WO2022000271A1 - 电解液和包含其的电化学装置和电子装置 - Google Patents

电解液和包含其的电化学装置和电子装置 Download PDF

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Publication number
WO2022000271A1
WO2022000271A1 PCT/CN2020/099306 CN2020099306W WO2022000271A1 WO 2022000271 A1 WO2022000271 A1 WO 2022000271A1 CN 2020099306 W CN2020099306 W CN 2020099306W WO 2022000271 A1 WO2022000271 A1 WO 2022000271A1
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substituted
compounds
group
unsubstituted
electrolyte
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English (en)
French (fr)
Inventor
张丽兰
唐超
刘俊飞
郑建明
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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Priority to PCT/CN2020/099306 priority Critical patent/WO2022000271A1/zh
Priority to CN202080005779.XA priority patent/CN112956063B/zh
Publication of WO2022000271A1 publication Critical patent/WO2022000271A1/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the technical field of energy storage, and in particular, to an electrolyte and an electrochemical device and an electronic device including the same.
  • Electrochemical devices such as lithium-ion batteries
  • the solvent or additives in the electrolyte react on the surface of the positive and negative electrodes to generate a large amount of gas, especially when the battery is under extreme conditions, for example, during the high-temperature storage process at full charge, with the extension of the storage time, it will As a result, the continuous reaction between the positive and negative electrodes and the electrolyte causes more and more gas to accumulate in the battery and greatly reduces the safety of the battery. Therefore, it is necessary to develop a new electrolyte additive, which can form a stable protective layer on the electrode surface, so that the battery can effectively avoid the risk of flatulence even under extreme storage conditions.
  • the present application provides an electrolyte, which can provide a stable protective layer on the positive and negative electrodes of an electrochemical device, so that the electrochemical The device can achieve good electrochemical properties, eg, good high temperature storage performance.
  • any one of M 1 to M 5 is M 7 -OLi group; and at least one of M 1 to M 5 is M 8 -CN group; the rest are not M 7 -OLi group and M 8 -CN group
  • M 1 to M 5 of the group are each independently selected from hydrogen, substituted or unsubstituted C 1-12 alkoxy, halogen, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted Substituted C 2-12 alkenyl, substituted or unsubstituted C 2-12 alkynyl, nitro, sulfonic acid, aldehyde, carboxyl, silyl or substituted or unsubstituted C 6-12 aryl group, wherein when substituted, the substituent is halogen;
  • M 6 , M 7 and M 8 are each independently selected from C 0-5 hydrocarbylene, C 1-5 hydrocarbylene substituted by halogen.
  • compounds of formula (I) of the present application include at least one of compounds of formula I-1 to formula I-6:
  • R 1 -R 14 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1-12 alkoxy, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted Substituted C 2-12 alkenyl, substituted or unsubstituted C 2-12 alkynyl, nitro, sulfonic acid, aldehyde, carboxyl, silyl or substituted or unsubstituted C 6-12 aryl group, wherein when substituted, the substituent is halogen; and n is 0-5.
  • compounds of Formula I include at least one of the following Compounds 1 to 16:
  • the content of the compound of formula I described herein is about 0.01% to about 10% based on the total mass of the electrolyte.
  • the electrolyte solution of the present application further includes at least one of additive A, additive B or additive C, wherein the additive A includes nitrile compounds, acid anhydride compounds, ether compounds, and phosphate ester compounds , at least one of phosphite compounds or borate compounds; the additive B comprises at least one of sulfate compounds, sulfite compounds, fluorocarbonates or unsaturated carbonates; the Additive C contains at least one of sulfonate-based compound, sulfone-based compound or lithium salt additive.
  • additive A includes nitrile compounds, acid anhydride compounds, ether compounds, and phosphate ester compounds , at least one of phosphite compounds or borate compounds
  • the additive B comprises at least one of sulfate compounds, sulfite compounds, fluorocarbonates or unsaturated carbonates
  • the Additive C contains at least one of sulfonate-based compound, sulfone-based compound or lithium salt additive.
  • the content of the additive A is about 0.01% to about 10%; the content of the additive B is about 0.01% to about 10%; the content of the additive C is From about 0.01% to about 5%.
  • the nitrile compound includes at least one of the following compounds: succinonitrile, adiponitrile, 1,3,5-pentanetricarbonitrile, 1,3,6-hexanetricarbonitrile, 1,2, 6-Hexanetricarbonitrile, fumaric nitrile or ethylene glycol (bispropionitrile) ether;
  • the acid anhydride compounds include at least one of the following compounds: citric anhydride, succinic anhydride, maleic anhydride, trifluoromethyl maleic anhydride, dimethyl maleic anhydride or propane sulfonic anhydride;
  • Ether compounds include at least one of the following compounds: 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether or perfluorobutyl ether;
  • Phosphate compounds include at least one of the following compounds: triphenyl phosphate, tris(trifluoroethyl) phosphate or triallyl phosphate;
  • Phosphite compounds include at least one of the following compounds: triphenyl phosphite or trimethylsilyl phosphite;
  • the borate compound includes at least one of the following compounds: tris(hexafluoroisopropyl) borate, trimethylsilyl borate, trimethylene borate, triisopropyl borate, tributyl borate, boric acid triethyl ester or tripropyl borate;
  • Sulfate compounds include at least one of the following compounds: vinyl sulfate, vinyl bisulfate, vinyl methyl sulfate, vinyl ethyl sulfate or vinyl propyl sulfate;
  • the sulfite compounds include at least one of the following compounds: vinyl sulfite, methyl vinyl sulfite, ethyl vinyl sulfite, propyl vinyl sulfite or propylene sulfite;
  • Fluorocarbonates include at least one of the following compounds: fluoroethylene carbonate, methyl trifluoroethyl carbonate or trifluoromethyl ethylene carbonate;
  • Unsaturated carbonates include at least one of the following compounds: ethylene ethylene carbonate or vinylene carbonate;
  • Sulfonate compounds include at least one of the following compounds: 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, propenyl-1,3- Sultone, methylene methanedisulfonate or chain bissulfonate;
  • Sulfone compounds include at least one of the following compounds: sulfolane, sulfolane or 3-sulfolane;
  • Lithium salt additives include at least one of the following compounds: lithium 4,5-dicyano-2-(trifluoromethyl)imidazolium, lithium difluorophosphate, lithium tetrafluoroborate, lithium bisfluorosulfonimide, Lithium bistrifluorosulfonimide, lithium oxalate borate, or lithium bisfluorooxalate borate.
  • the present application also provides an electrochemical device comprising a positive electrode and an electrolyte according to the present application, the positive electrode including a positive electrode active material.
  • the cathode active material includes at least one element selected from Al, Zr, or Mg.
  • the content a of Al is less than 1%
  • the content b of Zr is less than 1%
  • the content c of Mg is less than 0.5%.
  • the positive electrode material includes Al and Mg, and the content thereof satisfies the following condition: 0.005 ⁇ a/c ⁇ 500.
  • the present application also provides an electronic device comprising the electrochemical device according to the present application.
  • a term may refer to a range of variation less than or equal to ⁇ 10% of the numerical value, such as less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, Less than or equal to ⁇ 2%, less than or equal to ⁇ 1%, less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%.
  • the difference between two values is less than or equal to ⁇ 10% of the mean of the values (eg, less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, less than or equal to ⁇ 2%, less than or equal to ⁇ 1%, less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%), then the two values are considered to be "about" the same.
  • a list of items joined by the terms "one of,” “one of,” “one of,” or other similar terms can mean that any of the listed items one.
  • the phrase “one of A and B” means A only or B only.
  • the phrase “one of A, B, and C” means A only; B only; or C only.
  • Item A may contain a single element or multiple elements.
  • Item B may contain a single element or multiple elements.
  • Item C may contain a single element or multiple elements.
  • a list of items joined by the terms "at least one of,” “at least one of,” “at least one of,” or other similar terms may mean the listed items any combination of .
  • the phrase “at least one of A and B” means A only; B only; or A and B.
  • the phrase "at least one of A, B, and C” means A only; or B only; C only; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C.
  • Item A may contain a single element or multiple elements.
  • Item B may contain a single element or multiple elements.
  • Item C may contain a single element or multiple elements.
  • a “Cn-m” group refers to a group having "n” to “m” carbon atoms, where “n” and “m” are integers.
  • a “C 1-12 “hydrocarbyl group is a hydrocarbyl group having 1 to 12 carbon atoms
  • a “C 0 “hydrocarbylene group refers to a covalent bond.
  • hydrocarbyl encompasses alkyl, alkenyl, alkynyl, cycloalkyl, aryl groups.
  • a hydrocarbyl group is expected to be a straight chain hydrocarbon structure having 1 to 20 carbon atoms.
  • Hydrocarbyl is also intended to be a branched or cyclic hydrocarbon structure having 3 to 20 carbon atoms. When specifying a hydrocarbyl group having a particular carbon number, it is intended to encompass all geometric isomers having that carbon number.
  • the hydrocarbyl group herein may also be a hydrocarbyl group of 1 to 15 carbon atoms, a hydrocarbyl group of 1 to 10 carbon atoms, a hydrocarbyl group of 1 to 5 carbon atoms, a hydrocarbyl group of 5 to 20 carbon atoms, a hydrocarbyl group of 5 to 15 carbon atoms or a hydrocarbon group of 5 to 10 carbon atoms.
  • hydrocarbyl groups may be optionally substituted.
  • hydrocarbyl groups can be substituted with halogen, alkyl, aryl or heteroaryl groups including fluorine, chlorine, bromine and iodine.
  • hydrocarbylene refers to a straight or branched chain divalent hydrocarbon group linking an aryl group in the compounds of the present application to a -OLi or -CN group, wherein hydrocarbyl is as defined above.
  • exemplary hydrocarbylene groups include, but are not limited to: methylene, ethylene, propylene, n-butylene, vinylene, propenylene, n-butenylene, propynylene, n-butyne Base et al.
  • the point of attachment of the hydrocarbylene to the aryl nucleus and to the -OLi or -CN group can be one carbon or any two carbons in the hydrocarbylene. Unless specifically stated otherwise in the specification, hydrocarbylene groups are optionally substituted.
  • hydrocarbyloxy refers to an L-O- group where L is alkyl, alkenyl, alkynyl, cycloalkyl, aryl.
  • the hydrocarbyloxy group herein may be a hydrocarbyloxy group of 1 to 20 carbon atoms, and may also be a hydrocarbyloxy group of 1 to 15 carbon atoms, a hydrocarbyloxy group of 1 to 10 carbon atoms, a hydrocarbyloxy group of 1 to 5 carbon atoms Hydrocarbyloxy, hydrocarbyloxy of 5 to 20 carbon atoms, hydrocarbyloxy of 5 to 15 carbon atoms, or hydrocarbyloxy of 5 to 10 carbon atoms.
  • alkyl is intended to be a straight chain saturated hydrocarbon structure having from 1 to 20 carbon atoms. "Alkyl” is also contemplated to be a branched or cyclic hydrocarbon structure having 3 to 20 carbon atoms.
  • the alkyl group can be an alkyl group of 1 to 20 carbon atoms, an alkyl group of 1 to 10 carbon atoms, an alkyl group of 1 to 5 carbon atoms, an alkyl group of 5 to 20 carbon atoms, an alkyl group of 5 to 15 carbon atoms An alkyl group of carbon atoms or an alkyl group of 5 to 10 carbon atoms.
  • butyl is meant to include n-butyl, sec-butyl, isobutyl, tert-butyl and cyclobutyl;
  • propyl includes n-propyl, isopropyl and cyclopropyl.
  • alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, octyl, cyclopropyl, cyclobutyl, norbornyl Base et al. Additionally, alkyl groups can be optionally substituted.
  • cycloalkyl encompasses cyclic alkyl groups.
  • the cycloalkyl group may be a cycloalkyl group of 3 to 20 carbon atoms, a cycloalkyl group of 6 to 20 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms.
  • the cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. Additionally, cycloalkyl groups may be optionally substituted.
  • alkenyl refers to a monovalent unsaturated hydrocarbon group which may be straight or branched and having at least one and usually 1, 2 or 3 carbon-carbon double bonds. Unless otherwise defined, the alkenyl group typically contains from 2 to 20 carbon atoms, for example, it may be alkenyl of 2 to 20 carbon atoms, alkenyl of 6 to 20 carbon atoms, alkenyl of 2 to 10 carbon atoms group or an alkenyl group of 2 to 6 carbon atoms.
  • Representative alkenyl groups include, for example, vinyl, n-propenyl, isopropenyl, n-but-2-enyl, but-3-enyl, n-hex-3-enyl, and the like. Additionally, alkenyl groups may be optionally substituted.
  • alkynyl refers to a monovalent unsaturated hydrocarbon group which may be straight or branched and having at least one and usually one, two or three carbon-carbon triple bonds. Unless otherwise defined, the alkynyl group typically contains from 2 to 20 carbon atoms, for example, it may be alkynyl of 2 to 20 carbon atoms, alkynyl of 6 to 20 carbon atoms, alkynyl of 2 to 10 carbon atoms alkynyl or alkynyl of 2 to 6 carbon atoms.
  • alkynyl groups include, for example, ethynyl, prop-2-ynyl (n-propynyl), n-but-2-ynyl, n-hex-3-ynyl, and the like. Additionally, alkynyl groups may be optionally substituted.
  • aryl encompasses both monocyclic and polycyclic ring systems.
  • a polycyclic ring may have two or more rings in which two carbons are two adjacent rings (the rings are "fused"), wherein at least one of the rings is aromatic, such as other Rings can be cycloalkyl, cycloalkenyl, aryl, heterocycle and/or heteroaryl.
  • the aryl group may be a C6-50 aryl group, a C6-40 aryl group, a C6-30 aryl group, a C6-20 aryl group, or a C6-10 aryl group.
  • aryl groups include, for example, phenyl, methylphenyl, propylphenyl, isopropylphenyl, benzyl, and naphth-1-yl, naphth-2-yl, and the like. Additionally, aryl groups can be optionally substituted.
  • heterocyclyl encompasses both aromatic and non-aromatic cyclic groups.
  • a heteroaromatic cyclic group also means a heteroaryl group.
  • the heteroaromatic ring group and the heteronon-aromatic ring group are C 1-50 heterocyclyl, C 1-40 heterocyclyl, C 1-30 heterocyclyl including at least one heteroatom , C 1-20 heterocyclyl, C 1-10 heterocyclyl, C 1-6 heterocyclyl. Examples are morpholinyl, piperidinyl, pyrrolidinyl, and the like, and cyclic ethers, such as tetrahydrofuran, tetrahydropyran, and the like. Additionally, heterocyclyl groups may be optionally substituted.
  • heteroaryl encompasses monocyclic heteroaromatic groups that may include one to three heteroatoms, such as pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, Pyrazine and pyrimidine etc.
  • heteroaryl also includes polycyclic heteroaromatic systems having two or more rings in which two atoms are shared by two adjacent rings (the rings being "fused"), wherein the At least one of the rings is heteroaryl and the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocycle and/or heteroaryl.
  • a heteroaryl group can be a C6-50 heteroaryl, a C6-40 heteroaryl, a C6-30 heteroaryl, a C6-20 heteroaryl, or a C6-10 heteroaryl.
  • heteroaryl groups can be optionally substituted.
  • heteroatom encompasses O, S, P, N, B, or isosteres thereof.
  • halogen may be F, Cl, Br or I.
  • cyano encompasses organics containing the organic group CN.
  • the substituents may be selected from the group consisting of halogen, alkyl, cycloalkyl, alkenyl, aryl, and heteroaryl.
  • any one of M 1 to M 5 is M 7 -OLi group; and at least one of M 1 to M 5 is M 8 -CN group; the rest are not M 7 -OLi group and M 8 -CN group
  • M 1 to M 5 of the group are each independently selected from hydrogen, C 1-12 alkoxy, halogen, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted C 2-12 alkene group, substituted or unsubstituted C 2-12 alkynyl, nitro, sulfonic acid group, aldehyde group, carboxyl group, silicon group or substituted or unsubstituted C 6-12 aryl group, wherein when substituted , the substituent is halogen; wherein M 6 , M 7 and M 8 are each independently selected from C 0-5 hydrocarbylene, C 1-5 hydrocarbylene substituted by halogen.
  • one, two or three M 8 -CN groups are included in M 1 to M 5 of the compounds of Formula I above.
  • C 0-5 hydrocarbylene includes, but is not limited to: covalent bond, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec Butyl, tert-butyl, pentyl, vinyl, ethynyl, propenyl, propynyl.
  • compounds of Formula I of the present application include at least one of compounds of Formulas 1-1 to 1-6:
  • R 1 to R 14 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1-12 alkoxy, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted Substituted C 2-12 alkenyl, substituted or unsubstituted C 2-12 alkynyl, nitro, sulfonic acid, aldehyde, carboxyl, silyl or substituted or unsubstituted C 6-12 aryl group, wherein when substituted, the substituent is halogen; and n is 0-5.
  • R 1 to R 14 in the compounds of Formula I-1 to Formula I-6 are each independently selected from: hydrogen, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted Substituted C2-12 alkenyl or substituted or unsubstituted C2-12 alkynyl.
  • compounds of Formula I include at least one of the following Compounds 1 to 16:
  • the content of the compound of formula I described in the present application is about 0.01% to about 10%, for example, the content of the compound of formula I may be 0.01%, 0.05%, 1.0%, 2.0%, 3.0%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 8.0%, 9.0%, 10%, or the range between any of the above contents, when adding When the concentration is lower than 0.01%, the additive cannot effectively form a film at the interface because the concentration is too low. When the concentration is higher than 10%, it will lead to serious lithium precipitation at the interface of the negative electrode. Lithium salt makes the discharge capacity of normal temperature cycle low, which affects the actual capacity of the battery.
  • the electrolyte solution of the present application further includes at least one of additive A, additive B or additive C, wherein additive A includes nitrile compounds, acid anhydride compounds, ether compounds, phosphate ester compounds, At least one of phosphoric acid ester compounds or boric acid ester compounds;
  • Additive B comprises at least one of sulfuric ester compounds, sulfite compounds, fluorocarbonate or unsaturated carbonate;
  • Additive C comprises sulfonic acid ester At least one of compounds, sulfones, or lithium salt additives.
  • the electrolyte of the present application may comprise a compound of formula I above in combination with any one, two, or three of the following additives: unsaturated carbonates, eg, ethylene ethylene carbonate or vinylene carbonate ; Sulfonate compounds, such as 1,3-propane sultone; Sulfate compounds, such as vinyl sulfate; Fluorocarbonate compounds, such as fluoroethylene carbonate; Lithium salt additives, such as, Lithium difluorophosphate; nitriles such as succinonitrile and adiponitrile.
  • unsaturated carbonates eg, ethylene ethylene carbonate or vinylene carbonate
  • Sulfonate compounds such as 1,3-propane sultone
  • Sulfate compounds such as vinyl sulfate
  • Fluorocarbonate compounds such as fluoroethylene carbonate
  • Lithium salt additives such as, Lithium difluorophosphate
  • nitriles such as succin
  • the content of the above-mentioned Additive A and Additive B may be about 0.01% to about 10%; 1.0%, 2.0%, 3.0%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 8.0%, 9.0%, 10%, or a range between any of the above .
  • the content of the additive C is about 0.01% to about 5% based on the total mass of the electrolyte; for example, the content of the additive C may be 0.01%, 0.05%, 1.0%, 1.5%, 2.0%, 2.5% %, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, or a range between any of the above contents.
  • the total content of the above-mentioned Additive A, Additive B and Additive C does not exceed 20%.
  • the nitrile compound includes at least one of the following compounds: succinonitrile, adiponitrile, 1,3,5-pentanetricarbonitrile, 1,3,6-hexanetricarbonitrile, 1,3,6-hexanetricarbonitrile 2,6-hexanetricarbonitrile, fumaric nitrile or ethylene glycol (bispropionitrile) ether.
  • the acid anhydride compound includes at least one of the following compounds: citracic anhydride, succinic anhydride, maleic anhydride, trifluoromethyl maleic anhydride, dimethyl maleic anhydride, or propane sulfonic anhydride.
  • the ether compound includes at least one of the following compounds: 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether or perfluorobutyl ether.
  • the phosphate-based compound includes at least one of the following compounds: triphenyl phosphate, tris(trifluoroethyl) phosphate, or triallyl phosphate.
  • the phosphite compound includes at least one of the following compounds: triphenyl phosphite or trimethylsilyl phosphite.
  • the borate compound includes at least one of the following compounds: tris(hexafluoroisopropyl) borate, trimethylsilyl borate, trimethylene borate, triisopropyl borate, Tributyl borate, triethyl borate or tripropyl borate.
  • Additive A can form an effective passivation layer on the cathode, and the passivation layer has little effect on the SEI (solid electrolyte interface) impedance, and has good conductivity for ions and electrons. It is used in combination with the compound of formula I. Both the positive and negative interfaces have a good protective effect.
  • the sulfate-based compound includes at least one of the following compounds: vinyl sulfate, vinyl bisulfate, vinyl methyl sulfate, vinyl ethyl sulfate, or vinyl propyl sulfate.
  • the sulfite-based compound includes at least one of the following compounds: vinyl sulfite, vinyl methyl sulfite, vinyl ethyl sulfite, vinyl propyl sulfite, or propylene sulfite .
  • the fluorocarbonate comprises at least one of the following compounds: fluoroethylene carbonate, methyl trifluoroethyl carbonate, or trifluoromethyl ethylene carbonate.
  • the unsaturated carbonate includes at least one of the following compounds: ethylene ethylene carbonate or vinylene carbonate.
  • Additive B can form effective interface protection at the negative electrode interface, and works together with the compound of formula I to ensure that the battery has a relatively stable CEI (cathode electrolyte interface) protective layer in the initial state, and at the same time, it will continue to protect the surface layer during long-term high-temperature storage and cycling. CEI repairs, thereby effectively improving the long-term storage and cycling performance of the battery.
  • CEI cathode electrolyte interface
  • the sulfonate compound includes at least one of the following compounds: 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, propylene yl-1,3-sultone, methylene methanedisulfonate or chain bissulfonate.
  • the sulfone compound includes at least one of the following compounds: sulfolane, sulfolane, or 3-sulfolene.
  • the lithium salt additive includes at least one of the following compounds: 4,5-dicyano-2-(trifluoromethyl)imidazolium lithium, lithium difluorophosphate, lithium tetrafluoroborate, bisfluorolithium Lithium sulfonimide, lithium bistrifluorosulfonimide, lithium oxalate borate, or lithium bisfluorooxalate borate.
  • the additive C and the compound of formula I work together to form an effective passivation layer at the interface of the positive and negative electrodes, and the redox activity of the additive is low. Repair with SEI, thereby effectively improving the long-term storage and cycling performance of the battery. 3.
  • the electrolyte solution of the present application further comprises an organic solvent selected from at least one of cyclic carbonate, chain carbonate, carboxylate or sulfone solvents.
  • the cyclic carbonate is selected from at least one of ethylene carbonate or propylene carbonate;
  • the chain carbonate is selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and propyl methyl carbonate Or at least one in ethyl propyl carbonate;
  • Carboxylic acid ester is selected from at least one in ethyl acetate, ethyl propionate, propyl propionate, propyl acetate, ethyl difluoroacetate or difluoroethyl acetate ;
  • Sulfone solvent is selected from sulfolane, n-butyl sulfone, sulfolane, cyclohexyl sulfone, 2,4-dimethyl sulfolane, 3-methyl-3-sulfolane, n-butyl sulfoxide, di-n-octane At least one of the sulf
  • the present application also provides an electrochemical device comprising the electrolyte according to the present application.
  • the electrochemical device of the present application includes any device in which an electrochemical reaction occurs, and specific examples thereof include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, or capacitors.
  • the electrochemical device is a lithium secondary battery, including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
  • the electrochemical device is a lithium-ion battery.
  • the electrochemical device may further include a positive electrode including a current collector and a positive electrode active material layer disposed on the current collector.
  • the positive electrode active material contains at least one element selected from Al, Zr, or Mg.
  • the positive electrode active material may include Al and Zr, Al and Mg, Zr and Mg, or a combination of Al, Zr and Mg.
  • the Al content a is less than 1% based on the total mass of the positive active material, for example, the Al content a may be less than 0.9%, less than 0.8%, less than 0.7%, less than 0.6%, less than 0.5%, or A range between any two of the above numerical values or between any of the above numerical values and zero.
  • the Zr content b is less than 1% based on the total mass of the positive active material, for example, the Zr content b may be less than 0.9%, less than 0.8%, less than 0.7%, less than 0.6%, less than 0.5%, or A range between any two of the above numerical values or between any of the above numerical values and zero.
  • the Mg content c is less than 0.5% based on the total mass of the positive active material, for example, the Mg content c may be less than 0.5%, less than 0.4%, less than 0.3%, less than 0.2%, less than 0.1%, or A range between any two of the above numerical values or between any of the above numerical values and zero.
  • the positive electrode material includes Al and Mg, and the content thereof satisfies the following condition: 0.005 ⁇ a/c ⁇ 500.
  • the ratio of a/c can be 0.004, 0.01, 0.1, 1, 10, 20, 50, 80, 100, 120, 140, 180, 200, 230, 250, 270, 300, 350, 400, 420, 450 , 499, etc.
  • the content of Al and Mg within this range can more effectively improve the overall performance of the battery.
  • the positive active material includes a compound that reversibly intercalates and deintercalates lithium ions.
  • the positive electrode active material may include a composite oxide containing lithium and at least one element selected from cobalt, manganese, and nickel.
  • the positive active material is selected from lithium cobalt oxide (LiCoO 2 ), lithium nickel manganese cobalt ternary material, lithium manganate (LiMn 2 O 4 ), lithium nickel manganate (LiNi 0.5 Mn 1.5 O 4 ) or at least one of lithium iron phosphate (LiFePO 4 ).
  • the cathode active material layer may have a coating on the surface, or may be mixed with another compound having a coating.
  • the coating may comprise an oxide from a coating element, a hydroxide of the coating element, an oxyhydroxide of the coating element, an oxycarbonate of the coating element, or a coating element At least one coating element compound selected from hydroxycarbonate.
  • the compound used for the coating can be amorphous or crystalline.
  • the coating elements contained in the coating may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, F or their at least one of the mixtures.
  • the coating can be applied by any method as long as the method does not adversely affect the performance of the positive electrode active material.
  • the method may include any coating method well known to those of ordinary skill in the art, such as spraying, dipping, and the like.
  • the positive active material layer further includes a binder, and optionally a conductive material.
  • the binder can improve the bonding of the positive electrode active material particles to each other, and can also improve the bonding of the positive electrode active material and the current collector.
  • binders include polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene-containing Oxygen polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylic (esterified) styrene-butadiene rubber, epoxy resin, Nylon etc.
  • the positive electrode active material layer may further include a conductive material, thereby imparting conductivity to the electrode.
  • the conductive material may include any conductive material as long as it does not cause unwanted chemical changes.
  • non-limiting examples of conductive materials include carbon-based materials (eg, natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, etc.), metal-based materials (eg, metal powders) , metal fibers, etc., including, for example, copper, nickel, aluminum, silver, etc.), conductive polymers (eg, polyphenylene derivatives), and mixtures thereof.
  • the current collector for the positive electrode of the secondary battery according to the present application may be aluminum (Al), but is not limited thereto.
  • the electrochemical device according to the present application may further include a negative electrode including a current collector and a negative electrode active material layer disposed on the current collector.
  • a negative electrode including a current collector and a negative electrode active material layer disposed on the current collector.
  • the specific types of negative electrode active materials are not specifically limited, and can be selected according to requirements.
  • the negative electrode active material is selected from natural graphite, artificial graphite, mesophase microcarbon spheres (abbreviated as MCMB), hard carbon, soft carbon, silicon, silicon-carbon composite, Li-Sn At least one of an alloy, a Li-Sn-O alloy, Sn, SnO, SnO 2 , a spinel-structured lithiated TiO 2 -Li 4 Ti 5 O 12 or a Li-Al alloy.
  • non-limiting examples of carbon materials include crystalline carbon, amorphous carbon, and mixtures thereof.
  • Crystalline carbon can be amorphous or flake-shaped, platelet-shaped, spherical or fibrous natural graphite or artificial graphite.
  • the amorphous carbon can be soft carbon, hard carbon, mesophase pitch carbide, calcined coke, and the like.
  • the anode active material layer may include a binder, and optionally a conductive material.
  • binders include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyfluoro Ethylene, ethylene oxide-containing polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene Rubber, epoxy resin, nylon, etc.
  • the anode active material layer may include a conductive material, thereby imparting conductivity to the electrode.
  • the conductive material may include any conductive material as long as it does not cause unwanted chemical changes.
  • conductive materials include carbon-based materials (eg, natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, etc.), metal-based materials (eg, metal powders) , metal fibers, etc., such as copper, nickel, aluminum, silver, etc.), conductive polymers (eg, polyphenylene derivatives), and mixtures thereof.
  • the current collector for the negative electrodes described herein can be selected from copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, conductive metal clad polymer substrates, and combinations thereof .
  • the electrochemical device of the present application is provided with a separator between the positive electrode and the negative electrode to prevent short circuits.
  • the material and shape of the separator used in the electrochemical device of the present application are not particularly limited.
  • the separator includes a polymer or inorganic or the like formed from a material that is stable to the electrolyte of the present application.
  • the release film may include a substrate layer and a surface treatment layer.
  • the substrate layer is a non-woven fabric, film or composite film with a porous structure
  • the material of the substrate layer is selected from polyethylene, polypropylene, polyethylene terephthalate or polyimide at least one of them.
  • a polypropylene porous membrane, a polyethylene porous membrane, a polypropylene non-woven fabric, a polyethylene non-woven fabric or a polypropylene-polyethylene-polypropylene porous composite membrane can be selected.
  • At least one surface of the substrate layer is provided with a surface treatment layer, and the surface treatment layer may be a polymer layer or an inorganic layer, or a layer formed by mixing polymers and inorganic substances.
  • the inorganic layer includes inorganic particles and a binder.
  • the inorganic particles are selected from the group consisting of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium dioxide, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide , at least one of boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide or barium sulfate.
  • the binder is selected from the group consisting of polyvinylidene fluoride, copolymers of vinylidene fluoride-hexafluoropropylene, polyamides, polyacrylonitrile, polyacrylates, polyacrylic acids, polyacrylates, polyethylene pyrrolidines At least one of ketone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene or polyhexafluoropropylene.
  • the polymer layer contains a polymer.
  • the material of the polymer is selected from polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly(vinylidene fluoride) At least one of fluoroethylene-hexafluoropropylene).
  • the present application also provides an electronic device comprising the electrochemical device according to the present application.
  • the electrochemical device according to the present application is suitable for electronic equipment in various fields.
  • the use of the electrochemical device of the present application is not particularly limited, and it can be used for any use known in the art.
  • the electrochemical devices of the present application may be used in, but are not limited to, the following electronic devices: notebook computers, pen input computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers , Headphones, VCRs, LCD TVs, Portable Cleaners, Portable CD Players, Mini Discs, Transceivers, Electronic Notepads, Calculators, Memory Cards, Portable Recorders, Radios, Backup Power, Motors, Cars, Motorcycles Cars, power-assisted bicycles, bicycles, lighting equipment, toys, game consoles, clocks, power tools, flashlights, cameras, large household batteries and lithium-ion capacitors, etc.
  • the present application achieves the following unexpected technical effects: during the chemical formation process of the compound of formula I provided by the present application, very stable CEI and SEI protective films are easily formed on the surfaces of the positive and negative electrodes.
  • the protective film is fully fused with the substrate, and on the negative electrode, the protective film can provide a complexation point with lithium ions, so that rapid ion transport can be performed, and at the same time, the large amount of electrolyte deposition on the negative electrode due to irreversible reduction can be effectively suppressed.
  • the protective film can reduce the reaction between the positive electrode and the electrolyte, while inhibiting the dissolution of metal ions, ultimately improving the high-temperature storage performance of electrochemical devices (eg, lithium-ion batteries).
  • the film-forming effect of the electrolyte solution of the present application on the positive and negative electrodes can be improved.
  • the formed protective film has more excellent high temperature stability, thereby further improving the high temperature storage performance of the electrochemical device (eg, lithium ion battery) of the present application.
  • ethylene carbonate, propylene carbonate and diethyl carbonate are uniformly mixed in a mass ratio of 1:1:1 to obtain a non-aqueous organic solvent.
  • 1 mol/L lithium hexafluorophosphate (LiPF 6 ) was added to the non-aqueous organic solvent to obtain a base electrolyte.
  • LiPF 6 lithium hexafluorophosphate
  • other additives were added according to the amounts and types provided in the table below to obtain the electrolytes of the respective examples and comparative examples.
  • the positive electrode active material, the binder polyvinylidene fluoride (PVDF) and the conductive agent Super-P were dissolved in N-methylpyrrolidone (NMP) in a mass ratio of 96:2:2 and mixed uniformly to prepare a positive electrode slurry.
  • NMP N-methylpyrrolidone
  • the positive electrode slurry was uniformly coated on the positive electrode current collector aluminum foil with a thickness of 12 ⁇ m, and the positive electrode active material layer was obtained by baking at 120 °C for 1 h, and then the positive electrode was obtained by compacting, slitting and welding tabs.
  • the negative electrode active material graphite powder, silicon oxide powder, sodium carboxymethyl cellulose thickener (CMC) and binder styrene-butadiene rubber are dissolved in water in a mass ratio of 81:15:2:2, fully mixed and stirred to obtain a negative electrode slurry
  • the negative electrode slurry was uniformly coated on the negative electrode current collector copper foil with a thickness of 12 ⁇ m, baked at 120 °C for 1 h, and then compacted to obtain the negative electrode active material layer, and then the electrode tabs were cut and welded to obtain the negative electrode.
  • a 12 ⁇ m polypropylene film was used as the separator.
  • the positive electrode, the separator and the negative electrode are stacked in order so that the separator is in the middle of the positive and negative electrodes for isolation, and then rolled into a square bare cell.
  • the bare cell is put into an aluminum foil packaging bag, baked at 80°C to remove water, and then injected with the corresponding electrolyte.
  • Battery capacity retention rate 400th cycle discharge capacity ⁇ first cycle discharge capacity ⁇ 100%
  • the positive electrode materials used in Examples 1 to 23 and Comparative Example 1 are ternary nickel-cobalt-manganese (LiNi 0.8 Co 0.1 Mn 0.1 O 2 , NCM811), wherein the doping amount of Al is 0.15%, and the doping amount of Zr is 0.007 %, and the doping amount of Mg is 0.1%.
  • the specific test results are shown in Table 1 below.
  • Examples 1 to 23 in the above table added the compound of formula I with different contents and types, and comparative example 1 did not add the compound of formula I.
  • the thickness growth rate of the battery at high temperature storage is 45%, and after the compound of formula I is added, the thickness of the battery increases significantly.
  • the reason for the improvement is due to the fact that the compound of formula I of the present application can produce a stable protective film on the surfaces of the positive and negative electrodes during the formation process, thereby reducing the further reaction between the positive and negative electrodes and the electrolyte during the high-temperature storage process of the battery, and finally reducing storage.
  • the purpose of flatulence and improving high temperature storage performance is due to the fact that the compound of formula I of the present application can produce a stable protective film on the surfaces of the positive and negative electrodes during the formation process, thereby reducing the further reaction between the positive and negative electrodes and the electrolyte during the high-temperature storage process of the battery, and finally reducing storage. The purpose of flatulence and improving high temperature storage performance.
  • Embodiments 24 to 52 illustrate examples of using the compound of formula I of the present application in combination with other additives, wherein the positive electrode material used is ternary nickel cobalt manganese (LiNi 0.8 Co 0.1 Mn 0.1 O 2 , NCM811), wherein Al
  • the doping amount of Zr is 0.15%, the doping amount of Zr is 0.007%, and the doping amount of Mg is 0.1%.
  • Table 2 The specific test results are shown in Table 2 below.
  • Examples 24 to 52 demonstrate that the compounds of formula I of the present application can be used in combination with other types of additives to further improve the high temperature storage and cycling performance of electrochemical devices.
  • the positive electrode materials used in Examples 53 to 69 were ternary nickel-cobalt-manganese (LiNi 0.5 Co 0.2 Mn 0.3 O 2 , NCM523), and the doping amounts of each element were shown in Table 3 below.

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Abstract

一种电解液，其包含式（I）化合物，其中，M1至M5中任意一个为M7-OLi基团；且M1至M5中至少一个为M8-CN基团；其余不为M7-OLi基团和M8-CN基团的M1至M5各自独立地选自氢、经取代或未经取代的C1-12烷氧基、卤素、经取代或未经取代的C1-12烷基、经取代或未经取代的C2-12烯基、经取代或未经取代的C2-12炔基、硝基、磺酸基、醛基、羧基、硅基或经取代或未经取代的C6-12芳基，其中当取代时，取代基为卤素；其中M6、M7和M8各自独立地选自C0-5亚烃基、被卤素取代的C1-5亚烃基。还提供一种电化学装置和电子装置。该电解液能够为电化学装置提供良好的高温存储性能。

Description

电解液和包含其的电化学装置和电子装置 技术领域
本申请涉及储能技术领域，尤其涉及一种电解液以及包括其的电化学装置和电子装置。
背景技术
电化学装置，如锂离子电池，在多方面的优点使其被广泛应用于各种电子设备中。在锂电池化成过程中，电解液中的溶剂或添加剂在正负极表面反应产生大量气体，尤其当电池在极端条件下，例如，在满充高温存储过程中，随着存储时间的延长，会导致正负极与电解液的持续反应，使电池内积聚的气体越来越多，电池安全性大大降低。因此，需要开发一种新的电解液添加剂，其可在电极表面形成稳定的保护层，使得电池即使在极端存储条件下也能够有效的避免胀气风险。
发明内容
为了克服现有技术中锂离子电池在高温存储过程中易胀气的问题，本申请提供一种电解液，其能够在电化学装置的正负极提供稳定的保护层，从而使得本申请的电化学装置能够获得良好的电化学特性，例如，良好的高温存储性能。
本申请的目的可至少通过如下技术方案实现：
一种电解液，其包含式I化合物：
Figure PCTCN2020099306-appb-000001
其中，M 1至M 5中任意一个为M 7-OLi基团；且M 1至M 5中至少一个为M 8-CN基团；其余不为M 7-OLi基团和M 8-CN基团的M 1至M 5各自独立地选自氢、经取代或未经取代的C 1-12烷氧基、卤素、经取代或未经取代的C 1-12烷基、经取代或未经取代的C 2-12烯基、经取代或未经取代的C 2-12炔基、硝基、磺酸基、醛基、羧基、硅基或经取代或未经取代的C 6-12芳基，其中当经取代时，取代基为卤素；
其中M 6、M 7和M 8各自独立地选自C 0-5亚烃基、被卤素取代的C 1-5亚烃基。
在一些实施例中，本申请的式(I)化合物包括式I-1至式I-6化合物中的至少一种：
Figure PCTCN2020099306-appb-000002
其中，R 1-R 14各自独立地选自氢、卤素、经取代或未经取代的C 1-12烷氧基、经取代或未经取代的C 1-12烷基、经取代或未经取代的C 2-12烯基、经取代或未经取代的C 2-12炔基、硝基、磺酸基、醛基、羧基、硅基或经取代或未经取代的C 6-12芳基，其中当经取代时，取代基为卤素；且n为0-5。
在一些实施例中，式I化合物包括以下化合物1至化合物16中的至少一种：
Figure PCTCN2020099306-appb-000003
Figure PCTCN2020099306-appb-000004
在一些实施例中，基于电解液的总质量，本申请所述的式I化合物的含量为约0.01％至约10％。
在一些实施例中，本申请的电解液还包含添加剂A、添加剂B或添加剂C中的至少一种，其中，所述添加剂A包含腈类化合物、酸酐类化合物、醚类化合物、磷酸酯类化合物、亚磷酸酯类化合物或硼酸酯类化合物中的至少一种；所述添加剂B包含硫酸酯类化合物、亚硫酸酯类化合物、氟代碳酸酯或不饱和碳酸酯中的至少一种；所述添加剂C包含磺酸酯类化合物、砜类化合物或锂盐添加剂中的至少一种。
在一些实施例中，基于电解液的总质量，所述添加剂A的含量为约0.01％至约10％；所述添加剂B的含量为约0.01％至约10％；所述添加剂C的含量为约0.01％至约5％。
在一些实施例中，腈类化合物包括以下化合物中的至少一种：丁二腈、己二腈、1,3,5-戊三甲腈、1,3,6-己三甲腈、1,2,6-己三甲腈、反丁烯二腈或乙二醇(双丙腈)醚；
酸酐类化合物包括以下化合物中的至少一种：柠槺酸酐、丁二酸酐、马来酸酐、三氟甲基马来酸酐、二甲基马来酸酐或丙烷磺酸酐；
醚类化合物包括以下化合物中的至少一种：1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚或全氟丁醚；
磷酸酯类化合物包括以下化合物中的至少一种：三苯基磷酸酯、三(三氟乙基)磷酸酯或磷酸三烯丙酯；
亚磷酸酯类化合物包括以下化合物中的至少一种：三苯基亚磷酸酯或三甲基硅基亚磷酸酯；
硼酸酯类化合物包括以下化合物中的至少一种：硼酸三(六氟异丙基)酯、三甲基硅基硼酸酯、硼酸三亚甲酯、硼酸三异丙酯、硼酸三丁酯、硼酸三乙酯或硼酸三丙酯；
硫酸酯类化合物包括以下化合物中的至少一种：硫酸乙烯酯、双硫酸乙烯酯、甲基硫酸乙烯酯、乙基硫酸乙烯酯或丙基硫酸乙烯酯；
亚硫酸酯类化合物包括以下化合物中的至少一种：亚硫酸乙烯酯、甲基亚硫酸乙烯酯、乙基亚硫酸乙烯酯、丙基亚硫酸乙烯酯或亚硫酸丙烯酯；
氟代碳酸酯包括以下化合物中的至少一种：氟代碳酸乙烯酯、甲基三氟乙基碳酸酯或三氟甲基碳酸乙烯酯；
不饱和碳酸酯包括以下化合物中的至少一种：碳酸乙烯亚乙酯或碳酸亚乙烯酯；
磺酸酯类化合物包括以下化合物中的至少一种：1,3-丙烷磺内酯、1,4-丁烷磺内酯、2,4-丁烷磺内酯、丙烯基-1,3-磺酸内酯、甲烷二磺酸亚甲酯或链状双磺酸酯；
砜类化合物包括以下化合物中的至少一种：环丁砜、环戊砜或3-环丁烯砜；
锂盐类添加剂包括以下化合物中的至少一种：4,5-二氰基-2-(三氟甲基)咪唑锂、二氟磷酸锂、四氟硼酸锂、双氟磺酰亚胺锂、双三氟磺酰亚胺锂、草酸硼酸锂或双氟草酸硼酸锂。
本申请还提供一种电化学装置，其包含正极和根据本申请的电解液，正极包括正极活性材料。
在一些实施例中，正极活性材料包含选自Al、Zr或Mg中的至少一种元素。
在一些实施例中，基于正极活性材料总质量，Al的含量a小于1％，Zr的含量b小于1％，Mg的含量c小于0.5％。
在一些实施例中，正极材料包含Al和Mg，并且其含量满足以下条件：0.005<a/c<500。
本申请还提供一种电子装置，其包含根据本申请的电化学装置。
具体实施方式
本申请的实施例将会被详细的描示在下文中。在此所描述的有关实施例为说明性质的且用于提供对本申请的基本理解。本申请的实施例不应该被解释为对本申请的限制。
如本文中所使用，术语“约”用以描述及说明小的变化。当与事件或情形结合使用时，所述术语可指代其中事件或情形精确发生的例子以及其中事件或情形极近似地发生的例子。举例来说，当结合数值使用时，术语可指代小于或等于所述数值的±10％的变化范围，例如小于或等于±5％、小于或等于±4％、小于或等于±3％、小于或等于±2％、小于或等于±1％、小于或等于±0.5％、小于或等于±0.1％、或小于或等于±0.05％。举例来说，如果两个数值之间的差值小于或等于所述值的平均值的±10％(例如小于或等于±5％、小于或等于±4％、小于或等于±3％、小于或等于±2％、小于或等于±1％、小于或等于±0.5％、小于或等于±0.1％、或小于或等于±0.05％)，那么可认为所述两个数值“约”相同。
另外，有时在本文中以范围格式呈现量、比率和其它数值。应理解，此类范围格式是用于便利及简洁起见，且应灵活地理解，不仅包含明确地指定为范围限制的数值，而且包含涵盖于所述范围内的所有个别数值或子范围，如同明确地指定每一数值及子范围一般。
在具体实施方式及权利要求书中，由术语“中的一者”、“中的一个”、“中的一种”或其他相似术语所连接的项目的列表可意味着所列项目中的任一者。例如，如果列出项目A及B，那么短语“A及B中的一者”意味着仅A或仅B。在另一实例中，如果列出项目A、B及C，那么短语“A、B及C中的一者”意味着仅A；仅B；或仅C。项目A可包含单个元件或多个元件。项目B可包含单个元件或多个元件。项目C可包含单个元件或多个元件。
在具体实施方式及权利要求书中，由术语“中的至少一者”、“中的至少一个”、“中的至少一种”或其他相似术语所连接的项目的列表可意味着所列项目的任何组合。例如，如果列出项目A及B，那么短语“A及B中的至少一者”意味着仅A；仅B；或A及B。在另一实例中，如果列出项目A、B及C，那么短语“A、B及C中的至少一者”意味着仅A；或仅B；仅C；A及B(排除C)；A及C(排除B)；B及C(排除A)；或A、B及C的全部。项目A可包含单个元件或多个元件。项目B可包含单个元件或多个元件。项目C可包含单个元件或多个元件。
本申请中使用下列定义(除非另外明确地说明)：
为简单起见，“Cn-m”基团是指具有“n”至“m”个碳原子的基团，其中“n”和“m”是整数。例如，“C 1-12”烃基是具有1至12个碳原子的烃基，“C 0”亚烃基是指共价键。
术语“烃基”涵盖烷基、烯基、炔基、环烷基、芳基。例如，烃基预期是具有1至20个碳原子的直链烃结构。“烃基”还预期是具有3至20个碳原子的支链或环状烃结构。当指定具有具体碳数的烃基时，预期涵盖具有该碳数的所有几何异构体。本文中烃基还可以为1至15个碳原子的烃基、1至10个碳原子的烃基、1至5个碳原子的烃基、5至20个碳原子的烃基、5至15个碳原子的烃基或5至10个碳原子的烃基。另外，烃基可以是任选地被取代的。例如，烃基可被包括氟、氯、溴和碘在内的卤素、烷基、芳基或杂芳基取代。
术语“亚烃基”是指将本申请化合物中的芳基与-OLi或-CN基团连接的直链或支链二价烃基，其中烃基的定义如上文所述。示例性的亚烃基包括但不限于：亚甲基、亚乙基、亚丙基、亚正丁基、亚乙烯基、亚丙烯基、亚正丁烯基、亚丙炔基、亚正丁炔基等。亚烃基与芳基母核以及与-OLi或-CN基团的连接点可以是该亚烃基中的一个碳或任意两个碳。除说明书中另有具体说明外，亚烃基是任选取代的。
术语“烃氧基”指L-O-基团，其中L为烷基、烯基、炔基、环烷基、芳基。本文中烃氧基可为1至20个碳原子的烃氧基，还可以为1至15个碳原子的烃氧基、1至10个碳原子的烃氧基、1至5个碳原子的烃氧基、5至20个碳原子的烃氧基、5至15个碳原子的烃氧基或5至10个碳原子的烃氧基。
术语“烷基”预期是具有1至20个碳原子的直链饱和烃结构。“烷基”还预期是具有3至20个碳原子的支链或环状烃结构。例如，烷基可为1至20个碳原子的烷基、1至10个碳原子的烷基、1至5个碳原子的烷基、5至20个碳原子的烷基、5至15个碳原子的烷基或5至10个碳原子的烷基。当指定具有具体碳数的烷基时，预期涵盖具有该碳数的所有几何异构体；因此，例如，“丁基”意思是包括正丁基、仲丁基、异丁基、叔丁基和环丁基；“丙基”包括正丙基、异丙基和环丙基。烷基实例包括，但不限于甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、环丁基、正戊基、异戊基、新戊基、环戊基、甲基环戊基、乙基环戊基、正己基、异己基、环己基、正庚基、辛基、环丙基、环丁基、降冰片基等。另外，烷基可以是任选地被取代的。
术语“环烷基”涵盖环状烷基。环烷基可为3至20个碳原子的环烷基、6至20个 碳原子的环烷基、3至10个碳原子的环烷基、3至6个碳原子的环烷基。例如，环烷基可为环丙基、环丁基、环戊基、环己基等。另外，环烷基可以是任选地被取代的。
术语“烯基”是指可为直链或具支链且具有至少一个且通常1个、2个或3个碳碳双键的单价不饱和烃基团。除非另有定义，否则所述烯基通常含有2至20个碳原子，例如可以为2至20个碳原子的烯基、6至20个碳原子的烯基、2至10个碳原子的烯基或2至6个碳原子的烯基。代表性烯基包括(例如)乙烯基、正丙烯基、异丙烯基、正-丁-2-烯基、丁-3-烯基、正-己-3-烯基等。另外，烯基可以是任选地被取代的。
术语“炔基”是指可为直链或具支链且具有至少一个且通常具有1个、2个或3个碳碳三键的单价不饱和烃基团。除非另有定义，否则所述炔基通常含有2至20个碳原子，例如可以为2至20个碳原子的炔基、6至20个碳原子的炔基、2至10个碳原子的炔基或2至6个碳原子的炔基。代表性炔基包括(例如)乙炔基、丙-2-炔基(正-丙炔基)、正-丁-2-炔基、正-己-3-炔基等。另外，炔基可以是任选地被取代的。
术语“芳基”涵盖单环系统和多环系统。多环可以具有其中两个碳为两个邻接环(所述环是“稠合的”)共用的两个或更多个环，其中所述环中的至少一者是芳香族的，例如其它环可以是环烷基、环烯基、芳基、杂环和/或杂芳基。例如，芳基可为C 6-50芳基、C 6-40芳基、C 6-30芳基、C 6-20芳基或C 6-10芳基。代表性芳基包括(例如)苯基、甲基苯基、丙基苯基、异丙基苯基、苯甲基和萘-1-基、萘-2-基等等。另外，芳基可以是任选地被取代的。
术语“杂环基”涵盖芳香族和非芳香族环状基团。杂芳香族环状基团还意指杂芳基。在一些实施例中，杂芳香族环基团和杂非芳香族环基团为包括至少一个杂原子的C 1-50杂环基、C 1-40杂环基、C 1-30杂环基、C 1-20杂环基、C 1-10杂环基、C 1-6杂环基。例如吗啉基、哌啶基、吡咯烷基等，以及环醚，例如四氢呋喃、四氢吡喃等。另外，杂环基可以是任选地被取代的。
如本文所用，术语“杂芳基”涵盖可以包括一到三个杂原子的单环杂芳香族基团，例如吡咯、呋喃、噻吩、咪唑、噁唑、噻唑、三唑、吡唑、吡啶、吡嗪和嘧啶等。术语杂芳基还包括具有其中两个原子为两个邻接环(所述环是“稠合的”)共用的两个或更多个环的多环杂芳香族系统，其中所述环中的至少一者是杂芳基，其它环可以是环烷基、环烯基、芳基、杂环和/或杂芳基。例如杂芳基可为C 6-50杂芳基、C 6-40杂芳基、C 6-30杂芳基、C 6-20杂芳基或C 6-10杂芳基。另外，杂芳基可以是任选地被取代的。
如本文所用，术语“杂原子”涵盖O、S、P、N、B或其电子等排体。
如本文所用，术语“卤素”可为F、Cl、Br或I。
如本文所用，术语“氰基”涵盖含有机基团CN的有机物。
当上述取代基经取代时，取代基可选自由以下组成的群组：卤素、烷基、环烷基、烯基、芳基和杂芳基。
一、电解液
1、式I化合物
本申请提供一种电解液，其包含式I化合物：
Figure PCTCN2020099306-appb-000005
其中，M 1至M 5中任意一个为M 7-OLi基团；且M 1至M 5中至少一个为M 8-CN基团；其余不为M 7-OLi基团和M 8-CN基团的M 1至M 5各自独立地选自氢、C 1-12烷氧基、卤素、经取代或未经取代的C 1-12烷基、经取代或未经取代的C 2-12烯基、经取代或未经取代的C 2-12炔基、硝基、磺酸基、醛基、羧基、硅基或经取代或未经取代的C 6-12芳基，其中当经取代时，取代基为卤素；其中M 6、M 7和M 8各自独立地选自C 0-5亚烃基、被卤素取代的C 1-5亚烃基。
在一些实施例中，上述式I化合物的M 1至M 5中包括一个、两个或三个M 8-CN基团。
在根据本申请所述的式I化合物中，“C 0-5亚烃基”包括但不限于：共价键、甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、乙烯基、乙炔基、丙烯基、丙炔基。
在一些实施例中，本申请的式I化合物包括式I-1至式I-6化合物中的至少一种：
Figure PCTCN2020099306-appb-000006
Figure PCTCN2020099306-appb-000007
其中，R 1至R 14各自独立地选自氢、卤素、经取代或未经取代的C 1-12烷氧基、经取代或未经取代的C 1-12烷基、经取代或未经取代的C 2-12烯基、经取代或未经取代的C 2-12炔基、硝基、磺酸基、醛基、羧基、硅基或经取代或未经取代的C 6-12芳基，其中当经取代时，取代基为卤素；且n为0-5。
在一些实施例中，式I-1至式I-6化合物中的R 1至R 14各自独立地选自：氢、经取代或未经取代的C 1-12烷基、经取代或未经取代的C 2-12烯基或经取代或未经取代的C 2-12炔基。
在一些实施例中，式I化合物包括以下化合物1至化合物16中的至少一种：
Figure PCTCN2020099306-appb-000008
Figure PCTCN2020099306-appb-000009
在一些实施例中，基于电解液的总质量，本申请所述的式I化合物的含量为约0.01％至约10％，例如，式I化合物的含量可以为0.01％、0.05％、1.0％、2.0％、3.0％、4.0％、4.5％、5.0％、5.5％、6.0％、6.5％、7.0％、8.0％、9.0％、10％，或者为上述含量任意两者之间的范围，当添加量低于0.01％时，因浓度太低，导致添加剂无法有效在界面成膜，而当高于含量高于10％时，则会导致负极界面严重析锂，同时因在成膜过程消耗大量导电锂盐，使常温循环的放电容量偏低，影响电池的实际容量发挥。
2、其他添加剂
在一些实施例中，本申请的电解液还包含添加剂A、添加剂B或添加剂C中的至少一种，其中，添加剂A包含腈类化合物、酸酐类化合物、醚类化合物、磷酸酯类化合物、亚磷酸酯类化合物或硼酸酯类化合物中的至少一种；添加剂B包含硫酸酯类化合物、亚硫酸酯类化合物、氟代碳酸酯或不饱和碳酸酯中的至少一种；添加剂C包含磺酸酯类化合物、砜类化合物或锂盐添加剂中的至少一种。
在一些实施例中，本申请的电解液可以包含上述式I化合物与以下添加剂中任意一种、两种或三种的组合：不饱和碳酸酯，例如，碳酸乙烯亚乙酯或碳酸亚乙烯酯；磺酸酯类化合物，例如，1,3-丙烷磺内酯；硫酸酯类化合物，例如，硫酸乙烯酯；氟代碳酸酯化合物，例如，氟代碳酸乙烯酯；锂盐类添加剂，例如，二氟磷酸锂；腈类化合物，例如，丁二腈和己二腈。
在一些实施例中，基于电解液的总质量，上述添加剂A和添加剂B的含量各自可以为约0.01％至约10％；例如，添加剂A和添加剂B的含量各自可以为0.01％、0.05％、1.0％、2.0％、3.0％、4.0％、4.5％、5.0％、5.5％、6.0％、6.5％、7.0％、8.0％、9.0％、10％，或者为上述含量任意两者之间的范围。
在一些实施例中，基于电解液的总质量，添加剂C的含量为约0.01％至约5％；例如，添加剂C的含量可以为0.01％、0.05％、1.0％、1.5％、2.0％、2.5％、3.0％、3.5％、4.0％、 4.5％、5.0％，或者为上述含量任意两者之间的范围。
在一些实施例中，上述添加剂A、添加剂B和添加剂C的总含量不超过20％。
(1)添加剂A
在一些实施例中，腈类化合物包括以下化合物中的至少一种：丁二腈、己二腈、1,3,5-戊烷三甲腈、1,3,6-己烷三甲腈、1,2,6-己烷三甲腈、反丁烯二腈或乙二醇(双丙腈)醚。
在一些实施例中，酸酐类化合物包括以下化合物中的至少一种：柠槺酸酐、丁二酸酐、马来酸酐、三氟甲基马来酸酐、二甲基马来酸酐或丙烷磺酸酐。
在一些实施例中，醚类化合物包括以下化合物中的至少一种：1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚或全氟丁醚。
在一些实施例中，磷酸酯类化合物包括以下化合物中的至少一种：三苯基磷酸酯、三(三氟乙基)磷酸酯或磷酸三烯丙酯。
在一些实施例中，亚磷酸酯类化合物包括以下化合物中的至少一种：三苯基亚磷酸酯或三甲基硅基亚磷酸酯。
在一些实施例中，硼酸酯类化合物包括以下化合物中的至少一种：硼酸三(六氟异丙基)酯、三甲基硅基硼酸酯、硼酸三亚甲酯、硼酸三异丙酯、硼酸三丁酯、硼酸三乙酯或硼酸三丙酯。
添加剂A可在阴极形成有效钝化层，且该钝化层对SEI(solid electrolyte interface)阻抗的影响较小，对离子和电子都具有较好的导通性，与式Ⅰ化合物组合使用，对正负极界面都具有较好的保护效果。
(2)添加剂B
在一些实施例中，硫酸酯类化合物包括以下化合物中的至少一种：硫酸乙烯酯、双硫酸乙烯酯、甲基硫酸乙烯酯、乙基硫酸乙烯酯或丙基硫酸乙烯酯。
在一些实施例中，亚硫酸酯类化合物包括以下化合物中的至少一种：亚硫酸乙烯酯、甲基亚硫酸乙烯酯、乙基亚硫酸乙烯酯、丙基亚硫酸乙烯酯或亚硫酸丙烯酯。
在一些实施例中，氟代碳酸酯包括以下化合物中的至少一种：氟代碳酸乙烯酯、甲基三氟乙基碳酸酯或三氟甲基碳酸乙烯酯。
在一些实施例中，不饱和碳酸酯包括以下化合物中的至少一种：碳酸乙烯亚乙酯或碳酸亚乙烯酯。
添加剂B可在负极界面形成有效界面保护，与式Ⅰ化合物共同作用，可保证电池在 初始状态具有较稳定的CEI(cathode electrolyte interface)保护层，同时在长期的高温存储和循环过程中持续对表层CEI进行修复，从而有效改善电池的长期存储和循环性能。
(3)添加剂C
在一些实施例中，磺酸酯类化合物包括以下化合物中的至少一种：1,3-丙烷磺内酯、1,4-丁烷磺内酯、2,4-丁烷磺内酯、丙烯基-1,3-磺酸内酯、甲烷二磺酸亚甲酯或链状双磺酸酯。
在一些实施例中，砜类化合物包括以下化合物中的至少一种：环丁砜、环戊砜或3-环丁烯砜。
在一些实施例中，锂盐类添加剂包括以下化合物中的至少一种：4,5-二氰基-2-(三氟甲基)咪唑锂、二氟磷酸锂、四氟硼酸锂、双氟磺酰亚胺锂、双三氟磺酰亚胺锂、草酸硼酸锂或双氟草酸硼酸锂。
添加剂C与式Ⅰ化合物共同作用，可在正负极界面都形成有效钝化层，且添加剂氧化还原活性较低，可持续在界面缓慢反应，在长期的高温存储和循环过程中持续对表层CEI和SEI进行修复，从而有效改善电池的长期存储和循环性能。3、其他
在一些实施例中，本申请的电解液还包含有机溶剂，其选自环状碳酸酯、链状碳酸酯、羧酸酯或砜类溶剂中的至少一种。
在一些实施例中，环状碳酸酯选自碳酸乙烯酯或碳酸丙烯酯中的至少一种；链状碳酸酯选自碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯或碳酸乙丙酯中的至少一种；羧酸酯选自乙酸乙酯、丙酸乙酯、丙酸丙酯、乙酸丙酯、二氟乙酸乙酯或乙酸二氟乙酯中的至少一种；砜类溶剂选自环丁砜、正丁砜、环戊砜、环己砜、2,4-二甲基环丁砜、3-甲基-3-环丁烯砜、正丁基亚砜、二正辛砜四甲基亚砜中的至少一种。
二、电化学装置
本申请还提供一种电化学装置，其包含根据本申请的电解液。
本申请的电化学装置包括发生电化学反应的任何装置，它的具体实例包括所有种类的一次电池、二次电池、燃料电池、太阳能电池或电容。特别地，所述电化学装置是锂二次电池，包括锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池。在一些实施例中，所述电化学装置是锂离子电池。
正极
根据本申请的电化学装置还可包括正极，其包括集流体和设置在集流体上的正极活性材料层。正极活性材料包含选自Al、Zr或Mg中的至少一种元素。例如，正极活性材料可以包括Al和Zr、Al和Mg、Zr和Mg、或者Al、Zr和Mg的组合。
在一些实施例中，基于正极活性材料总质量，Al的含量a小于1％，例如，Al的含量a可以小于0.9％、小于0.8％、小于0.7％、小于0.6％、小于0.5％、或者为上述数值任意两者之间或上述任意数值与零之间的范围。
在一些实施例中，基于正极活性材料总质量，Zr的含量b小于1％，例如，Zr的含量b可以小于0.9％、小于0.8％、小于0.7％、小于0.6％、小于0.5％、或者为上述数值任意两者之间或上述任意数值与零之间的范围。
在一些实施例中，基于正极活性材料总质量，Mg的含量c小于0.5％，例如，Mg的含量c可以小于0.5％、小于0.4％、小于0.3％、小于0.2％、小于0.1％、或者为上述数值任意两者之间或上述任意数值与零之间的范围。
在一些实施例中，正极材料包含Al和Mg，并且其含量满足以下条件：0.005<a/c<500。例如，a/c的比值可以为0.004、0.01、0.1、1、10、20、50、80、100、120、140、180、200、230、250、270、300、350、400、420、450、499等。Al和Mg含量在此范围内，能更加有效的提高电池整体性能。
在一些实施例中，正极活性材料包括可逆地嵌入和脱嵌锂离子的化合物。在一些实施例中，正极活性材料可以包括复合氧化物，所述复合氧化物含有锂以及从钴、锰和镍中选择的至少一种元素。在又一些实施例中，正极活性材料选自钴酸锂(LiCoO 2)、锂镍锰钴三元材料、锰酸锂(LiMn 2O 4)、镍锰酸锂(LiNi 0.5Mn 1.5O 4)或磷酸铁锂(LiFePO 4)中的至少一种。
在一些实施例中，正极活性材料层可以在表面上具有涂层，或者可以与具有涂层的另一化合物混合。
在一些实施例中，所述涂层可以包括从涂覆元素的氧化物、涂覆元素的氢氧化物、涂覆元素的羟基氧化物、涂覆元素的碳酸氧盐(oxycarbonate)或涂覆元素的羟基碳酸盐(hydroxycarbonate)中选择的至少一种涂覆元素化合物。
用于涂层的化合物可以是非晶的或结晶的。
在一些实施例中，在涂层中含有的涂覆元素可以包括Mg、Al、Co、K、Na、Ca、Si、Ti、V、Sn、Ge、Ga、B、As、Zr、F或它们的混合物中的至少一种。
可以通过任何方法来施加涂层，只要所述方法不对正极活性材料的性能产生不利影响即可。例如，所述方法可以包括对本领域普通技术人员来说众所周知的任何涂覆方法，例如喷涂、浸渍等。
在一些实施例中，正极活性材料层还包含粘合剂，并且可选地还包括导电材料。
粘合剂可提高正极活性材料颗粒彼此间的结合，并且还可提高正极活性材料与集流体的结合。在一些实施例中，粘合剂的非限制性示例包括聚乙烯醇、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧化的聚氯乙烯、聚氟乙烯、含亚乙基氧的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏1,1-二氟乙烯、聚乙烯、聚丙烯、丁苯橡胶、丙烯酸(酯)化的丁苯橡胶、环氧树脂、尼龙等。
正极活性材料层还可包括导电材料，从而赋予电极导电性。所述导电材料可以包括任何导电材料，只要它不引起不想要的化学变化。在一些实施例中，导电材料的非限制性示例包括基于碳的材料(例如，天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维等)、基于金属的材料(例如，金属粉、金属纤维等，包括例如铜、镍、铝、银等)、导电聚合物(例如，聚亚苯基衍生物)和它们的混合物。
在一些实施例中，用于根据本申请的二次电池的正极的集流体可以是铝(Al)，但不限于此。
负极
根据本申请的电化学装置还可包括负极，其包括集流体和设置在集流体上的负极活性材料层。负极活性材料的具体种类均不受到具体的限制，可根据需求进行选择。
具体地，在一些实施例中，所述负极活性材料选自天然石墨、人造石墨、中间相微碳球(简称为MCMB)、硬碳、软碳、硅、硅-碳复合物、Li-Sn合金、Li-Sn-O合金、Sn、SnO、SnO 2、尖晶石结构的锂化TiO 2-Li 4Ti 5O 12或Li-Al合金中的至少一种。
在一些实施例中，碳材料的非限制性示例包括结晶碳、非晶碳和它们的混合物。结晶碳可以是无定形的或片形的、小片形的、球形的或纤维状的天然石墨或人造石墨。非晶碳可以是软碳、硬碳、中间相沥青碳化物、煅烧焦等。
在一些实施例中，负极活性材料层可以包含粘合剂，并且可选地还包括导电材料。
粘合剂可提高负极活性材料颗粒彼此间的结合和负极活性材料与集流体的结合。在一些实施例中，粘合剂的非限制性示例包括聚乙烯醇、羧甲基纤维素、羟丙基纤维素、二乙酰基 纤维素、聚氯乙烯、羧化的聚氯乙烯、聚氟乙烯、含亚乙基氧的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏1,1-二氟乙烯、聚乙烯、聚丙烯、丁苯橡胶、丙烯酸(酯)化的丁苯橡胶、环氧树脂、尼龙等。
负极活性材料层可包括导电材料，从而赋予电极导电性。所述导电材料可以包括任何导电材料，只要它不引起不想要的化学变化。在一些实施例中，导电材料的非限制性示例包括基于碳的材料(例如，天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维等)、基于金属的材料(例如，金属粉、金属纤维等，例如铜、镍、铝、银等)、导电聚合物(例如，聚亚苯基衍生物)和它们的混合物。
在一些实施例中，用于本申请所述的负极的集流体可以选自铜箔、镍箔、不锈钢箔、钛箔、泡沫镍、泡沫铜、覆有导电金属的聚合物基底和它们的组合。
隔离膜
在一些实施例中，本申请的电化学装置在正极与负极之间设有隔离膜以防止短路。本申请的电化学装置中使用的隔离膜的材料和形状没有特别限制。在一些实施例中，隔离膜包括由对本申请的电解液稳定的材料形成的聚合物或无机物等。
例如，隔离膜可包括基材层和表面处理层。
在一些实施例中，基材层为具有多孔结构的无纺布、膜或复合膜，基材层的材料选自聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯或聚酰亚胺中的至少一种。具体的，在一些实施例中，可选用聚丙烯多孔膜、聚乙烯多孔膜、聚丙烯无纺布、聚乙烯无纺布或聚丙烯-聚乙烯-聚丙烯多孔复合膜。
在一些实施例中，基材层的至少一个表面上设置有表面处理层，表面处理层可以是聚合物层或无机物层，也可以是混合聚合物与无机物所形成的层。
在一些实施例中，无机物层包括无机颗粒和粘结剂。在一些实施例中，无机颗粒选自氧化铝、氧化硅、氧化镁、氧化钛、二氧化铪、氧化锡、二氧化铈、氧化镍、氧化锌、氧化钙、氧化锆、氧化钇、碳化硅、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙或硫酸钡中的至少一种。在一些实施例中，粘结剂选自聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯或聚六氟丙烯中的至少一种。
聚合物层中包含聚合物。在一些实施例中，聚合物的材料选自聚酰胺、聚丙烯腈、丙烯酸酯聚合物、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚偏氟乙烯或聚(偏氟乙烯-六氟丙烯)中的至少一种。
三.电子装置
本申请还提供一种电子装置，其包括根据本申请的电化学装置。
根据本申请的电化学装置适用于各种领域的电子设备。本申请的电化学装置的用途没有特别限定，其可用于现有技术中已知的任何用途。在一个实施例中，本申请的电化学装置可用于，但不限于以下电子装置：笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
本申请实现了以下意料不到的技术效果：本申请提供的式I化合物在化成过程中，容易在正负极表面形成非常稳定的CEI和SEI保护膜。该保护膜与基体充分融合，在负极上，该保护膜可提供与锂离子的络合点，因此可以进行快速的离子传输，同时能够有效抑制电解质因不可逆还原而在负极上的大量沉积。在正极上，该保护膜可减少正极与电解液的反应，同时抑制金属离子溶出，最终改善电化学装置(例如，锂离子电池)的高温存储性能。此外，本申请的电化学装置通过控制正极材料中掺杂元素Al、Zr、Mg含量，并在此基础上加入式I化合物，可使本申请的电解液在正负极上的成膜效果更好，使得所形成的保护膜具有更优异的高温稳定性，从而进一步提高本申请的电化学装置(例如，锂离子电池)的高温存储性能。
四、实施例
下面结合实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。
实施例
1、制备方法
(1)电解液的制备
在干燥房中，将碳酸乙烯酯、碳酸丙烯酯和碳酸二乙酯按1:1:1的质量比混合均匀， 得到非水有机溶剂。向非水有机溶剂中加入1mol/L六氟磷酸锂(LiPF 6)，得到基础电解液。在该基础电解液中，根据下文表格中提供的用量和种类分别添加其他添加剂以得到各个实施例和对比例的电解液。
(2)正极制备
将正极活性材料、粘结剂聚偏二氟乙烯(PVDF)和导电剂Super-P按质量比96:2:2溶于N-甲基吡咯烷酮(NMP)中混合均匀制成正极浆料。将正极浆料均匀地涂布在厚度为12μm的正极集流体铝箔上，120℃烘烤1h得到正极活性材料层，之后经过压实、分切、焊接极耳得到正极。
(3)负极制备
将负极活性材料石墨粉末、氧化硅粉末、羧甲基纤维素钠增稠剂(CMC)和粘结剂丁苯橡胶按质量比81:15:2:2溶于水中，充分混合搅拌得到负极浆料，将负极浆料均匀地涂布在厚度为12μm的负极集流体铜箔上，在120℃烘烤1h，之后经过压实得到负极活性材料层，之后分切、焊接极耳得到负极。
(4)电池的制备
以12μm的聚丙烯薄膜作为隔离膜。将正极、隔离膜、负极按顺序叠好，使隔离膜处于正负极中间起到隔离的作用，然后卷绕成方形的裸电芯。将裸电芯装入铝箔包装袋，在80℃烘烤除水后，注入相应电解液，经过真空封装、静置、化成、整形等工序，即完成锂离子电池的制备。
2、测试方法
使用以下方法测试实施例和对比例中所制备锂离子电池的性能。
(1)高温存储测试
存储前，以恒定电流0.5C充电至3.65V，然后用厚度测试仪测试电池厚度，得到D1，继续0.5C充电至4.2V，恒压充电至电流为0.05C，然后将锂离子电池置于60℃高温箱中存储30天，待电池冷却后再次测量其厚度，得到D2：
电池厚度增长率＝(D2－D1)÷D1×100％
(2)45℃循环测试：
将电池放置在45℃烘箱中，以恒定电流0.5C充电至4.2V，恒压充电至电流为0.05C， 0.5C放电至2.8V，循环400周：
电池容量保持率＝第400圈放电容量÷首圈放电容量×100％
3、测试结果
实施例1至23和对比例1
实施例1至23和对比例1中使用的正极材料为三元镍钴锰(LiNi 0.8Co 0.1Mn 0.1O 2，NCM811)，其中，Al的掺杂量为0.15％，Zr的掺杂量0.007％，Mg的掺杂量为0.1％。具体测试结果如以下表1所示。
表1.实施例1至23和对比例1的测试结果
Figure PCTCN2020099306-appb-000010
Figure PCTCN2020099306-appb-000011
上表中的实施例1至23添加不同含量及不同类型的式I化合物，对比例1未添加式I化合物。由上表中的数据可以看出，当电解液中不添加根据本申请的式I化合物时，电池高温存储的厚度增长率为45％，而添加了式I化合物后，电池的厚度增长得到明显改善，原因归结于本申请的式I化合物在化成的过程中，能够在正负极表面均产生稳定的保护膜，从而减少电池在高温存储过程中正负极与电解液的进一步反应，最终达到减少存储胀气和改善高温存储性能的目的。
实施例1至7分别在电解液中添加不同含量的化合物1。由实施例1至7的测试结果可以看出，当式I化合物的用量在0.01重量％至10重量％的范围内时，可保证完全溶解，从而提供良好的成膜效果并且明显地改善电化学装置的高温存储性能。当式I化合物的用量超出本申请的范围时，则改善效果不明显。一方面，当式I化合物的用量过高时，其不能完全溶解，未起到成膜保护作用；另一方面，式I化合物含量过高易降低或阻止电解液中其它改善存储的添加剂反应成膜，削弱正负极保护，导致高温存储性能的改善不明显。
由实施例17至23的测试结果可以看出，不同式I化合物的组合使用也同样能够改善电化学装置的高温存储性能。
实施例24至52
实施例24至52举例示出本申请的式I化合物与其他添加剂组合使用的实例，其中，使用的正极材料为三元镍钴锰(LiNi 0.8Co 0.1Mn 0.1O 2，NCM811)，其中，Al的掺杂量为0.15％，Zr的掺杂量0.007％，Mg的掺杂量为0.1％。具体测试结果如以下表2所示。
表2.实施例24至52的测试结果
Figure PCTCN2020099306-appb-000012
Figure PCTCN2020099306-appb-000013
实施例24至52表明本申请的式I化合物与其他类型的添加剂可以组合使用以进一步改善电化学装置的高温存储和循环性能。
例如，从上表中的测试结果可以看出，在式I化合物的基础上，额外添加以下化合物中的的一种、两种或三种都可以实现更进一步的改善效果：VC(碳酸亚乙烯酯)、PS(1,3-丙烷磺内酯)、DTD(硫酸乙烯酯)、FEC(氟代碳酸乙烯酯)、Li 2PO 2F 2(二氟磷酸锂)、ADN(己二腈)、SN(丁二腈)、HTCN(1,3,6-己三甲腈)或酸酐，这些组合可以实现更优异的高温存储性能和/或循环性能。
实施例53至69
实施例53至69中使用的正极材料为三元镍钴锰(LiNi 0.5Co 0.2Mn 0.3O 2，NCM523)，其中各元素的掺杂量如以下表3中所示。
表3.实施例53至69的测试结果
Figure PCTCN2020099306-appb-000014
Figure PCTCN2020099306-appb-000015
由上表中实施例53至69的测试结果可以看出，当正极材料中Al的掺杂量a<1％，Zr的掺杂量b<1％，Mg的掺杂量c<0.5％时，电池具有较好的高温存储性能和循环性能。
整个说明书中对“一些实施例”、“部分实施例”、“一个实施例”、“另一举例”、“举例”、“具体举例”或“部分举例”的引用，其所代表的意思是在本申请中的至少一个实施例或举例包含了该实施例或举例中所描述的特定特征、结构、材料或特性。因此，在整个说明书中的各处所出现的描述，例如：“在一些实施例中”、“在实施例中”、“在一个实施例中”、“在另一个举例中”，“在一个举例中”、“在特定举例中”或“举例“，其不必然是引用本申请中的相同的实施例或示例。此外，本文中的特定特征、结构、材料或特性可以以任何合适的方式在一个或多个实施例或举例中结合。
尽管已经演示和描述了说明性实施例，本领域技术人员应该理解上述实施例不能被解释为对本申请的限制，并且可以在不脱离本申请的精神、原理及范围的情况下对实施例进行改变，替代和修改。

Claims (11)

  1. 一种电解液，其包含式I化合物：
    Figure PCTCN2020099306-appb-100001
    其中，M 1至M 5中任意一个为M 7-OLi基团；且M 1至M 5中至少一个为M 8-CN基团；其余不为M 7-OLi基团和M 8-CN基团的M 1至M 5各自独立地选自氢、经取代或未经取代的C 1-12烷氧基、卤素、经取代或未经取代的C 1-12烷基、经取代或未经取代的C 2-12烯基、经取代或未经取代的C 2-12炔基、硝基、磺酸基、醛基、羧基、硅基或经取代或未经取代的C 6-12芳基，其中当经取代时，取代基为卤素；
    其中M 6、M 7和M 8各自独立地选自C 0-5亚烃基、被卤素取代的C 1-5亚烃基。
  2. 根据权利要求1所述的电解液，其中所述式(I)化合物包括式I-1至式I-6化合物中的至少一种：
    Figure PCTCN2020099306-appb-100002
    其中，R 1至R 14各自独立地选自氢、卤素、经取代或未经取代的C 1-12烷氧基、经取代或未经取代的C 1--12烷基、经取代或未经取代的C 2-12烯基、经取代或未经取代的C 2-12炔基、硝 基、磺酸基、醛基、羧基、硅基或经取代或未经取代的C 6-12芳基，其中当经取代时，取代基为卤素；且n为0-5的整数。
  3. 根据权利要求1所述的电解液，其中所述式I化合物包括以下化合物中的至少一种：
    Figure PCTCN2020099306-appb-100003
  4. 根据权利要求1所述的电解液，其中基于所述电解液的总质量，所述式I化合物的含量为0.01％至10％。
  5. 根据权利要求1-4中任一权利要求所述的电解液，其还包含添加剂A、添加剂B或添加剂C中的至少一种，其中，所述添加剂A包含腈类化合物、酸酐类化合物、醚类化合物、磷酸酯类化合物、亚磷酸酯类化合物或硼酸酯类化合物中的至少一种；所述添 加剂B包含硫酸酯类化合物、亚硫酸酯类化合物、氟代碳酸酯或不饱和碳酸酯中的至少一种；所述添加剂C包含磺酸酯类化合物、砜类化合物或锂盐添加剂中的至少一种；且
    基于所述电解液的总质量，所述添加剂A的含量为0.01％至10％；所述添加剂B的含量为0.01％至10％；所述添加剂C的含量为0.01％至5％。
  6. 根据权利要求5所述的电解液，其中：
    所述腈类化合物包括以下化合物中的至少一种：丁二腈、己二腈、1,3,5-戊烷三甲腈、1,3,6-己烷三甲腈、1,2,6-己烷三甲腈、反丁烯二腈或乙二醇(双丙腈)醚；
    所述酸酐类化合物包括以下化合物中的至少一种：柠槺酸酐、丁二酸酐、马来酸酐、三氟甲基马来酸酐、二甲基马来酸酐或丙烷磺酸酐；
    所述醚类化合物包括以下化合物中的至少一种：1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚或全氟丁醚；
    所述磷酸酯类化合物包括以下化合物中的至少一种：三苯基磷酸酯、三(三氟乙基)磷酸酯或磷酸三烯丙酯；
    所述亚磷酸酯类化合物包括以下化合物中的至少一种：三苯基亚磷酸酯或三甲基硅基亚磷酸酯；
    所述硼酸酯类化合物包括以下化合物中的至少一种：硼酸三(六氟异丙基)酯、三甲基硅基硼酸酯、硼酸三亚甲酯、硼酸三异丙酯、硼酸三丁酯、硼酸三乙酯或硼酸三丙酯；
    所述硫酸酯类化合物包括以下化合物中的至少一种：硫酸乙烯酯、双硫酸乙烯酯、甲基硫酸乙烯酯、乙基硫酸乙烯酯或丙基硫酸乙烯酯；
    所述亚硫酸酯类化合物包括以下化合物中的至少一种：亚硫酸乙烯酯、甲基亚硫酸乙烯酯、乙基亚硫酸乙烯酯、丙基亚硫酸乙烯酯或亚硫酸丙烯酯；
    所述氟代碳酸酯包括以下化合物中的至少一种：氟代碳酸乙烯酯、甲基三氟乙基碳酸酯或三氟甲基碳酸乙烯酯；
    所述不饱和碳酸酯包括以下化合物中的至少一种：碳酸乙烯亚乙酯或碳酸亚乙烯酯；
    所述磺酸酯类化合物包括以下化合物中的至少一种：1,3-丙烷磺内酯、1,4-丁烷磺内酯、2,4-丁烷磺内酯、丙烯基-1,3-磺酸内酯、甲烷二磺酸亚甲酯或链状双磺酸酯；
    所述砜类化合物包括以下化合物中的至少一种：环丁砜、环戊砜或3-环丁烯砜；
    所述锂盐类添加剂包括以下化合物中的至少一种：4,5-二氰基-2-(三氟甲基)咪唑锂、二氟磷酸锂、四氟硼酸锂、双氟磺酰亚胺锂、双三氟磺酰亚胺锂、草酸硼酸锂或双氟草酸硼酸锂。
  7. 一种电化学装置，其包含正极和权利要求1-6中任一权利要求所述的电解液，所述正极包括正极活性材料。
  8. 根据权利要求7所述的电化学装置，其中所述正极活性材料包含选自Al、Zr或Mg中的至少一种元素。
  9. 根据权利要求8所述的电化学装置，其中基于所述正极活性材料总质量，所述Al的含量a小于1％，所述Zr的含量b小于1％，所述Mg的含量c小于0.5％。
  10. 根据权利要求9所述的电化学装置，其中，所述正极材料包含Al和Mg，并且其含量满足以下条件：0.005<a/c<500。
  11. 一种电子装置，其包含权利要求7-10中任一权利要求所述的电化学装置。
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