WO2016090738A1 - Électrolyte et batterie au lithium-ion l'utilisant - Google Patents

Électrolyte et batterie au lithium-ion l'utilisant Download PDF

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Publication number
WO2016090738A1
WO2016090738A1 PCT/CN2015/071563 CN2015071563W WO2016090738A1 WO 2016090738 A1 WO2016090738 A1 WO 2016090738A1 CN 2015071563 W CN2015071563 W CN 2015071563W WO 2016090738 A1 WO2016090738 A1 WO 2016090738A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte
electrolytic solution
double bond
group
structural formula
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PCT/CN2015/071563
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English (en)
Chinese (zh)
Inventor
杨丽美
李松
Original Assignee
东莞新能源科技有限公司
宁德新能源科技有限公司
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Publication of WO2016090738A1 publication Critical patent/WO2016090738A1/fr

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Classifications

    • 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
    • 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
    • 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
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • 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

  • This application belongs to the field of batteries, and in particular relates to a non-aqueous electrolyte and a lithium ion battery using the same.
  • Lithium-ion batteries have significant advantages such as high specific energy, large specific power, long cycle life and small self-discharge. They are widely used in electronic products such as mobile communication, digital cameras and video cameras, and become a hot spot for energy storage and power battery development. . With the wide application of lithium ion batteries, high requirements have been placed on their environmental adaptability, and lithium ion batteries have been used in various environments.
  • lithium ion secondary batteries are becoming smaller and lighter, the requirements for energy density are becoming higher and higher, and the solution is to increase the operating voltage and energy density of the battery.
  • electrolyte has a significant impact on the high temperature performance and high-pressure performance of the battery.
  • U.S. Patent No. 5,471, 862 replaces the ether in the electrolyte with a chain carboxylate to form an electrolyte containing a mixed solvent of a chain carboxylate, a cyclic carbonate and a chain carbonate, thereby avoiding side reactions of the ether and the negative electrode.
  • the low-temperature cycle performance and high-temperature storage performance of the lithium ion battery are obviously improved, but the carboxylic acid ester solvent may have an unavoidable side reaction with the negative electrode.
  • some inhibitors are added to the electrolyte.
  • an inhibitor particularly a carbonate-based inhibitor containing a double bond, undergoes an irreversible decomposition reaction due to a high voltage of the cathode, and loses the side reaction. effect.
  • an electrolyte which can be used for a long period of time in a high voltage condition for use in a lithium ion battery, capable of working normally for a long period of time under a working voltage higher than 4.35 V, and ensuring a battery High temperature performance.
  • the chain carboxylic acid ester is selected from at least one of the compounds having the chemical structural formula of Formula I:
  • R 1 is one selected from the group consisting of an alkyl group having 2 to 3 carbon atoms and a halogenated alkyl group having 2 to 3 carbon atoms; and R 2 is selected from an alkyl group having 3 to 7 carbon atoms and a carbon number. It is one of 3 to 7 haloalkyl groups; R 2 has a carbon number of not less than the number of carbon atoms of R 1 .
  • the haloalkyl group is a group formed by losing any one hydrogen atom on a halogenated alkane molecule having at least one hydrogen atom.
  • the alkyl group is a group formed by the loss of any one hydrogen atom on the alkane molecule.
  • the alkane is selected from any one of a linear alkane, a branched alkane, and a cycloalkane.
  • R 3 is hydrogen or R 3 is one selected from the group consisting of alkyl groups having 1 to 10 carbon atoms
  • R 4 is hydrogen or R 4 is one selected from the group consisting of alkyl groups having 1 to 10 carbon atoms;
  • R 5 and R 6 are not hydrogen at the same time.
  • the chain carboxylic acid ester is present in an amount of 10% to 40% by mass in the electrolyte.
  • the upper limit of the mass percentage range of the chain carboxylic acid ester in the electrolytic solution is 30% or 20%, and the lower limit is 10%.
  • the chain carboxylic acid ester is at least one selected from the group consisting of propyl propionate, butyl propionate, butyl butyrate, and n-amyl propionate.
  • VC vinylene carbonate
  • VEC ethylene carbonate
  • the electrolyte contains a dialkyl carbonate.
  • the dialkyl carbonate is diethyl carbonate.
  • the electrolyte contains fluoroethylene carbonate.
  • the fluoroethylene carbonate has a mass percentage in the electrolyte of from 1% to 7%.
  • the electrolyte consists of a non-aqueous organic solvent and a lithium salt.
  • the composition consists of a base ester and a fluoroethylene carbonate.
  • the lithium salt is at least one selected from the group consisting of an organic lithium salt or an inorganic lithium salt.
  • the lithium salt contains at least one of a fluorine element, a boron element, and a phosphorus element.
  • the lithium salt is selected from lithium hexafluorophosphate LiPF 6 , lithium bistrifluoromethanesulfonimide LiN(CF 3 SO 2 ) 2 (abbreviated as LiTFSI), lithium bis(fluorosulfonyl)imide Li (N(SO) 2 F) 2 ) (abbreviated as LiFSI), lithium bis(oxalate) borate LiB(C 2 O 4 ) 2 (abbreviated as LiBOB), lithium difluorooxalate borate LiBF 2 (C 2 O 4 ) (abbreviated as LiDFOB) One.
  • LiTFSI lithium bistrifluoromethanesulfonimide LiN(CF 3 SO 2 ) 2
  • LiFSI lithium bis(fluorosulfonyl)imide Li (N(SO) 2 F) 2 )
  • LiBOB lithium bis(oxalate) borate LiB(C 2 O 4 ) 2
  • LiDFOB lithium difluoroox
  • the concentration of the lithium salt in the electrolyte is from 0.5 M to 1.5 M. Further preferably, the concentration of the lithium salt in the electrolytic solution is from 0.8 M to 1.2 M.
  • a lithium ion battery is provided, characterized in that the electrolyte is at least one selected from the above electrolytes.
  • the lithium ion battery includes a cathode current collector, a cathode film coated on the cathode current collector, a cathode current collector, and an anode membrane coated on the anode current collector, a separator, and an electrolyte.
  • the positive electrode film includes a positive electrode active material, a binder, and a conductive agent.
  • the negative electrode membrane includes a negative electrode active material, a binder, and a conductive agent.
  • the positive electrode active material is at least one selected from the group consisting of lithium cobaltate LiCoO 2 , lithium nickel manganese cobalt ternary material, lithium iron phosphonate, and lithium manganate.
  • the negative active material is graphite and/or silicon.
  • the electrolyte solution provided by the present application can effectively inhibit the decomposition reaction of an unsaturated carbon bond cyclic carbonate having a concentration of not more than 1% by weight in an electrolyte at a high voltage, without being saturated.
  • the presence of a carbon-bonded cyclic carbonate can significantly inhibit the side reaction between the cathode and the carboxylic acid ester in the electrolyte, and the two can be used in combination to complement each other and benign.
  • the electrolyte provided in the present application can be used for high voltage conditions for a long time for lithium ion electricity. In the pool, it can work normally for a long time under the condition that the working voltage is higher than 4.35V, and the high temperature performance of the battery is guaranteed.
  • vinylene carbonate is abbreviated as VC; ethylene carbonate is abbreviated as VEC; ethylene carbonate is abbreviated as EC; diethyl carbonate is abbreviated as DEC; fluoroethylene carbonate (abbreviated as FEC); cobalt Lithium acid is abbreviated as LCO.
  • the relationship between the percentage, the additive content, and the mass percentage of the additive in the electrolyte is shown in Table 1.
  • the positive electrode active material lithium cobaltate (the molecular formula is LiCoO 2 ), the conductive agent acetylene black, the binder polyvinylidene fluoride (abbreviated as PVDF) in an appropriate ratio of 96:2:2 in the appropriate amount of N-methylpyrrolidone (abbreviation)
  • the mixture was thoroughly stirred in a solvent of NMP) to form a uniform positive electrode slurry.
  • This slurry was coated on a positive current collector Al foil, dried, and cold pressed to obtain a positive electrode tab.
  • the anode active material graphite, the conductive agent acetylene black, the binder styrene-butadiene rubber (abbreviated as SBR), and the thickener sodium carboxymethylcellulose (abbreviated as CMC) are in an appropriate amount according to a weight ratio of 95:2:2:1.
  • SBR binder styrene-butadiene rubber
  • CMC thickener sodium carboxymethylcellulose
  • a PE porous polymer film was used as the separator.
  • the positive electrode tab, the separator, and the anode tab are stacked in this order, so that the separator is in the middle of the positive anode to function as an isolation, and then wound to obtain a bare cell.
  • the bare cells were placed in an outer bag, and the electrolytes L1 # to L13 # obtained in Example 1 and the electrolytes DL1 # DL8 # obtained in the comparative examples were respectively injected into the dried battery, and vacuum-sealed and statically.
  • the process of setting, forming, shaping, and the like completes the preparation of a lithium ion battery.
  • the lithium ion batteries using the electrolytic solutions L1 # to L13 # obtained in Example 1 were respectively referred to as batteries C1 # to C13 #
  • the lithium ion batteries using the electrolytic solutions DL1 # to DL8 # obtained in Comparative Example 1 were respectively recorded as batteries DC1 # ⁇ DC8 # .
  • the lithium ion secondary batteries C1 # to C13 # and DC1 # to DC8 # are respectively charged to a charge cut-off voltage of 4.35 V and a constant voltage of 4.35 V to a current of 0.025 C at a constant current of 0.5 C.
  • the battery was discharged at a rate of 0.5 C to 3.0 V, and the discharge capacity was recorded as the discharge capacity before the battery was stored. After that, it is charged at a constant current of 0.5C to 4.35V, and then charged at a constant voltage of 4.35V until the current is 0.025C, so that it is in a fully charged state of 4.35V, and the thickness and internal resistance of the battery before storage are tested; then, it is placed at 85 ° C. In the incubator, after 24 hours of storage, take it out and test its thickness again, which is recorded as the thickness and internal resistance of the battery after high temperature storage.
  • Thickness expansion ratio (%) (thickness after storage - thickness before storage) ⁇ thickness before storage ⁇ 100%.
  • Internal resistance increase rate (%) (internal resistance after storage - internal resistance before storage) ⁇ internal resistance before storage ⁇ 100%
  • Capacity retention rate (%) residual capacity after storage (mAh) ⁇ discharge capacity before storage (mAh) ⁇ 100%
  • Capacity recovery rate (%) reversible capacity after storage (mAh) ⁇ pre-storage discharge capacity (mAh) ⁇ 100%
  • a cyclic carbonate containing an unsaturated carbon bond can prevent a side reaction between the anode and the electrolyte containing a carboxylate, the excessive addition amount causes the gas to react at a high voltage cathode.
  • the carbon chain length of the chain carboxylate and the cyclic carbonate containing an unsaturated carbon bond which is related to the oxidation reaction of the two at the high voltage cathode.
  • the chain carboxylic acid ester is selected from compounds having the structural formula of formula I (the number of carbon atoms in R 2 is not less than the number of carbon atoms of R 1 ), the cyclic carbonate containing an unsaturated carbon bond is at the high voltage cathode
  • the gas production response will be significantly reduced. This may be due to the fact that the chain carboxylic acid esters have a coating inhibiting effect on the surface of the high voltage cathode. This effect has a significant effect on systems containing no more than 1% cyclic carbonate content of unsaturated carbon bonds.
  • the electrolyte has a chain carboxylate having a structural formula represented by Formula I (the number of carbon atoms in R 2 is not less than the number of carbon atoms in R 1 ) and a cyclic carbonate containing an unsaturated carbon bond
  • the content of the cyclic carbonate containing an unsaturated carbon bond in the electrolyte is not more than 1%, both the adverse reaction of the anode and the carboxylate is avoided, and the unsaturated carbon of the unsaturated bond at a high voltage is suppressed.
  • the gas production reaction of the ester is not more than 1%, both the adverse reaction of the anode and the carboxylate is avoided, and the unsaturated carbon of the unsaturated bond at a high voltage is suppressed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un électrolyte qui comprend un solvant organique non aqueux et un sel de lithium. Le solvant organique non aqueux contient un ester carboxylique linéaire et un carbonate cyclique dont la formule chimique structurale contient une double liaison C = C. La teneur du carbonate cyclique dont la formule chimique structurale contient la double liaison C = C n'est pas supérieure à 1 % en pourcentage massique dans l'électrolyte. L'électrolyte peut être utilisé pendant une longue durée dans des conditions de tension élevée, peut être utilisé dans une batterie au lithium-ion, peut fonctionner normalement pendant une longue durée dans la situation où la tension de fonctionnement est supérieure à 4,35 V et assure la propriété à haute température d'une batterie.
PCT/CN2015/071563 2014-12-12 2015-01-26 Électrolyte et batterie au lithium-ion l'utilisant WO2016090738A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410765234.5A CN104466251B (zh) 2014-12-12 2014-12-12 一种电解液及使用该电解液的锂离子电池
CN201410765234.5 2014-12-12

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WO2016090738A1 true WO2016090738A1 (fr) 2016-06-16

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CN104752769A (zh) * 2015-04-10 2015-07-01 宁德新能源科技有限公司 非水电解液及使用该电解液的锂离子电池
CN106207261B (zh) * 2015-05-25 2021-01-15 松下知识产权经营株式会社 电解液及电池
CN105006595B (zh) * 2015-08-18 2017-05-03 天津科技大学 基于碳酸甘油酯类化合物的电解液添加剂及锂离子电池
CN108242568A (zh) * 2016-12-26 2018-07-03 宁德时代新能源科技股份有限公司 电解液及二次电池

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CN101090165A (zh) * 2006-06-14 2007-12-19 三洋电机株式会社 二次电池用非水电解液及使用了它的非水电解液二次电池
WO2012002396A1 (fr) * 2010-06-30 2012-01-05 日本ゼオン株式会社 Composition de liant destinée à une électrode de batterie non aqueuse, composition de solution électrolytique destinée à une batterie non aqueuse, et utilisation associée

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