fig. 10. The capacitance retention is as high as 98% at 100 cycles at 55 ° C, indicating that the combination of positive electrode / fluorinated electrolyte provides very good high temperature cycle performance.</p><p num="0090">Example 11 (Comparison example) CF₂HCO₂CH₃LiMn with a non-aqueous electrolyte composition containing: EC (70:30) and fluoroethylene carbonate_1.5Ni_0.42Fe_0.08O₄/ Li high temperature cycle performance of half cell CF₂HCO₂CH₃Using a non-aqueous electrolyte composition containing: EC (70:30) and fluoroethylene carbonate additive (1%), LiMn as described above._1.5Ni_0.42Fe_0.08O₄A / Li half-cell was made. This LiMn_1.5Ni_0.42Fe_0.08O₄The / Li half-cell cycle was performed between 3.5 and 4.95 V at 60 mA / g at 55 ° C.</p><p num="0091"> The cycle performance data is shown in Fig. 11. Capacity retention at 100 cycles at 55 ° C is only 23%, indicating that this positive / fluorinated electrolyte combination has very low high temperature cycle performance.</p><p num="0092">Examples 12-22 LiMn having a non-aqueous electrolyte composition containing various fluorinated solvents_1.5Ni_0.5O₄/ Li₄Ti₅O₁₂Full cell high temperature cycle performance The following fabrication description is typical of the fabrication used in subsequent examples.</p><p num="0093">LiMn_1.5Ni_0.42Fe_0.08O₄Preparation of positive electrode active material Iron-doped LiMn by the hydroxide precursor method described by Liu et al. (J. Phys. Chem. C 113, 15073-15079, 2009)._1.5Ni_0.5O₄Was synthesized. For this preparation, 401 g of manganese (II) acetate tetrahydrate (Sigma-Aldrich), 115 g of nickel (II) acetate tetrahydrate (Sigma-Aldrich), and 15.2 g of iron (II) acetate anhydrous. Things (Alfa Aesar, Ward Hill, MA) was weighed on a balance and then dissolved in 5 L of deionized water to prepare an acetate solution. KOH pellets were dissolved in 10 L of deionized water in a 30 L reactor to give a 3.0 M solution. The acetate solution was transferred to an addition funnel and quickly dropped into the stirring reactor to precipitate the mixed hydroxide material. After adding 5 L of all acetate solution to the reactor, stirring was continued for 1 hour. The stirring was then stopped and the hydroxide precipitate was allowed to settle overnight. After settling, the liquid was removed from the reactor and 15 L of fresh deionized water was added. The contents of the reactor were agitated and settled again to remove the liquid. This cleaning process was repeated. The precipitate was then transferred to two (evenly divided) coarse glass frit filtration funnels covered with Dacron® paper. The recovered solid was washed with deionized water until the pH of the filtrate reached 6.0 (pH of deionized wash water), and an additional 20 L of deionized water was added to each filtered cake. Finally, the cake was dried overnight in a vacuum oven at 120 ° C. The yield at this point was usually 80-90%.</p><p num="0094"> The filtered cake of this hydroxide precipitate was ground and mixed with lithium carbonate. This step was performed in batches of 60 g using a Fritsch Pulverisette automatic mortar and pestle (Fritsch USA, Goshen, NY). In each batch, the hydroxide precipitate was weighed and then ground alone in Pulveresette for 5 minutes. Then stoichiometry + a slight excess of lithium carbonate was added to the system. For 53 g of hydroxide, 11.2 g of lithium carbonate was added. Grinding was continued for a total of 60 minutes, stopping every 10-15 minutes and scraping the material from the surface of the mortar and pestle with a sharp metal spatula. If the material agglomerated due to moisture, it was sifted once on a 40 mesh screen during grinding and then ground again.</p><p num="0095"> The crushed material was fired in a shallow rectangular alumina tray in an air box furnace. The dimensions of the tray were 158 mm x 69 mm, each containing about 60 g of material. The firing procedure consisted of raising from room temperature to 900 ° C in 15 hours, maintaining at 900 ° C for 12 hours, and then cooling to room temperature in 15 hours.</p><p num="0096">LiMn_1.5Ni_0.42Fe_0.08O₄Fabrication of positive electrode LiMn prepared as described above_1.5Ni_0.42Fe_0.08O₄A positive electrode was made using a spinel positive electrode material. The binder was obtained as a 12% solution of polyvinylidene fluoride in NMP (KFL # 1120, Kureha America Corp, New York, NY). Carbon black (0.260 g, acetylene black, Denka Corp. New York, NY, uncompressed), 3.88 g of NMP, and PVDF solution (2.16 g) above are mixed in a 15 mL vial with a fluoropolymer cap and sinky ARE. Using a -310 centrifuge (Sinky Co., Ltd., Japan), mixing with the centrifuge was performed 3 times at 2,000 rpm for 1 minute each. The positive electrode material (2.08 g) was ground for about 1 hour using a mortar and pestle. Next, the positive electrode material and 0.70 g of NMP were added to the vial, and the mixture was mixed again with a centrifuge at 2,000 rpm for 1 minute three times to form a positive electrode paste. The total weight of the paste was 9.08 g (solid content 28.6%). Place the vial in an ice bath and rotor stator (Model PT 10-35) GT, 7.5mm diameter stator, Kinematicia, Bohemia NY) was used to perform two 15-minute homogenizations at 6500 rpm each, and then two more 15-minute homogenizations at 9500 rpm each. During each of the four homogenization times, the homogenizer was moved to another location in the paste vial. The paste was cast onto untreated aluminum foil using a doctor blade at a gate height of 0.25 mm and dried in a vacuum oven at 100 ° C. for 15 minutes. The resulting 50 mm wide positive electrode was placed on a 125 μm thick brass sheet and two 38 mm wide and 37 μm thick brass shim strips were placed on both sides of the positive electrode to adjust the gap thickness of the calendar. used. The positive electrode and shim were covered with a second brass sheet 125 μm thick and the assembly was passed through a calendar using a steel roll with a diameter of 100 mm, first at ambient temperature of 560 kg and then with a nip force of 680 kg. The average positive electrode thickness decreased from 67 μm before calendaring to 45 μm. Further positive electrodes were prepared in the same manner except that the gate height of the doctor blade was increased to 0.29 mm and the positive electrode was dried.</p><p num="0097">Fabrication of lithium titanate negative electrode Carbon black (0.39g, acetylene black, Denka Corp., New York NY, uncompressed), PVDF solution (3.00g, 13% in NMP, KFL # 9130, Kureha America Corp, New York NY), and 6.03g of NMP Was mixed, and each was mixed with a centrifuge at 2,000 rpm for 60 seconds three times. Li₄Ti₅O₁₂The powder (3.12 g, Nanomyte BE-10, NEI Corporation, Somerset, NJ) and an additional 1.10 g of NMP were added to the mixture of carbon black and PVDF above and the resulting paste was added at 2,000 rpm for 60 seconds each. Mixing with a centrifuge was performed 3 times. The vials were placed in an ice bath and homogenized twice at 6500 rpm for 15 minutes each using a rotor stator, followed by two homogenizations at 9500 rpm for 15 minutes each. The obtained paste was placed in a mortar and crushed by hand using a pestle to further remove agglomerates. The paste was then cast onto untreated aluminum foil 25 μm thick using a doctor blade with a gate height of 0.29 mm. The paste was dried in a convection oven (model FDL-115, Binder Inc., Great River, NY) at 100 ° C for 15 minutes. The thickness of the negative electrode was 71 μm. The obtained negative electrode having a width of 50 mm was calendar-processed by a method similar to that of the positive electrode described above. The average negative electrode thickness decreased from 71 μm before calendar processing to 53 μm after calendar processing.</p><p num="0098">LiMn_1.5Ni_0.42Fe_0.08O₄/ Li₄Ti₅O₁₂Full cell manufacturing A non-aqueous electrolyte lithium ion CR2032 coin cell was made for electrochemical evaluation. The circular negative and positive electrodes are punched out, placed in a heater in a subchamber in the glove box, dried under reduced pressure at 100 ° C. overnight, and placed in an argon glove box (with Vacuum Atmospheres, Hawthorne CA, HE-493 purifier). Moved. For the electrode diameter, a 14.1 mm positive electrode was used with a 16.0 mm negative electrode, or a 10.1 mm positive electrode was used with a 12.3 mm negative electrode. The positive electrode was restricted in all cells, and the Fe-LNMO weight ratio of lithium titanate weight exceeded 1.0 in all cells. Coin cell parts (case, spacer, corrugated spring, gasket, and lid) and coin cell crimper were obtained from Hosen Co., Ltd. (Osaka, Japan). The separator used was a microporous polyolefin separator (CG2325, Celgard, Charlotte, NC) with a thickness of 25 μm. The electrolytes used in each example are shown in Table 1.</p><p num="0099">LiMn_1.5Ni_0.42Fe_0.08O₄/ Li₄Ti₅O₁₂Full cell high temperature cycle LiMn_1.5Ni_0.42Fe_0.08O₄/ Li₄Ti₅O₁₂Full cells were cycled using commercially available battery testers (Series 4000, Maccor, Tulsa, OK) at 55 ° C. with voltage limits of 1.9 and 3.4 V. The first 29 cycles were performed using constant current charging and discharging at a rate of 60mA / (grams of Fe-LNMO). In the 30th cycle, the rate was reduced to 24mA / g. This set of 30 cycles (29 + 1) was repeated 10 times to make a total of 300 cycles. Table 1 shows the number of cycles until the discharge capacity drops to 80% of the initial discharge capacity of the first cycle. Table 2 also shows the average of the specific discharge capacities remaining in 297 to 299.</p><p num="0100"><tables num="2"><img id="000003" he="176" wi="153" file="JP6178317B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0101"> In various embodiments of the lithium ion battery of the present invention, the pair of dopant metal and fluorinated solvent is (i) selected from all groups of doping elements in all different and different combinations of all the individual components of all groups. Any one or more of all components of all groups of dopant metals disclosed herein, selected as one component or any subgroup of any size. Al, Cr, Fe, Ga, Zn, Co, Nb, Mo, Ti, Zr, Mg, V, and Cu) and (ii) fluorination in all various different combinations of individual components of all groups. Fluorinated solvents of Formula IIA, IIB, or Formula III disclosed herein, selected as described above as one component selected from all groups of solvents or any subgroup of any size. It can be formed from any one or more of all components of all groups of. Subgroups of components of the group of dopant metals or fluorinated solvents can be formed by excluding one or more components from each of the entire groups described above. As a result, the dopant metal or fluorination solvent (or combination thereof) can be formed from the entire group from all the various different combinations of the individual components listed above of any subgroup. It can be formed not only by components but also by components that do not include components excluded from the entire group forming the subgroup. In addition, the subgroup formed by excluding various components from the entire group in the above list is the entire group excluding the individual components from which the dopant metal or fluorinated solvent (or combination thereof) has been selected. It may be an individual component of the entire group so that it can be selected without including all other components of the group.</p><p num="0102"> Formulas IIA, IIB, and III set forth herein are: (1) all other mutable groups, while choosing from within one defined range of mutable groups, substituents, or coefficients of number. Keep the substituents or coefficients constant, (2) make the same selection of each of the other modifiable groups, substituents, or coefficients within the specified range, and keep the others constant. Represents one or all of the separate individual fluorinated solvent compounds that can be combined from each formula. In addition to selecting within a predetermined range of any of the mutable groups, substituents, or coefficients of only one of the components of the group represented by the range, multiple compounds are grouped, substituted groups. , Or can be represented by choosing from two or more, but not all, of the components of the entire group of numerical coefficients. A selection within the specified range of any mutable group, substituent, or number range may (i) contain only one component of the entire group represented by that range, or (ii) the entire. If a subgroup contains two or more, but not all, of the components of a group, the selected component is selected by excluding the components of the entire group that are not selected for the formation of that subgroup. To. In such cases, the compound, or compound, can be characterized by one or more definitions of modifiable groups, substituents, or coefficients that refer to the entire group of defined ranges of its variates. , Components excluded from the formation of subgroups are not included in the whole group.</p><p num="0103"> Unless otherwise specified or indicated in the context of use in the present specification, one embodiment of the subject matter of the present invention comprises, contains, contains, certain features or elements. When described or described as having, being composed of, or being a component, one or more features or elements are in the embodiment in addition to those explicitly described or described. Can exist in. However, another embodiment of the subject matter of the invention can be described or described as essentially consisting of a particular feature or element, in such embodiments the working principle and distinct features of that embodiment. There are no features or elements in the embodiment that substantially alter. Yet another embodiment of the subject matter of the invention can be described or described as consisting of specific features or elements, and in such embodiments, or non-substantial variants thereof, it is explicitly described or described. Only the features or elements that are to be present exist.</p><p num="0104"> Where numerical ranges are enumerated or defined herein, they include their endpoints, as well as all individual integers and fractions within that range, and all variations of these endpoints and internal integers and fractions. From the possible combinations of, each of the narrower ranges formed by forming a subgroup of the larger group of values within the stated range is also comparable as each of those narrow ranges is specified. Included in. If a numerical range is described herein as exceeding the values stated, then the range is nonetheless finite and its upper bound by the values available in the context of the invention described herein is. It becomes a boundary. If a range is stated herein to be less than the stated values, then the range is nevertheless bounded by its lower bound by a non-zero value. Unless otherwise specified in this specification or the circumstances of use indicate the opposite. (a) A set of compounds, monomers, oligomers, polymers, and / or other chemicals transforms derivatives of that set of components into two or more mixtures of any component and / or any of those derivatives. Including; (b) The quantities, sizes, ranges, formulations, parameters, and other quantities and characteristics described herein are approximate, not necessarily limited, especially when modified by the term "about". And / or may be larger or smaller (if necessary) than described, reflecting tolerances, conversions, rounding, measurement errors, etc., and in the context of the invention, the scope and functionality of the description. Out-of-range values that are and / or behaviorally equivalent may also be included in the listed values.</p><p num="0105"> The following is a summary of the present invention. 1. Lithium-ion battery: (a) With housing; (b) Negative and positive electrodes arranged in the housing and in conductive contact with each other. The positive electrode is a manganese positive electrode containing a lithium-containing manganese composite oxide having a spinel structure as an active material, and the lithium-containing manganese composite oxide is of the formula. Li_zMn_1.5Ni_xM_yO_4-d[During the ceremony, M is at least one metal selected from the group consisting of Al, Cr, Fe, Ga, Zn, Co, Nb, Mo, Ti, Zr, Mg, V, and Cu. 0.38 x &lt;0.5, 0 &lt;y 0.12, 0 d 0.3 0.00 &lt;z 1.1, z varies with the emission and uptake of lithium ions and electrons during charging and discharging] Represented by, with negative and positive; (c) A non-aqueous electrolyte composition that is disposed in the housing and provides an ionic conductive passage between the negative electrode and the positive electrode, at least one electrolyte salt, and at least one fluorinated acyclic. With a non-aqueous electrolyte composition comprising a formula carboxylic acid ester and / or at least one fluorinated acyclic carbonate; (d) A porous separator between the negative electrode and the positive electrode, Lithium-ion battery including. 2.M is at least one metal selected from the group consisting of Al, Cr, Fe, Ga, and Zn. 0.4 x &lt;0.5, 0 &lt;y 0.1, z = 1 and The lithium ion battery according to 1 above, wherein d = 0. 3. The fluorinated acyclic carboxylic acid ester is CH₃C (O) OCH₂CF₂H, CH₃C (O) OCH₂CF₃, And CH₃C (O) OCH₂CF₂CF₂The lithium ion battery according to 1 above, selected from one or more members of the group consisting of H. 4. The fluorinated acyclic carbonate is CH₃OC (O) OCH₂CF₂H, CH₃OC (O) OCH₂CF₃, And CH₃OC (O) OCH₂CF₂CF₂The lithium ion battery according to 1 above, selected from one or more members of the group consisting of H. 5. The lithium ion battery according to 1 above, wherein M in the equation (b) contains Fe. 6. The fluorinated acyclic carboxylic acid ester is CH₃CO₂CH₂CF₂The lithium ion battery according to 3 above, which comprises H. 7. The above 1. The non-aqueous electrolyte composition (c) contains a solvent mixture containing a fluorinated acyclic carboxylic acid ester and / or a fluorinated acyclic carbonate and at least one co-solvent. Lithium-ion battery. 8. The lithium ion battery according to 7 above, wherein the solvent mixture contains a fluorinated acyclic carboxylic acid ester and / or a fluorinated acyclic carbonate in an amount of about 50% by mass to about 80% by mass of the solvent mixture. 9. The lithium ion battery according to 7 above, wherein the solvent mixture contains a fluorinated acyclic carboxylic acid ester and / or a fluorinated acyclic carbonate in an amount of about 65% by mass to about 75% by mass of the solvent mixture. 10. The lithium ion battery according to 7 above, wherein the cosolvent contains ethylene carbonate. 11. The solvent mixture is CH₃CO₂CH₂CF₂The lithium ion battery according to 7 above, which comprises H and ethylene carbonate. 12.CH₃CO₂CH₂CF₂11. The lithium ion battery according to 11 above, wherein H constitutes from about 50% by mass to about 80% by mass of the solvent mixture. 13.CH₃CO₂CH₂CF₂11. The lithium ion battery according to 11 above, wherein H constitutes from about 65% by mass to about 75% by mass of the solvent mixture. 14. The non-aqueous electrolyte composition (c) is fluoroethylene carbonate and its derivatives. The lithium ion according to 1 above, further comprising an additive selected from the group consisting of ethylene sulfate and its derivatives, vinyl ethylene carbonate and its derivatives, vinylene carbonate and its derivatives, maleic anhydride and its derivatives, and vinyl acetate. battery. 15. The lithium ion battery according to 1 above, wherein the non-aqueous electrolyte composition (c) further contains a fluoroethylene carbonate. 16. The fluorinated acyclic carboxylic acid ester has the following structural formula: R¹--- C (O) O --- R²[During the ceremony, R¹Is CH₃, CH₂CH₃, CH₂CH₂CH₃, CH (CH₃)₂, CF₃, CF₂H, CFH₂, CF₂R³, CFHR³, And CH₂R^fSelected from the group consisting of R²Independently, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH (CH₃)₂, And CH₂R^fSelected from the group consisting of R³Is optionally replaced with at least one fluorine C₁~ C₃Alkyl group, R^fIs a C substituted with at least one fluorine₁~ C₃Alkyl group, R¹Or R²At least one of contains at least one fluorine, R¹Is CF₂If H, then R²Is CH₃is not it] Represented by The fluorinated acyclic carbonate has the following structural formula: R⁴--- OC (O) O --- R⁵[During the ceremony, R⁴And R⁵Independently, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH (CH₃)₂, And CH₂R^fSelected from the group consisting of R^fIs a C substituted with at least one fluorine₁~ C₃Alkyl group, R⁴Or R⁵At least one of them contains at least one fluorine] The lithium ion battery according to 1 above, which is represented by. 17. The electrolyte salt in the non-aqueous electrolyte composition (c) is: Lithium hexafluorophosphate, LiPF₃(CF₂CF₃)₃, Bis (trifluoromethanesulfonyl) imide lithium, Bis (perfluoroethanesulfonyl) imide lithium, (Fluorosulfonyl) (Nonafluorobutanesulfonyl) Imid Lithium, Bis (fluorosulfonyl) imide lithium, Lithium tetrafluoroborate, Lithium perchlorate, Lithium hexafluoroarsenate, Lithium trifluoromethanesulfonate, Tris (trifluoromethanesulfonyl) methidolithium, Lithium bis (oxalate) oxalate, Lithium difluoro (oxalate) oxalate, Li₂B₁₂F_12-xH_x[In the formula, x is 0-8], and Mixture of lithium fluoride and anion receptor The lithium ion battery according to 1 above, which is selected from one or more members of the group consisting of. 18. The lithium ion battery according to 17 above, wherein the electrolyte salt contains lithium hexafluorophosphate. 19. The lithium ion battery according to 1 above, wherein the negative electrode contains lithium titanate or graphite as an active material. 20. Electronically powered or assisted equipment, including the lithium-ion battery described in 1 above. 21. The device according to 20 above, manufactured as a means of transportation, computer, communication equipment, camera, radio, or power tool.</p>