WO2022199163A1 - Additif pour électrolyte non aqueux, électrolyte non aqueux et batterie au lithium-ion - Google Patents

Additif pour électrolyte non aqueux, électrolyte non aqueux et batterie au lithium-ion Download PDF

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Publication number
WO2022199163A1
WO2022199163A1 PCT/CN2021/140300 CN2021140300W WO2022199163A1 WO 2022199163 A1 WO2022199163 A1 WO 2022199163A1 CN 2021140300 W CN2021140300 W CN 2021140300W WO 2022199163 A1 WO2022199163 A1 WO 2022199163A1
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WO
WIPO (PCT)
Prior art keywords
lithium
aqueous electrolyte
carbonate
electrolyte solution
phosphate
Prior art date
Application number
PCT/CN2021/140300
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English (en)
Chinese (zh)
Inventor
白晶
毛冲
王霹霹
欧霜辉
黄秋洁
张元青
戴晓兵
Original Assignee
珠海市赛纬电子材料股份有限公司
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Publication of WO2022199163A1 publication Critical patent/WO2022199163A1/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
    • H01M10/0567—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 belongs to the technical field of lithium ion batteries, and particularly relates to electrolyte additives, non-aqueous electrolytes and lithium ion batteries.
  • Lithium-ion batteries are widely used because of their high energy density, high charge-discharge efficiency, small self-discharge, long service life, and environmental friendliness. At present, it has been applied to the fields of consumer electronics, aerospace, military, power tools and electric vehicles. With the development of technology, whether it is in the field of consumption or power batteries, people have higher and higher requirements for the endurance of lithium-ion batteries, and the development of high-energy density (mass energy density and volume energy density) lithium batteries has become the key.
  • the development of high-energy-density lithium batteries can be done in two ways. One is to develop new positive and negative electrode materials with high gram capacity; the other is to improve the charging and discharging voltage of lithium batteries. Increasing the charge-discharge voltage of lithium batteries can simultaneously improve the mass energy density and volumetric energy density of lithium batteries, and can also reduce the cost of lithium batteries, which has become a research hotspot.
  • the purpose of the present application is to provide a non-aqueous electrolyte additive, which can improve the cycle performance and high-temperature storage performance of a lithium ion battery under a high voltage system.
  • Another object of the present application is to provide a non-aqueous electrolyte solution, the non-aqueous electrolyte solution containing the above-mentioned non-aqueous electrolyte solution additive can improve the cycle performance and high-temperature storage performance of a lithium ion battery under a high voltage system.
  • Another object of the present application is to provide a lithium ion battery, the lithium ion battery containing the above non-aqueous electrolyte has better cycle performance and high temperature storage performance in a high-voltage system.
  • non-aqueous electrolyte additive including the compound shown in structural formula 1:
  • R 1 , R 2 , R 3 , and R 4 are each independently selected from an oxygen atom or a sulfur atom
  • R 5 , R 6 , R 7 , and R 8 are each independently selected from a hydrogen atom or a C1-C5 hydrocarbon group
  • R 10 is each independently selected from a hydrogen atom, a halogen atom, a C1-C5 hydrocarbon group or a C1-C5 halogenated hydrocarbon group
  • R 11 is selected from magnesium or zinc.
  • the present application provides a non-aqueous electrolyte additive with a special structure, which exists in the form of ion pairs in the electrolyte due to its weak ionization ability.
  • the orotic acid group in the additive will bring special metal (Mg, Zn) ions into the surface of the positive electrode while participating in the formation of nitrogen-containing CEI film, so as to participate in the formation of special metal (Mg, Zn) ions.
  • the coating layer is coated on the positive electrode surface so that the positive electrode material can withstand higher temperature and higher voltage, so the non-aqueous electrolyte additive can significantly improve the lithium ion battery in high voltage system
  • the imine group on the orotic acid group has the function of complexing with fluoride ions in the electrolyte, which can significantly remove hydrofluoric acid and further improve the lithium ion battery in high voltage system. cycle performance and high temperature storage performance.
  • R 5 , R 6 , R 7 and R 8 are each independently selected from a hydrogen atom, a C1-C5 straight-chain alkyl group or a C1-C5 branched-chain alkyl group.
  • R 9 and R 10 are each independently selected from hydrogen atom, halogen atom, C1-C5 chain alkyl, C2-C5 chain alkenyl, C2-C5 chain alkynyl or C1-C5 chain
  • the C1-C5 chain alkyl group refers to a straight-chain alkyl group or a branched chain alkyl group with 1 to 5 carbon atoms
  • the C2-C5 chain alkenyl group refers to a carbon atom number of 1 to 5.
  • C2-C5 chain alkynyl refers to straight-chain or branched alkynyl having 2 to 5 carbon atoms.
  • the compound represented by the structural formula 1 of the present application is selected from at least one of compounds 1 to 6:
  • the present application also provides a non-aqueous electrolyte solution, including a lithium salt, a non-aqueous organic solvent, and the above-mentioned non-aqueous electrolyte solution additive.
  • the non-aqueous electrolyte solution of the present application includes the above-mentioned non-aqueous electrolyte solution additive, and the non-aqueous electrolyte solution is applied to a lithium ion battery.
  • the orotic acid group in the non-aqueous electrolyte additive will take special metal (Mg, Zn) ions into the surface of the positive electrode while participating in the formation of nitrogen-containing CEI film to make it participate.
  • a coating layer containing special metal (Mg, Zn) ions is formed, and the coating layer is coated on the surface of the positive electrode so that the positive electrode material can withstand higher temperatures and higher voltages, so the non-aqueous electrolyte additive can significantly improve lithium The cycle performance and high temperature storage performance of the ion battery under high voltage system; at the same time, the imine group on the orotic acid group has the function of complexing with fluoride ions in the electrolyte, which can significantly remove hydrofluoric acid and further improve lithium Cycling performance and high temperature storage performance of ion batteries in high voltage systems.
  • special metal Mg, Zn
  • the mass percentage of the non-aqueous electrolyte additive of the present application in the non-aqueous electrolyte is 0.1-1%; specifically, it can be 0.1%, 0.2%, 0.5%, 0.8%, 1%, but not limited to the above. Recited values apply equally well to other non-recited values within that range.
  • the lithium salt of the present application is selected from lithium hexafluorophosphate (LiPF 6 ), lithium difluorophosphate (LiPO 2 F 2 ), lithium bis-oxalate borate (LiBOB), lithium difluorooxalate borate (LiODFB), difluorobisoxalate phosphoric acid Lithium (LiPF 2 (C 2 O 4 ) 2 ), Lithium Tetrafluoroborate (LiBF 4 ), Lithium Tetrafluorooxalate Phosphate (LiPF 4 (C 2 O 4 )), Lithium Bistrifluoromethanesulfonimide (LiN (SO 2 CF 3 ) 2 ), at least one of lithium bisfluorosulfonimide (Li[N(SO 2 F) 2 ), and lithium tetrafluoromalonate phosphate.
  • LiPF 6 lithium hexafluorophosphate
  • LiPO 2 F 2 lithium bis-oxa
  • the mass percentage of the lithium salt of the present application in the non-aqueous electrolyte is 10-20%; specifically, it can be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17% , 18%, 19%, 20%, but are not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the non-aqueous organic solvent of the present application is selected from ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), propylene carbonate (PC) , at least one of butyl acetate (n-BA), ⁇ -butyrolactone ( ⁇ -GBL), propyl propionate (n-PP), ethyl propionate (EP) and ethyl butyrate (EB) kind.
  • the non-aqueous organic solvent is preferably ethylene carbonate (EC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC).
  • the mass percentage of the non-aqueous organic solvent of the present application in the non-aqueous electrolyte is 60-80%, specifically 60%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 80%, but not limited to the recited values, and other non-recited values within the numerical range are also applicable.
  • the non-aqueous electrolyte solution of the present application further includes an auxiliary agent, and the mass percentage of the auxiliary agent in the non-aqueous electrolyte solution is 0.1-10.5%;
  • the auxiliary agent is selected from 2,2,2-trifluoroethyl methyl carbonate , 2,2,2-trifluorodiethyl carbonate, 2,2,2-trifluoroethylpropyl carbonate, vinylene carbonate (VC), fluoroethylene carbonate (FEC), diethyl pyrocarbonate Esters (DEPC), 1,3-Propane Sultone (PS), Vinyl Sulfate (DTD), 1,2-Difluoroethylene Carbonate (DFEC), Tris(trimethylsilane) Phosphate (TMSP) ), tris(trimethylsilane) phosphite (TMSPi), 4,4'-bi-1,3-dioxolane-2,2'-dione (BDC), 3,3-bisulfuric acid Vinyl Este
  • the additive can form a stable passivation film on the surface of the positive electrode, prevent the oxidative decomposition of the electrolyte on the surface of the positive electrode, inhibit the dissolution of transition metal ions from the positive electrode, improve the stability of the structure and interface of the positive electrode material, and significantly improve the high temperature of the lithium ion battery. Storage performance and cycle performance.
  • the auxiliary agent is selected from vinylene carbonate (VC), fluoroethylene carbonate (FEC), 1,3-propane sultone (PS), vinyl sulfate (DTD), tris(trimethylsilane) ) Phosphate (TMSP), Tris(trimethylsilane) phosphite (TMSPi), 4,4'-bi-1,3-dioxolane-2,2'-dione (BDC), 3, Vinyl 3-bisulfate (BDTD) or 1,2-difluoroethylene carbonate (DFEC), and the content is 0.1-2%, 0.2-6%, 0.2-2%, 0.2-2%, 0.1%, respectively ⁇ 1.5%, 0.1 to 1.5%, 0.1 to 1.5%, 0.1 to 1.5%, 0.1 to 1.5%.5%.
  • VC vinylene carbonate
  • FEC fluoroethylene carbonate
  • PS 1,3-propane sultone
  • DTD vinyl sulfate
  • TMSP tris(trimethyls
  • vinyl sulfate (DTD) is added to the electrolyte as an auxiliary agent, which can modify the SEI film components on the negative electrode surface of lithium ion batteries and increase the relative content of sulfur atoms and oxygen atoms, which contain lone pair electrons. , which can attract lithium ions, accelerate the shuttle of lithium ions in the SEI film, and reduce the battery interface impedance, thereby effectively improving the charge and discharge performance of lithium ion batteries.
  • 1,3-Propane sultone (PS) has good film-forming properties as an auxiliary agent, which can form a large number of CEI films containing sulfonic acid groups at the positive interface, inhibit the decomposition and gas production of FEC at high temperature, and improve lithium-ion batteries.
  • Tris(trimethylsilane) phosphate (TMSP) and tris(trimethylsilane) phosphite (TMSPi) can absorb moisture and free acid to improve the cycling performance of lithium-ion batteries.
  • the present application also provides a lithium ion battery, which includes a positive electrode and a negative electrode, and also includes the above-mentioned non-aqueous electrolyte, and the highest charging voltage is 4.53V.
  • the non-aqueous electrolyte of the lithium ion battery of the present application includes a non-aqueous electrolyte additive, and the non-aqueous electrolyte additive is a compound shown in structural formula 1.
  • the structural formula While participating in the formation of nitrogen-containing CEI film, the orotate group in 1 will bring special metal (Mg, Zn) ions into the surface of the positive electrode to participate in the formation of a coating layer containing special metal (Mg, Zn) ions.
  • the coating layer is coated on the surface of the positive electrode so that the positive electrode material can withstand higher temperature and higher voltage, so the non-aqueous electrolyte additive can significantly improve the cycle performance and high temperature storage performance of lithium ion batteries under high voltage systems
  • the imine group on the orotic acid group has the function of complexing with fluoride ions in the electrolyte, which can significantly remove hydrofluoric acid and further improve the cycle performance and high temperature storage performance of lithium ion batteries under high voltage systems.
  • the active material of the positive electrode of the present application is lithium cobalt oxide.
  • the active material of the negative electrode of the present application is natural graphite.
  • ethylene carbonate, diethyl carbonate and ethyl methyl carbonate were uniformly mixed in a mass ratio of 1:1:2 to obtain 79.8 g of water organic solvent, and then 0.2 g of compound 1 was added as an additive to obtain a mixed solution.
  • the mixed solution was sealed and packaged and placed in the freezing room (-4°C) for 2 hours and then taken out.
  • a nitrogen-filled glove box O 2 ⁇ 1ppm, H 2 O ⁇ 1ppm
  • Capacity retention rate discharge capacity of the last cycle / discharge capacity of the first cycle ⁇ 100%
  • DCIR boost rate DCIR of the last 50 laps / DCIR of the first lap ⁇ 100%
  • Capacity retention rate discharge capacity of the last cycle / discharge capacity of the first cycle ⁇ 100%
  • DCIR boost rate DCIR of the last 50 laps / DCIR of the first lap ⁇ 100%
  • the formed lithium-ion battery was charged to 4.53V at 1C constant current and constant voltage at room temperature, and the initial discharge capacity and thickness of the battery were measured, and then stored at 85°C for 8 hours, and then discharged to 3.0V at 1C, and the capacity retention of the battery was measured. and recovery capacity and battery thickness after storage. Calculated as follows:
  • Battery capacity retention rate (%) retained capacity / initial capacity ⁇ 100%;
  • Thickness swelling ratio (%) (battery thickness after storage ⁇ initial battery thickness)/initial battery thickness ⁇ 100%.
  • the coating layer of special metal (Mg, Zn) ions is coated on the surface of the positive electrode, so that the positive electrode material can withstand higher temperature and higher voltage, so the non-aqueous electrolyte additive can significantly improve the lithium ion battery. Cycling performance and high temperature storage performance under high voltage system.

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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)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
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Abstract

La présente invention concerne un additif pour électrolyte non aqueux, un électrolyte non aqueux et une batterie au lithium-ion, l'additif pour électrolyte non aqueux comprenant un composé représenté par la formule structurelle 1, dans laquelle R1, R2, R3 et R4 sont chacun indépendamment choisis parmi un atome d'oxygène ou un atome de soufre ; R5, R6, R7 et R8 sont chacun indépendamment choisis parmi un atome d'hydrogène ou un groupe hydrocarbyle en C1-C5 ; R9 et R10 sont chacun indépendamment choisis parmi un atome d'hydrogène, un atome d'halogène, un groupe hydrocarbyle en C1-C5 ou un groupe hydrocarbyle halogéné en C1-C5 ; et R11 est choisi parmi le magnésium ou le zinc. L'additif pour électrolyte non aqueux peut améliorer les performances de cyclage et les performances de stockage à haute température de la batterie au lithium-ion dans un système à haute tension.
PCT/CN2021/140300 2021-03-25 2021-12-22 Additif pour électrolyte non aqueux, électrolyte non aqueux et batterie au lithium-ion WO2022199163A1 (fr)

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CN202110323174.1A CN113067034B (zh) 2021-03-25 2021-03-25 非水电解液添加剂、非水电解液及锂离子电池
CN202110323174.1 2021-03-25

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CN113067034B (zh) * 2021-03-25 2022-05-27 珠海市赛纬电子材料股份有限公司 非水电解液添加剂、非水电解液及锂离子电池
CN114188607B (zh) * 2021-12-20 2022-09-06 珠海市赛纬电子材料股份有限公司 添加剂及使用该添加剂的电解液和锂离子电池
CN114566710B (zh) * 2022-02-23 2024-06-11 珠海市赛纬电子材料股份有限公司 一种用于快充的锂离子电池非水电解液及锂离子电池

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CN102820483A (zh) * 2011-06-07 2012-12-12 索尼公司 非水电解质电池、电池组、电子装置和电动车辆
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CN112510260A (zh) * 2020-11-27 2021-03-16 珠海市赛纬电子材料股份有限公司 电解液添加剂、非水电解液和锂离子电池
CN113067034A (zh) * 2021-03-25 2021-07-02 珠海市赛纬电子材料股份有限公司 非水电解液添加剂、非水电解液及锂离子电池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070105782A1 (en) * 2005-10-07 2007-05-10 Board Of Trustees Of Southern Illinois University Protectant Combinations for Reducing Toxicities
CN102820483A (zh) * 2011-06-07 2012-12-12 索尼公司 非水电解质电池、电池组、电子装置和电动车辆
CN111108632A (zh) * 2017-09-15 2020-05-05 戴森技术有限公司 具有热加工部件的高能量密度多层电池单元及其制造方法
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CN113067034A (zh) * 2021-03-25 2021-07-02 珠海市赛纬电子材料股份有限公司 非水电解液添加剂、非水电解液及锂离子电池

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