WO2019024408A1 - 锂离子电池非水电解液及锂离子电池 - Google Patents

锂离子电池非水电解液及锂离子电池 Download PDF

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WO2019024408A1
WO2019024408A1 PCT/CN2017/119264 CN2017119264W WO2019024408A1 WO 2019024408 A1 WO2019024408 A1 WO 2019024408A1 CN 2017119264 W CN2017119264 W CN 2017119264W WO 2019024408 A1 WO2019024408 A1 WO 2019024408A1
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group
carbonate
ion battery
lithium ion
electrolyte
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English (en)
French (fr)
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郑仲天
钟玲
胡时光
石桥
陈长春
邓朝晖
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Shenzhen Capchem Technology Co Ltd
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Shenzhen Capchem Technology Co Ltd
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Priority to EP17919901.3A priority Critical patent/EP3664211B1/en
Priority to US16/632,862 priority patent/US11380937B2/en
Publication of WO2019024408A1 publication Critical patent/WO2019024408A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • 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
    • 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
    • H01M10/056—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
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 invention belongs to the technical field of lithium ion battery electrolyte, and particularly relates to a lithium ion battery non-aqueous electrolyte and a lithium ion battery.
  • Lithium-ion batteries have made great progress in the field of portable electronic products due to their high operating voltage, high safety, long life and no memory effect. Especially with the development of new energy vehicles, lithium-ion batteries have great application prospects in power supply systems for new energy vehicles.
  • the non-aqueous electrolyte lithium ion battery is a key factor affecting the high and low temperature performance of the battery.
  • the additives in the non-aqueous electrolyte are particularly important for the performance of the high and low temperature performance of the battery.
  • the lithium ions in the positive electrode material of the battery are deintercalated and embedded in the carbon negative electrode through the electrolyte.
  • the electrolyte reacts on the surface of the carbon negative electrode to produce a compound such as Li 2 CO 3 , LiO, LiOH, etc., thereby forming a passivation film on the surface of the negative electrode, which is called a solid electrolyte interface film (SEI).
  • SEI solid electrolyte interface film
  • the SEI film formed during the initial charging process not only prevents the electrolyte from further decomposing on the surface of the carbon negative electrode, but also acts as a lithium ion tunneling, allowing only lithium ions to pass. Therefore, the SEI film determines the performance of the lithium ion battery.
  • the passivation film formed by vinylene carbonate has a large impedance, especially under low temperature conditions, it is prone to low-temperature charge and lithium deposition, which affects battery safety.
  • the fluoroethylene carbonate can also form a passivation film on the surface of the negative electrode to improve the cycle performance of the battery, and the passivation film formed has a relatively low impedance, which can improve the low-temperature discharge performance of the battery.
  • fluoroethylene carbonate produces more gas at high temperature storage, which significantly reduces the high temperature storage performance of the battery.
  • the object of the present invention is to provide a non-aqueous electrolyte for a lithium ion battery, which aims to solve the problems of high-temperature storage gas production and insufficient high-temperature cycle performance of a battery existing in a non-aqueous electrolyte of a lithium ion battery.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from a hydrogen atom, a fluorine atom, a cyano group, a hydrocarbon group having 1 to 5 carbon atoms or a halogenated hydrocarbon group, and the number of carbon atoms is An oxygen-containing hydrocarbon group of 1 to 5, a silicon-containing hydrocarbon group having 1 to 5 carbon atoms, X is a -OR 5 -CN group, and R 5 is a hydrocarbon group having 1 to 5 carbon atoms or a halogenated hydrocarbon group, m, n, z, y is an integer of 0 or 1, and m+n+y+z ⁇ 0.
  • the R 1 , R 2 , R 3 , and R 4 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, a butyl group, a fluorine-containing methyl group, and a fluorine-containing ethyl group.
  • Base fluoropropyl, fluorobutyl, methylene, ethylene, propylene, butylene, fluoromethylene, fluoroethylene, fluoropropylene, fluorobutylene
  • the compound of formula I is selected from the group consisting of
  • the compound of the formula (I) has a mass percentage of 0.1% to 10.0% based on 100% by mass of the total mass of the nonaqueous electrolyte of the lithium ion battery.
  • the lithium ion battery non-aqueous electrolyte further comprises at least one component of an unsaturated cyclic carbonate, a fluoro cyclic carbonate, a cyclic sultone, a cyclic sulfate, and a nitrile.
  • the unsaturated cyclic carbonate is selected from at least one of vinylene carbonate (abbreviated as VC), ethylene carbonate (abbreviated as VEC), and methylene ethylene carbonate;
  • VC vinylene carbonate
  • VEC ethylene carbonate
  • the fluorocyclic carbonate is selected from at least one of fluoroethylene carbonate (abbreviated as FEC), trifluoromethyl ethylene carbonate, and difluoroethylene carbonate;
  • FEC fluoroethylene carbonate
  • trifluoromethyl ethylene carbonate trifluoromethyl ethylene carbonate
  • difluoroethylene carbonate difluoroethylene carbonate
  • the cyclic sultone is at least one selected from the group consisting of 1,3-propane sultone (abbreviated as PS), 1,4-butane sultone, and propylene-1,3-sultone. ;
  • the cyclic sulfate is selected from at least one of vinyl sulfate (abbreviated as DTD) and 4-methylsulfate;
  • the nitrile is selected from the group consisting of succinonitrile (abbreviated as SN), adiponitrile (abbreviated as ADN), 1,2-bis(2-cyanoethoxy)ethane, 1,4-dicyano-2- At least one of butene, 1,3,6-hexanetrizonitrile, and 1,2,3-tris(2-cyanooxy)propane.
  • SN succinonitrile
  • ADN adiponitrile
  • 1,2-bis(2-cyanoethoxy)ethane 1,4-dicyano-2- At least one of butene, 1,3,6-hexanetrizonitrile, and 1,2,3-tris(2-cyanooxy)propane.
  • the mass percentage of the unsaturated cyclic carbonate is 0.1 to 5% based on 100% of the total mass of the nonaqueous electrolyte of the lithium ion battery; the quality of the fluorocyclic carbonate The percentage is 0.1-80%; the mass percentage of the cyclic sultone is 0.1-5%; the mass percentage of the cyclic sulfate is 0.1-5%; The mass percentage is from 0.1 to 5%.
  • the lithium ion battery nonaqueous electrolyte contains a solvent and a lithium salt
  • the solvent includes at least one of a cyclic carbonate, a chain carbonate, a fluorine-containing chain carbonate, a carboxylate, a fluorine-containing carboxylate, and a fluorine-containing hydrocarbon;
  • the cyclic carbonate is ethylene carbonate At least one of an ester, propylene carbonate and butylene carbonate;
  • the chain carbonate is dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate;
  • the carboxylic acid ester is acetic acid At least one of methyl ester, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl propionate;
  • the fluorine-containing aromatic hydrocarbon is selected from one or more fluorine-substituted benzene compounds;
  • the lithium salt is at least at least one of LiPF 6 , LiBF 4 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiC(SO 2 CF 3 ) 3 , and LiN(SO 2 F) 2 .
  • LiPF 6 LiBF 4 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiC(SO 2 CF 3 ) 3 , and LiN(SO 2 F) 2 .
  • the lithium ion battery non-aqueous electrolyte provided by the present invention has a compound of the formula I, and the non-aqueous electrolyte is used for a lithium ion battery.
  • the compound of the formula I can be given priority.
  • the reductive decomposition reaction occurs in the solvent molecule, and the reaction product forms a passivation film on the surface of the electrode, and the passivation film can inhibit further decomposition of the solvent molecule and the lithium salt.
  • the compound of the formula (Formula 1) can be complexed with the high-valent metal ions on the surface of the positive electrode material to improve the stability of the surface of the positive electrode material, inhibit the oxidative decomposition of the electrolyte on the surface of the positive electrode, and thereby can significantly improve the high-temperature storage of the battery and High temperature cycle performance.
  • another object of the present invention is to provide a lithium ion battery comprising the above nonaqueous electrolyte of a lithium ion battery.
  • a lithium ion battery comprising a positive electrode, a negative electrode, a separator for isolating the positive electrode and the negative electrode, and an electrolyte, the electrolyte being a nonaqueous electrolyte of a lithium ion battery as described above.
  • the active material of the positive electrode is LiNi x Co y Mn z L (1-xyz) O 2 , LiCo x ' L (1-x') O 2 , LiNi x" L' y' Mn (2-x "-y') at least one of O 4 and Li z ' MPO 4 , wherein L is at least one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ x + y + z ⁇ 1, 0 ⁇ x ' ⁇ 1, 0.3 ⁇ x" ⁇ 0.6, 0.01 ⁇ y' ⁇ 0.2, L' is Co, At least one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si, and Fe; 0.5 ⁇ z' ⁇ 1, and M is at least one of Fe, Mn, and Co.
  • the lithium ion battery provided by the present invention can suppress the decomposition of the electrolyte on the surface of the positive and negative electrodes due to the use of the nonaqueous electrolyte described above, so that the performance of the lithium ion battery is greatly improved.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from a hydrogen atom, a fluorine atom, a cyano group, a hydrocarbon group having 1 to 5 carbon atoms or a halogenated hydrocarbon group, and the number of carbon atoms is An oxygen-containing hydrocarbon group of 1 to 5, a silicon-containing hydrocarbon group having 1 to 5 carbon atoms, X is a -OR 5 -CN group, and R 5 is a hydrocarbon group having 1 to 5 carbon atoms or a halogenated hydrocarbon group, m, n, z, y is an integer of 0 or 1, and m+n+y+z ⁇ 0.
  • the R 1 , R 2 , R 3 , and R 4 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, a butyl group, a fluorine-containing methyl group, and a fluorine-containing ethyl group.
  • Base fluoropropyl, fluorobutyl, methylene, ethylene, propylene, butylene, fluoromethylene, fluoroethylene, fluoropropylene, fluorobutylene
  • fluorobutylene One kind.
  • each of the fluorine-containing methyl group, the fluorine-containing ethyl group, the fluorine-containing propyl group, the fluorine-containing butyl group, the methylene group, and the ethylene group preferably contains three fluorine atoms.
  • R 1 is selected from a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, a butyl group, a fluorine-containing methyl group, a fluorine-containing ethyl group, and the like.
  • R 1 may not be a hydrogen atom, a fluorine atom, a cyano group or an alkyl group, but may be an alkylene group corresponding to an alkyl group, and therefore, in the present invention
  • R 1 is selected from the group consisting of methylene, ethylene, propylene, butylene, fluorine-containing methylene, fluorine-containing ethylene, fluorine-containing propylene, fluorine-containing butylene;
  • R 2 , R 3 and R 4 corresponding thereto are selected from a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, a butyl group and a fluorine-containing methyl group.
  • R 2 , R 3 , and R 4 are selected from a methylene group, an ethylene group, a propylene group, and a butylene group.
  • R 2 is selected from a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, a butyl group, a fluorine-containing methyl group, a fluorine-containing ethyl group, a fluorine-containing propyl group, and a fluorine-containing group.
  • R 2 is selected from the group consisting of methylene, ethylene, propylene, butylene, fluoromethylene, fluoroethylene, fluoropropylene, fluorobutylene .
  • R 3 is selected from a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, a butyl group, a fluorine-containing methyl group, a fluorine-containing ethyl group, a fluorine-containing propyl group, and a fluorine-containing butyl group.
  • R 3 is selected from the group consisting of methylene, ethylene, propylene, butylene, fluorine-containing methylene, fluorine-containing ethylene, fluorine-containing propylene, and fluorine-containing butylene.
  • R 4 is selected from a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, a butyl group, a fluorine-containing methyl group, a fluorine-containing ethyl group, a fluorine-containing propyl group, and a fluorine-containing butyl group.
  • R 4 is selected from the group consisting of methylene, ethylene, propylene, butylene, fluorine-containing methylene, fluorine-containing ethylene, fluorine-containing propylene, and fluorine-containing butylene.
  • the compound of the formula (Formula I) has a mass percentage of 0.1% to 10.0% based on 100% by mass of the total mass of the lithium ion battery non-aqueous electrolyte.
  • the compound of the formula of the present invention as shown in Formula I may be as follows:
  • the synthesis of the compounds 5 to 6 can be carried out by reacting the compound 1 with an organic fluorinating agent, SelectfluorTM, to obtain a crude product, which is then purified by column chromatography or the like.
  • an organic fluorinating agent SelectfluorTM
  • the lithium ion battery nonaqueous electrolyte in the technical solution of the present invention comprises, in addition to the compound component of the formula I, an unsaturated cyclic carbonate, a fluorocyclic carbonate, a cyclic sultone. At least one of a cyclic sulfate and a nitrile. Since an unsaturated cyclic carbonate, a fluorinated cyclic carbonate, a cyclic sultone, a cyclic sulfate or a nitrile compound can be compounded with the compound of the formula I to form a passivation film on the surface of the electrode material, The stability of the electrode interface is further improved to further improve the performance of the battery.
  • the mass percentage of the unsaturated cyclic carbonate is 0.1 to 5% based on 100% by mass of the total mass of the nonaqueous electrolyte of the lithium ion battery; the quality of the fluorocyclic carbonate The percentage is 0.1-80%; the mass percentage of the cyclic sultone is 0.1-5%; the mass percentage of the cyclic sulfate is 0.1-5%; The mass percentage is from 0.1 to 5%.
  • the unsaturated cyclic carbonate further comprises at least one of vinylene carbonate, ethylene carbonate, and methylene ethylene carbonate.
  • the fluorinated cyclic carbonate is at least one of fluoroethylene carbonate, trifluoromethyl ethylene carbonate, and difluoroethylene carbonate.
  • the cyclic sultone is at least one of 1,3-propane sultone, 1,4-butane sultone, and propylene-1,3-sultone.
  • the cyclic sulfate is at least one of vinyl sulfate and 4-methylsulfate.
  • the nitrile is selected from the group consisting of succinonitrile (abbreviated as SN), adiponitrile (abbreviated as ADN), 1,2-bis(2-cyanoethoxy)ethane, 1,4-dicyano At least one of 2-butene, 1,3,6-hexanetrizonitrile, and 1,2,3-tris(2-cyanooxy)propane.
  • succinonitrile abbreviated as SN
  • ADN adiponitrile
  • 1,2-bis(2-cyanoethoxy)ethane 1,4-dicyano At least one of 2-butene, 1,3,6-hexanetrizonitrile, and 1,2,3-tris(2-cyanooxy)propane.
  • the lithium ion battery nonaqueous electrolytic solution of the present invention contains a solvent in addition to the above-mentioned components.
  • the solvent includes at least one of a cyclic carbonate, a chain carbonate, a fluorine-containing chain carbonate, a carboxylate, a fluorine-containing carboxylate, and a fluorine-containing aromatic hydrocarbon.
  • the cyclic carbonate is selected from at least one of ethylene carbonate, propylene carbonate and butylene carbonate.
  • the chain carbonate is at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and methyl propyl carbonate.
  • the fluorine-containing chain carbonate refers to a compound in which one or more hydrogen atoms in a chain carbonate are substituted with a fluorine atom.
  • the carboxylic acid ester is at least one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl propionate.
  • the fluorine-containing carboxylic acid ester means a compound in which one or more hydrogen hydrogen atoms in the carboxylic acid ester are substituted by a fluorine atom.
  • the fluorine-containing aromatic hydrocarbon means a compound in which one or more hydrogen hydrogen atoms in the aromatic hydrocarbon are substituted by a fluorine atom, and for example, may be specifically selected from one or more fluorine-substituted benzene compounds.
  • the amount of the above solvent to be added may vary within a wide range, and a conventional addition amount may be specifically employed.
  • the lithium ion battery nonaqueous electrolytic solution of the present invention contains a lithium salt in addition to the above-mentioned substance components.
  • the lithium salt is LiPF 6 , LiBF 4 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiC(SO 2 CF 3 ) 3 , LiN(SO 2 F) 2 At least one of them.
  • the amount of the above-mentioned lithium salt to be added may vary within a wide range, and a conventional addition amount may be specifically employed.
  • the non-aqueous electrolyte is used in a lithium ion battery because of a compound having a structural formula of the formula I
  • the compound represented by the formula I can be subjected to a reductive decomposition reaction in preference to a solvent molecule during the first charging.
  • the reaction product forms a passivation film on the surface of the electrode, which can inhibit further decomposition of solvent molecules and lithium salts.
  • the compound of the formula (Formula 1) can be complexed with the high-valent metal ions on the surface of the positive electrode material to improve the stability of the surface of the positive electrode material, inhibit the oxidative decomposition of the electrolyte on the surface of the positive electrode, and thereby can significantly improve the high-temperature storage of the battery and High temperature cycle performance.
  • an embodiment of the present invention further provides a lithium ion battery.
  • the lithium ion battery includes a positive electrode, a negative electrode, a separator for isolating the positive electrode and the negative electrode, and an electrolyte, the electrolyte being a nonaqueous electrolyte of a lithium ion battery as described above .
  • the cathode active material is selected from the group consisting of LiNi x Co y Mn z L (1-xyz) O 2 , LiCo x ' L (1-x') O 2 , LiNi x" L' y' Mn (2-x "-y') at least one of O 4 and Li z ' MPO 4 , wherein L is at least one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ x + y + z ⁇ 1, 0 ⁇ x ' ⁇ 1, 0.3 ⁇ x" ⁇ 0.6, 0.01 ⁇ y' ⁇ 0.2, L' is Co, At least one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si, Fe; 0.5 ⁇ z' ⁇ 1, M is at least one of Fe, Mn, and Co
  • the separator is a conventional separator in the field of lithium ion batteries, and thus the present invention is not required to be further limited.
  • the lithium ion battery provided by the embodiment of the present invention can suppress the decomposition of the electrolyte on the surface of the positive and negative materials due to the use of the nonaqueous electrolyte described above, so that the performance of the lithium ion battery is greatly improved.
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.4V LiCoO 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is a non-aqueous electrolyte, and The total weight of the non-aqueous electrolyte was 100%, and the components contained in the mass percentage shown in Example 14 of Table 2 were contained.
  • a 4.4V LiCoO 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is a non-aqueous electrolyte, and The total weight of the non-aqueous electrolyte was 100%, and the components contained in the mass percentage shown in Example 15 of Table 2 were contained.
  • a 4.4V LiCoO 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is a non-aqueous electrolyte, and The total weight of the non-aqueous electrolyte was 100%, and the components contained in the mass percentage shown in Example 16 of Table 2 were contained.
  • a 4.4V LiCoO 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is a non-aqueous electrolyte, and The total weight of the non-aqueous electrolyte was 100%, and the components contained in the mass percentage shown in Example 2 of Table 2 were contained.
  • a 4.4V LiCoO 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is a non-aqueous electrolyte, and The non-aqueous electrolyte had a total weight of 100% and contained the components in the mass percentage shown in Example 18 of Table 2.
  • a 4.4V LiCoO 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is a non-aqueous electrolyte, and The total weight of the non-aqueous electrolyte was 100%, and the components contained in the mass percentage shown in Example 19 of Table 2 were contained.
  • a 4.4V LiCoO 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is a non-aqueous electrolyte, and The total weight of the non-aqueous electrolyte was 100%, and the components contained in the mass percentage shown in Example 20 of Table 2 were contained.
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is non-aqueous electrolysis
  • a 4.4V LiCoO 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is a non-aqueous electrolyte, and The total weight of the non-aqueous electrolyte was 100%, and the components contained in the mass percentage shown in Comparative Example 7 of Table 2 were contained.
  • a 4.4V LiCoO 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is a non-aqueous electrolyte, and The total weight of the non-aqueous electrolyte was 100%, and the components contained in the mass percentage shown in Comparative Example 8 of Table 2 were contained.
  • a 4.4V LiCoO 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is a non-aqueous electrolyte, and The total weight of the non-aqueous electrolyte was 100%, and the components contained in the mass percentage shown in Comparative Example 9 of Table 2 were contained.
  • a 4.4V LiCoO 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is a non-aqueous electrolyte, and The total weight of the non-aqueous electrolyte was 100%, and the components contained in the mass percentage shown in Comparative Example 10 of Table 2 were contained.
  • the lithium ion batteries prepared in the above Examples 1 to 20 and Comparative Examples 1 to 10 were subjected to relevant performance tests.
  • the test performance includes high temperature cycle performance test and high temperature storage performance test.
  • the specific test methods are as follows:
  • the lithium ion batteries prepared in Examples 1 to 20 and Comparative Examples 1 to 10 were placed in an oven at a constant temperature of 45 ° C, and charged at a constant current of 1 C to 4.2 V (LiNi 0.5 Co 0.2 Mn 0.3 O 2 / artificial graphite battery). Or 4.4V (LiCoO 2 / artificial graphite battery), then constant voltage charging until the current drops to 0.02C, and then discharge to 3.0V with a constant current of 1C, so cycle, record the first discharge capacity and the last discharge capacity.
  • 4.2 V LiNi 0.5 Co 0.2 Mn 0.3 O 2 / artificial graphite battery
  • 4.4V LiCoO 2 / artificial graphite battery
  • Capacity retention rate last discharge capacity / first discharge capacity ⁇ 100%.
  • the lithium ion battery after the formation was charged to 4.2 V (LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery) or 4.4 V (LiCoO 2 /artificial graphite battery) at a normal temperature with a constant current of 1 C, and the initial discharge of the battery was measured.
  • the capacity and the initial battery thickness were then stored in a 60 ° C environment for 30 days, and then discharged at 1 C to 3 V, and the battery holding capacity and recovery capacity and the battery thickness after storage were measured. Calculated as follows:
  • Battery capacity retention rate (%) retention capacity / initial capacity ⁇ 100%;
  • Battery capacity recovery rate (%) recovery capacity / initial capacity ⁇ 100%;
  • Thickness expansion ratio (%) (battery thickness after storage - initial battery thickness) / initial battery thickness ⁇ 100%.
  • the battery capacity retention rate of the battery at 45 ° C and 1 C cycle increased from 65.5% to 80.3%, 81.6%, 80.9%, and 84.8%, respectively;
  • the battery capacity retention rate increased from 70.5% to 80.3%, 82.6%, 80.5%, and 84.9%, respectively; the battery thickness expansion rate decreased from 21.6% to 10.8%, 11.8%, 12.9%, and 13.8%, respectively.
  • the non-aqueous electrolyte of the lithium ion battery provided by the invention can effectively improve the high-temperature storage performance and high-temperature cycle performance of the lithium ion battery.
  • the battery capacity retention rate of the battery at 45 ° C and 1 C cycle increased from 60.1% to 70.4% and 72.1%, respectively;
  • the battery capacity retention rate increased from 62.5% to 72.1% and 73.5%, respectively; the battery thickness expansion rate decreased from 25.5% to 15.5% and 16.7%, respectively.

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Abstract

为解决现有锂离子电池电解液存在的电池高温储存产气、高温循环性能不足等问题，本发明提供一种锂离子电池非水电解液。所述锂离子电池非水电解液含有结构式如式I所示的化合物，其中，所述式I中，R1、R2、R3、R4各自独立选自氢原子、氟原子、氰基、碳原子数为1-5的烃基或卤代烃基、碳原子数为1-5的含氧烃基、碳原子数为1-5的含硅烃基，X为-O-R5-CN基团，R5为碳原子数1-5的烃基或卤代烃基，m、n、z、y为0或1的整数，且m+n+y+z≠0。所述非水电解液用于锂离子电池时，能够抑制电解液在电极表面分解，改善电池的高温储存性能，且产气少，电池的膨胀率小，从而有效改善锂离子电池的高温循环性能、高温存储性能。

Description

锂离子电池非水电解液及锂离子电池 技术领域
本发明属于锂离子电池电解液技术领域，尤其涉及一种锂离子电池非水电解液及锂离子电池。
背景技术
锂离子电池因其工作电压高、安全性高、长寿命、无记忆效应等特点，在便携式电子产品领域中取得了长足的发展。尤其是伴随着新能源汽车的发展，锂离子电池在新能源汽车用动力电源系统表现巨大的应用前景。
在非水电解液锂离子电池中，非水电解液是影响电池高低温性能的关键因素。特别地，非水电解液中的添加剂对电池高低温性能的发挥尤其重要。而在锂离子电池初始充电过程中，电池正极材料中的锂离子脱嵌出来，通过电解液嵌入碳负极中。由于其高反应性，电解液在碳负极表面反应产生Li 2CO 3、LiO、LiOH等化合物，从而在负极表面形成钝化膜，该钝化膜称为固体电解液界面膜(SEI)。在初始充电过程中形成的SEI膜，不仅阻止电解液进一步在碳负极表面分解，而且起到锂离子隧道作用，只允许锂离子通过。因此，SEI膜决定了锂离子电池性能的好坏。
为了提高锂离子电池的各项性能，许多科研者通过往电解液中添加不同的负极成膜添加剂(如碳酸亚乙烯酯、氟代碳酸乙烯酯、碳酸乙烯亚乙酯)来改善SEI膜的质量，从而改善电池的各项性能。
如日本特开2000-123867号的专利中提出通过在电解液中添加碳酸亚乙烯酯来提高电池特性。碳酸亚乙烯酯能够优先于溶剂分子在负极表面发生还原分解反应，能在负极表面形成钝化膜，阻止电解液在电极表面进一步分解，从而提高电池的循环性能。但添加碳酸亚乙烯酯后，电池在高温储存中过程中容易 产生气体，导致电池发生鼓胀。
此外，碳酸亚乙烯酯形成的钝化膜阻抗较大，尤其在低温条件下，容易发生低温充电析锂，影响电池安全性。氟代碳酸乙烯酯也能在负极表面形成钝化膜，改善电池的循环性能，且形成的钝化膜阻抗比较低，能够改善电池的低温放电性能。但氟代碳酸乙烯酯在高温储存产生更多的气体，明显降低电池高温储存性能。
因此，有必要对目前非水电解液做更深入的研究，开发出有利于提高锂离子电池性能的新的非水电解液。
发明内容
本发明的目的在于提供一种锂离子电池非水电解液，旨在解决现有锂离子电池非水电解液存在的电池高温储存产气、高温循环性能不足等问题。
为了达到上述目的，本发明采用了如下的技术方案：
一种锂离子电池非水电解液，含有结构式如式I所示的化合物：
Figure PCTCN2017119264-appb-000001
其中，所述式I中，R 1、R 2、R 3、R 4各自独立选自氢原子、氟原子、氰基、碳原子数为1-5的烃基或卤代烃基、碳原子数为1-5的含氧烃基、碳原子数为1-5的含硅烃基，X为-O-R 5-CN基团，R 5为碳原子数1-5的烃基或卤代烃基，m、n、z、y为0或1的整数，且m+n+y+z≠0。
优选的，所述R 1、R 2、R 3、R 4各自独立地选自氢原子、氟原子、氰基、甲基、乙基、丙基、丁基、含氟甲基、含氟乙基、含氟丙基、含氟丁基、亚甲基、亚乙基、亚丙基、亚丁基、含氟亚甲基、含氟亚乙基、含氟亚丙基、含氟亚丁基中的一种。优选的，所述如式I所示的化合物选自：
化合物1：
Figure PCTCN2017119264-appb-000002
化合物2：
Figure PCTCN2017119264-appb-000003
化合物3：
Figure PCTCN2017119264-appb-000004
化合物4
Figure PCTCN2017119264-appb-000005
化合物5：
Figure PCTCN2017119264-appb-000006
化合物6
Figure PCTCN2017119264-appb-000007
化合物7
Figure PCTCN2017119264-appb-000008
优选的，以所述锂离子电池非水电解液的总质量为100％计，所述结构式如式I所示的化合物的质量百分含量为0.1％～10.0％。
优选的，所述锂离子电池非水电解液还包含不饱和环状碳酸酯、氟代环状碳酸酯、环状磺酸内酯、环状硫酸酯、腈类中的至少一种组分。
优选的，所述不饱和环状碳酸酯选自碳酸亚乙烯酯(缩写为VC)、碳酸乙烯亚乙酯(缩写为VEC)、亚甲基碳酸乙烯酯中的至少一种；
所述氟代环状碳酸酯选自氟代碳酸乙烯酯(缩写为FEC)、三氟甲基碳酸乙烯酯、双氟代碳酸乙烯酯中的至少一种；
所述环状磺酸内酯选自1,3-丙烷磺内酯(缩写为PS)、1,4-丁烷磺内酯、丙烯基-1,3-磺酸内酯中的至少一种；
所述环状硫酸酯选自硫酸乙烯酯(缩写为DTD)、4-甲基硫酸乙烯酯中的至少一种；
所述腈类选自丁二腈(缩写为SN)、己二腈(缩写为ADN)、1,2-二(2-氰乙氧基)乙烷、1,4-二氰基-2-丁烯、1,3,6-己烷三腈、1,2,3-三(2-氰氧基)丙烷中的至少一种。
优选的，以所述锂离子电池非水电解液的总质量为100％计，所述不饱和环状碳酸酯的质量百分含量为0.1～5％；所述氟代环状碳酸酯的质量百分含量为0.1～80％；所述环状磺酸内酯的质量百分含量为0.1～5％；所述环状硫酸酯的质 量百分含量为0.1～5％；所述腈类的质量百分含量为0.1～5％。
优选的，所述锂离子电池非水电解液包含溶剂和锂盐；
所述溶剂包括环状碳酸酯、链状碳酸酯、含氟链状碳酸酯、羧酸酯、含氟羧酸酯、含氟香烃中的至少一种；所述环状碳酸酯为碳酸乙烯酯、碳酸丙烯酯和碳酸丁烯酯中的至少一种；所述链状碳酸酯为碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯；所述羧酸酯为乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯中的至少一种；所述含氟芳香烃选自一个或多个氟取代的苯化合物；
所述锂盐为LiPF 6、LiBF 4、LiN(SO 2CF 3) 2、LiN(SO 2C 2F 5) 2、LiC(SO 2CF 3) 3、LiN(SO 2F) 2中的至少一种。
本发明提供的锂离子电池非水电解液，由于含有结构式如式I所示的化合物，将该非水电解液用于锂离子电池，在首次充电过程中，如结构式I所示的化合物能够优先于溶剂分子发生还原分解反应，其反应产物在电极表面形成一层钝化膜，该钝化膜能够抑制溶剂分子及锂盐的进一步分解。此外，结构式如式1所示的化合物能够与正极材料表面的高价态金属离子络合，提高正极材料表面的稳定性，抑制电解液在正极表面的氧化分解，从而能够明显改善电池的高温储存及高温循环性能。
相应地，本发明的另一目的在于提供一种含有上述锂离子电池非水电解液的锂离子电池。
一种锂离子电池，包括正极、负极、用于隔离所述正极和所述负极的隔膜、以及电解液，所述电解液为如上所述的锂离子电池非水电解液。
优选地，所述正极的活性物质为LiNi xCo yMn zL (1-x-y-z)O 2、LiCo x’L (1-x’)O 2、LiNi x”L’ y’Mn (2-x”-y’)O 4、Li z’MPO 4中的至少一种，其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe中的至少一种，0≤x≤1，0≤y≤1，0≤z≤1，0＜x+y+z≤1，0<x’≤1，0.3≤x”≤0.6，0.01≤y’≤0.2，L’为Co、Al、Sr、Mg、Ti、Ca、Zr、Zn、Si、Fe中的至少一种；0.5≤z’≤1，M为Fe、Mn、Co中的至少一种。
本发明提供的锂离子电池，由于采用了上述所述的非水电解液，能够抑制电解液在正负极材料表面的分解，使得锂离子电池的性能得到了很大的提升。
具体实施方式
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明实施例提供了一种锂离子电池非水电解液，该锂离子电池非水电解液中含有结构式如式I所示的化合物：
Figure PCTCN2017119264-appb-000009
其中，所述式I中，R 1、R 2、R 3、R 4各自独立选自氢原子、氟原子、氰基、碳原子数为1-5的烃基或卤代烃基、碳原子数为1-5的含氧烃基、碳原子数为1-5的含硅烃基，X为-O-R 5-CN基团，R 5为碳原子数1-5的烃基或卤代烃基，m、n、z、y为0或1的整数，且m+n+y+z≠0。
优选的，所述R 1、R 2、R 3、R 4各自独立地选自氢原子、氟原子、氰基、甲基、乙基、丙基、丁基、含氟甲基、含氟乙基、含氟丙基、含氟丁基、亚甲基、亚乙基、亚丙基、亚丁基、含氟亚甲基、含氟亚乙基、含氟亚丙基、含氟亚丁基中的一种。优选的，含氟甲基、含氟乙基、含氟丙基、含氟丁基、亚甲基、亚乙基中各自优选含三个氟原子。
本领域技术人员可以理解的，当m为0时，R 1选自氢原子、氟原子、氰基、甲基、乙基、丙基、丁基、含氟甲基、含氟乙基、含氟丙基、含氟丁基；当m为1时，R 1不可能为氢原子、氟原子、氰基以及烷基等，而应为烷基所对应的亚烷基，因此，本发明中，当m为1时，R 1选自亚甲基、亚乙基、亚丙基、亚 丁基、含氟亚甲基、含氟亚乙基、含氟亚丙基、含氟亚丁基；类似的，当n、z或y为0时，与其对应的R 2、R 3、R 4选自氢原子、氟原子、氰基、甲基、乙基、丙基、丁基、含氟甲基、含氟乙基、含氟丙基、含氟丁基；当n、z或y为1时，R 2、R 3、R 4选自亚甲基、亚乙基、亚丙基、亚丁基、含氟亚甲基、含氟亚乙基、含氟亚丙基、含氟亚丁基。需要注意的是，m为0或者1仅对R 1所表示的基团存在影响，而对R 2、R 3、R 4所表示的基团无影响。同样的，n、z或y为0或者1的选择对其他基团的影响与上述m类似。即，当n为0时，R 2选自氢原子、氟原子、氰基、甲基、乙基、丙基、丁基、含氟甲基、含氟乙基、含氟丙基、含氟丁基；当n为1时，R 2选自亚甲基、亚乙基、亚丙基、亚丁基、含氟亚甲基、含氟亚乙基、含氟亚丙基、含氟亚丁基。当x为0时，R 3选自氢原子、氟原子、氰基、甲基、乙基、丙基、丁基、含氟甲基、含氟乙基、含氟丙基、含氟丁基；当x为1时，R 3选自亚甲基、亚乙基、亚丙基、亚丁基、含氟亚甲基、含氟亚乙基、含氟亚丙基、含氟亚丁基。当y为0时，R 4选自氢原子、氟原子、氰基、甲基、乙基、丙基、丁基、含氟甲基、含氟乙基、含氟丙基、含氟丁基；当y为1时，R 4选自亚甲基、亚乙基、亚丙基、亚丁基、含氟亚甲基、含氟亚乙基、含氟亚丙基、含氟亚丁基。
优选地，以所述锂离子电池非水电解液的总质量为100％计，所述结构式如式I所示的化合物的质量百分含量为0.1％～10.0％。
具体地，本发明结构式如式I所示的化合物可以是如下所示：
Figure PCTCN2017119264-appb-000010
化合物1；
Figure PCTCN2017119264-appb-000011
化合物2；
Figure PCTCN2017119264-appb-000012
化合物3；
Figure PCTCN2017119264-appb-000013
化合物4；
Figure PCTCN2017119264-appb-000014
化合物5；
Figure PCTCN2017119264-appb-000015
化合物6；
Figure PCTCN2017119264-appb-000016
化合物7。
对于上述化合物1-7，本领域技术人员可根据其结构式，按照公知的知识推倒出其合成方法。例如，化合物1～4的合成见反应式(1)，反应步骤如下：1)在碱性催化剂作用下，对应的多元醇与碳酸二甲酯发生酯交换反应，得到部分酯交换后的醇酯类中间体；2)中间体再与丙烯腈或丁烯腈类化合物反应得到粗产物；3)粗产物经柱层析等提纯后得到。
Figure PCTCN2017119264-appb-000017
化合物5～6的合成可采用化合物1与有机氟化剂SelectfluorTM反应得到粗品，再经柱层析等提纯后得到。
本发明技术方案中的锂离子电池非水电解液，除了包含结构式如式I所示的化合物组分外，还包含不饱和环状碳酸酯、氟代环状碳酸酯、环状磺酸内酯、环状硫酸酯、腈类中的至少一种。由于不饱和环状碳酸酯、氟代环状碳酸酯、环状磺酸内酯、环状硫酸酯或腈类化合物能够与式I所示的化合物配合，共同在电极材料表面形成钝化膜，进一步提高电极界面的稳定性，从而进一步提高电池的性能。
进一步地，以所述锂离子电池非水电解液的总质量为100％计，所述不饱和环状碳酸酯的质量百分含量为0.1～5％；所述氟代环状碳酸酯的质量百分含量为0.1～80％；所述环状磺酸内酯的质量百分含量为0.1～5％；所述环状硫酸酯的质量百分含量为0.1～5％；所述腈类的质量百分含量为0.1～5％。
优选地，所述不饱和环状碳酸酯还包含碳酸亚乙烯酯、碳酸乙烯亚乙酯、亚甲基碳酸乙烯酯中的至少一种。
优选地，所述氟代环状碳酸酯为氟代碳酸乙烯酯、三氟甲基碳酸乙烯酯、双氟代碳酸乙烯酯中的至少一种。
优选地，所述的环状磺酸内酯为1,3-丙烷磺内酯、1,4-丁烷磺内酯、丙烯基 -1,3-磺酸内酯中的至少一种。
优选地，所述环状硫酸酯为硫酸乙烯酯、4-甲基硫酸乙烯酯中的至少一种。
优选地，所述腈类选自丁二腈(缩写为SN)、己二腈(缩写为ADN)、1,2-二(2-氰乙氧基)乙烷、1，4-二氰基-2-丁烯、1,3,6-己烷三腈、1,2,3-三(2-氰氧基)丙烷中的至少一种。
本发明的锂离子电池非水电解液除了包含上述物质组分外，还包含有溶剂。所述溶剂包括环状碳酸酯、链状碳酸酯、含氟链状碳酸酯、羧酸酯、含氟羧酸酯、含氟芳香烃中的至少一种。
优选地，所述环状碳酸酯选自碳酸乙烯酯、碳酸丙烯酯和碳酸丁烯酯中的至少一种。
所述链状碳酸酯选自碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯和碳酸甲丙酯中的至少一种。
所述含氟链状碳酸酯是指链状碳酸酯中的一个或多个氢原子被氟原子取代的化合物。
所述羧酸酯选自乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯中的至少一种。
所述含氟羧酸酯是指羧酸酯中的一个或多个氢氢原子被氟原子取代的化合物。
所述含氟芳香烃是指芳香烃中的一个或多个氢氢原子被氟原子取代的化合物，例如具体可选自一个或多个氟取代的苯化合物。
上述溶剂的添加量可在较大范围内变动，具体可采用常规添加量。
进一步地，本发明的锂离子电池非水电解液除了包含上述物质组分外，还包含有锂盐。
优选地，所述锂盐为LiPF 6、LiBF 4、LiN(SO 2CF 3) 2、LiN(SO 2C 2F 5) 2、LiC(SO 2CF 3) 3、LiN(SO 2F) 2中的至少一种。
上述锂盐的添加量可在较大范围内变动，具体可采用常规添加量。
本发明中，由于含有结构式如式I所示的化合物，将该非水电解液用于锂离子电池，在首次充电过程中，如结构式I所示的化合物能够优先于溶剂分子发生还原分解反应，其反应产物在电极表面形成一层钝化膜，该钝化膜能够抑制溶剂分子及锂盐的进一步分解。此外，结构式如式1所示的化合物能够与正极材料表面的高价态金属离子络合，提高正极材料表面的稳定性，抑制电解液在正极表面的氧化分解，从而能够明显改善电池的高温储存及高温循环性能。
在本发明上述锂离子非水电解液的前提下，本发明实施例还提供了一种锂离子电池。
在一实施例中，所述锂离子电池，包括正极、负极、用于隔离所述正极和所述负极的隔膜、以及电解液，所述电解液为如上所述的锂离子电池非水电解液。
具体的，所述正极活性材料选自LiNi xCo yMn zL (1-x-y-z)O 2、LiCo x’L (1-x’)O 2、LiNi x”L’ y’Mn (2-x”-y’)O 4、Li z’MPO 4中的至少一种，其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe中的至少一种，0≤x≤1，0≤y≤1，0≤z≤1，0＜x+y+z≤1，0<x’≤1，0.3≤x”≤0.6，0.01≤y’≤0.2，L’为Co、Al、Sr、Mg、Ti、Ca、Zr、Zn、Si、Fe中的至少一种；0.5≤z’≤1，M为Fe、Mn、Co中的至少一种。所述负极的活性材料选自人造石墨、天然石墨。当然，不限于所列举的这两种。
所述隔膜为锂离子电池领域的常规隔膜，因此本发明不需要再做详细的限定。
本发明实施例提供的锂离子电池，由于采用了上述所述的非水电解液，能够抑制电解液在正负极材料表面的分解，使得锂离子电池的性能得到了很大的提升。
为了更好的说明本发明的技术方案，下面结合具体实施例进行说明。
实施例1
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液， 且以所述非水电解液的总重量为100％计，含有表1实施例1所示质量百分含量的组分。
实施例2
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1实施例2所示质量百分含量的组分。
实施例3
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1实施例3所示质量百分含量的组分。
实施例4
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1实施例4所示质量百分含量的组分。
实施例5
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1实施例5所示质量百分含量的组分。
实施例6
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1实施例6所示质量百分含 量的组分。
实施例7
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1实施例7所示质量百分含量的组分。
实施例8
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1实施例8所示质量百分含量的组分。
实施例9
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1实施例9所示质量百分含量的组分。
实施例10
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1实施例10所示质量百分含量的组分。
实施例11
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1实施例11所示质量百分含量的组分。
实施例12
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1实施例12所示质量百分含量的组分。
实施例13
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1实施例13所示质量百分含量的组分。
实施例14
一种4.4V LiCoO 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表2实施例14所示质量百分含量的组分。
实施例15
一种4.4V LiCoO 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表2实施例15所示质量百分含量的组分。
实施例16
一种4.4V LiCoO 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表2实施例16所示质量百分含量的组分。
实施例17
一种4.4V LiCoO 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表2实施例17所示质量百分含量的组分。
实施例18
一种4.4V LiCoO 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表2实施例18所示质量百分含量的组分。
实施例19
一种4.4V LiCoO 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表2实施例19所示质量百分含量的组分。
实施例20
一种4.4V LiCoO 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表2实施例20所示质量百分含量的组分。
对比例1
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1对比例1所示质量百分含量的组分。
对比例2
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1对比例2所示质量百分含量的组分。
对比例3
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1对比例3所示质量百分含 量的组分。
对比例4
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1对比例4所示质量百分含量的组分。
对比例5
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1对比例5所示质量百分含量的组分。
对比例6
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表1对比例6所示质量百分含量的组分。
对比例7
一种4.4V LiCoO 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表2对比例7所示质量百分含量的组分。
对比例8
一种4.4V LiCoO 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表2对比例8所示质量百分含量的组分。
对比例9
一种4.4V LiCoO 2/人造石墨电池，包括正极、负极、设置在所述正极和所 述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表2对比例9所示质量百分含量的组分。
对比例10
一种4.4V LiCoO 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、以及电解液，其中，所述电解液为非水电解液，且以所述非水电解液的总重量为100％计，含有表2对比例10所示质量百分含量的组分。
为了验证本发明的锂离子电池非水电解液对电池性能的影响，下面对上述实施例1～20及对比例1～10制备的锂离子电池进行相关的性能测试。测试的性能包括高温循环性能测试、高温储存性能测试，各项的具体测试方法如下：
一、高温循环性能测试
将实施例1～20及对比例1～10制备的锂离子电池置于恒温45℃的烘箱中，以1C的电流恒流充电至4.2V(LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池)或4.4V(LiCoO 2/人造石墨电池)，再恒压充电至电流下降至0.02C，然后以1C的电流恒流放电至3.0V，如此循环，记录第1次的放电容量和最后一次的放电容量。
按下式计算高温循环的容量保持率：
容量保持率＝最后一次的放电容量/第1次的放电容量×100％。
二、高温储存性能测试
将化成后的锂离子电池在常温下用1C恒流恒压充至4.2V(LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池)或4.4V(LiCoO 2/人造石墨电池)，测量电池初始放电容量及初始电池厚度，然后在60℃环境中储存30天后，以1C放电至3V，测量电池的保持容量和恢复容量及储存后电池厚度。计算公式如下：
电池容量保持率(％)＝保持容量/初始容量×100％；
电池容量恢复率(％)＝恢复容量/初始容量×100％；
厚度膨胀率(％)＝(储存后电池厚度-初始电池厚度)/初始电池厚度×100％。
表1 实施例1～13及对比例1～6的非水电解液制成电池后相应电池的性能
Figure PCTCN2017119264-appb-000018
Figure PCTCN2017119264-appb-000019
从表1的数据可见，对比对比例1与实施例1～实施例4，分别添加结构式I所示化合物1、化合物2、化合物3或化合物5，能够明显电池的高温储存性能及高温循环性能。
其中，45℃、1C循环500次电池容量保持率从65.5％分别提高到80.3％、81.6％、80.9％、84.8％；
60℃存储30天，电池容量保持率从70.5％分别提高到80.3％、82.6％、80.5％、84.9％；电池厚度膨胀率从21.6％分别下降到10.8％、11.8％、12.9％、13.8％。
对比实施例5与实施例1、实施例6～实施例7，随化合物1添加量增加，能够 进一步提高电池的高温储存及高温循环性能。对比实施例8～13与实施例1、对比例2～6的测试结果，在结构式I所示的化合物1基础上，进一步添加常规添加剂(VC、FEC、PS、DTD)或新型锂盐(LiN(SO 2F) 2)，也能够进一步提高电池的高温储存及高温循环性能。
可见，本发明提供的锂离子电池非水电解液可以有效的改善锂离子电池的高温储存性能及高温循环性能。
表2 实施例14～20及对比例7～10的非水电解液制成电池后相应电池的性能
Figure PCTCN2017119264-appb-000020
从表2的数据可见，对比对比例7与实施例14～实施例15，分别添加结构式I所示化合物1、化合物5，能够明显电池的高温储存性能及高温循环性能。
其中，45℃、1C循环300次电池容量保持率从60.1％分别提高到70.4％、72.1％、；
60℃存储30天，电池容量保持率从62.5％分别提高到72.1％、73.5％；电池厚度膨胀率从25.5％分别下降到15.5％、16.7％。
对比实施例14、实施例16～实施例20的测试结果可知，在结构式I所示的 化合物1基础上，进一步添加常规添加剂(FEC、PS、SN、ADN)，也能够进一步提高电池的高温储存及高温循环性能。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种锂离子电池非水电解液，其特征在于：含有结构式如式I所示的化合物：
    Figure PCTCN2017119264-appb-100001
    其中，所述式I中，R 1、R 2、R 3、R 4各自独立选自氢原子、氟原子、氰基、碳原子数为1-5的烃基或卤代烃基、碳原子数为1-5的含氧烃基、碳原子数为1-5的含硅烃基，X为-O-R 5-CN基团，R 5为碳原子数1-5的烃基或卤代烃基，m、n、z、y为0或1的整数，且m+n+y+z≠0。
  2. 如权利要求1所述的锂离子电池非水电解液，其特征在于：所述R 1、R 2、R 3、R 4各自独立地选自氢原子、氟原子、氰基、甲基、乙基、丙基、丁基、含氟甲基、含氟乙基、含氟丙基、含氟丁基亚甲基、亚乙基、亚丙基、亚丁基、含氟亚甲基、含氟亚乙基、含氟亚丙基、含氟亚丁基中的一种。
  3. 如权利要求1所述的锂离子电池非水电解液，其特征在于：所述如式I所示的化合物选自：
    Figure PCTCN2017119264-appb-100002
  4. 如权利要求1～3任一项所述的锂离子电池非水电解液，其特征在于：以所述锂离子电池非水电解液的总质量为100％计，所述结构式如式I所示的化合物的质量百分含量为0.1％～10.0％。
  5. 如权利要求1～3任一项所述的锂离子电池非水电解液，其特征在于：所述锂离子电池非水电解液还包含不饱和环状碳酸酯、氟代环状碳酸酯、环状磺酸内酯、环状硫酸酯、腈类中的至少一种。
  6. 如权利要求5所述的锂离子电池非水电解液，其特征在于：所述不饱和环状碳酸酯选自碳酸亚乙烯酯、碳酸乙烯亚乙酯、亚甲基碳酸乙烯酯中的至少一种；
    所述氟代环状碳酸酯选自氟代碳酸乙烯酯、三氟甲基碳酸乙烯酯、双氟代碳酸乙烯酯中的至少一种；
    所述环状磺酸内酯选自1,3-丙烷磺内酯、1,4-丁烷磺内酯、丙烯基-1,3-磺酸内酯中的至少一种；
    所述环状硫酸酯选自硫酸乙烯酯、4-甲基硫酸乙烯酯中的至少一种；
    所述腈类选自丁二腈、己二腈、1,2-二(2-氰乙氧基)乙烷、1,4-二氰基-2-丁烯、1,3,6-己烷三腈、1,2,3-三(2-氰氧基)丙烷中的至少一种。
  7. 如权利要求5所述的锂离子电池非水电解液，其特征在于：以所述锂离子电池非水电解液的总质量为100％计，所述不饱和环状碳酸酯的质量百分含量为0.1～5％；所述氟代环状碳酸酯的质量百分含量为0.1～80％；所述环状磺酸内酯的质量百分含量为0.1～5％；所述不饱和环状硫酸酯的质量百分含量为0.1～5％；所述腈类的质量百分含量为0.1～5％。
  8. 如权利要求1所述的锂离子电池非水电解液，其特征在于：所述锂离子电池非水电解液包含溶剂和锂盐；
    所述溶剂包括环状碳酸酯、链状碳酸酯、含氟链状碳酸酯、羧酸酯、含氟羧酸酯、含氟芳香烃中的至少一种；
    所述环状碳酸酯选自碳酸乙烯酯、碳酸丙烯酯和碳酸丁烯酯中的至少一种； 所述链状碳酸酯选自碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯中的至少一种；所述羧酸酯选自乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯中的至少一种；所述含氟芳香烃选自一个或多个氟取代的苯化合物中的至少一种；
    所述锂盐选自LiPF 6、LiBF 4、LiN(SO 2CF 3) 2、LiN(SO 2C 2F 5) 2、LiC(SO 2CF 3) 3、LiN(SO 2F) 2中的至少一种。
  9. 一种锂离子电池，包括正极、负极、用于隔离所述正极和所述负极的隔膜、以及电解液，其特征在于：所述电解液为如权利要求1～8任一项所述的锂离子电池非水电解液。
  10. 如权利要求9所述的锂离子电池，其特征在于，所述正极包括正极活性材料，所述正极的活性物质为LiNi xCo yMn zL (1-x-y-z)O 2、LiCo x’L (1-x’)O 2、LiNi x”L’ y’Mn (2-x”-y’)O 4、Li z’MPO 4中的至少一种，其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe中的至少一种，0≤x≤1，0≤y≤1，0≤z≤1，0＜x+y+z≤1，0<x’≤1，0.3≤x”≤0.6，0.01≤y’≤0.2，L’为Co、Al、Sr、Mg、Ti、Ca、Zr、Zn、Si、Fe中的至少一种；0.5≤z’≤1，M为Fe、Mn、Co中的至少一种。
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