CN111600074B - High-voltage lithium ion battery electrolyte and high-voltage lithium ion battery - Google Patents
High-voltage lithium ion battery electrolyte and high-voltage lithium ion battery Download PDFInfo
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- CN111600074B CN111600074B CN202010620725.6A CN202010620725A CN111600074B CN 111600074 B CN111600074 B CN 111600074B CN 202010620725 A CN202010620725 A CN 202010620725A CN 111600074 B CN111600074 B CN 111600074B
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- ion battery
- electrolyte
- lithium ion
- additive
- lithium
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 92
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 76
- 239000000654 additive Substances 0.000 claims abstract description 123
- 150000002825 nitriles Chemical class 0.000 claims abstract description 22
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 14
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- 239000006259 organic additive Substances 0.000 claims abstract 2
- 230000000996 additive effect Effects 0.000 claims description 78
- -1 1, 3-propylene sultone Chemical class 0.000 claims description 48
- 229910019142 PO4 Inorganic materials 0.000 claims description 26
- 239000010452 phosphate Substances 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 24
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- 150000008064 anhydrides Chemical class 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
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- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
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- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- 229910006763 Li—Sn—O Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010248 TiO2—Li4Ti5O12 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011329 calcined coke Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000006051 mesophase pitch carbide Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- OPUAWDUYWRUIIL-UHFFFAOYSA-L methanedisulfonate Chemical compound [O-]S(=O)(=O)CS([O-])(=O)=O OPUAWDUYWRUIIL-UHFFFAOYSA-L 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QJAVUVZBMMXBRO-UHFFFAOYSA-N tripentyl phosphate Chemical compound CCCCCOP(=O)(OCCCCC)OCCCCC QJAVUVZBMMXBRO-UHFFFAOYSA-N 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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
Landscapes
- 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
本发明属于电池技术领域，尤其涉及一种高电压锂离子电池电解液，包括锂盐、有机溶剂和添加剂，所述添加剂包括酸酐类添加剂、腈类添加剂、具有式Ⅰ所示结构的磷酸酯类添加剂和具有式Ⅱ所示结构的亚硫酸酯类添加剂中的至少一种。另外，本发明还涉及一种高电压锂离子电池。相比于现有技术，本发明的电解液具有更优的耐高温、高压性能，有利于改善高电压锂离子电池的高温存储和循环性能。The invention belongs to the technical field of batteries, and in particular relates to a high-voltage lithium-ion battery electrolyte, comprising lithium salts, organic solvents and additives. The additives include acid anhydride additives, nitrile additives, and phosphate esters having the structure shown in formula I At least one of the additives and the sulfite additives having the structure shown in formula II. In addition, the present invention also relates to a high-voltage lithium-ion battery. Compared with the prior art, the electrolyte of the present invention has better high temperature resistance and high pressure performance, which is beneficial to improve the high temperature storage and cycle performance of the high voltage lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a high-voltage lithium ion battery electrolyte and a high-voltage lithium ion battery.
Background
Compared with other batteries, the lithium ion battery has the advantages of light weight, small volume, high working voltage, high energy density, large output power, high charging efficiency, no memory effect, long cycle life and the like, is widely applied to the field of digital products such as mobile phones, notebook computers and the like, and is considered as one of the best choices of electric vehicles and large energy storage devices. At present, electronic digital products such as smart phones and tablet computers have higher and higher requirements on energy density of batteries, so that commercial lithium ion batteries are difficult to meet the requirements. The adoption of high-capacity anode materials or high-voltage anode materials is the most effective way for improving the energy density of the lithium ion battery.
However, in the high voltage battery, the oxidative decomposition phenomenon of the electrolyte is increased while the charge voltage of the positive electrode material is increased, thereby causing deterioration of the battery performance. In addition, a phenomenon that positive electrode metal ions are eluted during the use of a high-voltage battery is common, and especially after the battery is stored at a high temperature for a long time, the elution of the positive electrode metal ions is further accelerated, so that the retention capacity of the battery is low. The problems of poor high-temperature cycle and high-temperature storage performance of the current commercialized cobalt acid lithium battery with the voltage of more than 4.4V and the ternary-material high-voltage battery generally exist, and the problems are mainly reflected in that the thickness expansion and the internal resistance increase are large after high-temperature cycle, and the capacity is kept low after long-time high-temperature storage. The factors responsible for these problems are mainly: (1) oxidative decomposition of the electrolyte. Under high voltage, the oxidation activity of the positive electrode active material is high, so that the reactivity between the positive electrode active material and the electrolyte is increased, and under high temperature, the reaction between the high-voltage positive electrode and the electrolyte is further intensified, so that the oxidative decomposition product of the electrolyte is continuously deposited on the surface of the positive electrode, the surface characteristic of the positive electrode is degraded, and the internal resistance and the thickness of the battery are continuously increased. (2) The metal ions of the positive electrode active material are eluted and reduced. In one aspect, LiPF in an electrolyte at high temperatures6Very easily decomposed to produce HF and PF5. Wherein, HF can corrode the anode to cause the dissolution of metal ions, thereby destroying the structure of the anode material and causing the loss of capacity; on the other hand, at a high voltage, the electrolyte is easily oxidized at the positive electrode, and metal ions of the positive electrode active material are easily reduced and eluted into the electrolyte, thereby destroying the positive electrode material structure and causing a capacity loss. Meanwhile, metal ions dissolved out of the electrolyte easily penetrate through the SEI to reach the negative electrode to obtain electrons and are reduced into a metal simple substance, so that the SEI structure is damaged, the impedance of the negative electrode is continuously increased, the self-discharge of the battery is aggravated, the irreversible capacity is increased, and the performance is deteriorated.
Therefore, in the prior art, PS and/or nitrile additives are adopted to improve the high-temperature and high-pressure resistance of the electrolyte, although the high-temperature and high-pressure resistance of the electrolyte is improved to a certain extent by the two electrolyte additives, the improvement of the high-temperature performance is not obvious when the PS dosage is more than 4%, and the increase of the PS and nitrile dosages can deteriorate the cycle performance of the battery.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the electrolyte of the high-voltage lithium ion battery is provided, has better high-temperature and high-voltage resistance, and is beneficial to improving the high-temperature storage and cycle performance of the high-voltage lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-voltage lithium ion battery electrolyte comprises lithium salt, an organic solvent and an additive, wherein the additive comprises at least one of an anhydride additive, a nitrile additive, a phosphate additive with a structure shown in a formula I and a sulfite additive with a structure shown in a formula II,
wherein R0 and R are independently selected from alkyl, fluoroalkyl, alkenyl, alkynyl, phenyl, fluorophenyl, biphenyl or monofluorobiphenyl; R1-R5 are independently selected from fluorine atom or hydrogen atom; one of R6-R14 is fluorine atom or-CF3And the balance being hydrogen atoms; r15 is phenyl or fluorophenyl.
As an improvement of the high-voltage lithium ion battery electrolyte, the addition amount of the phosphate additive with the structure shown in the formula I and/or the sulfite additive with the structure shown in the formula II accounts for 0.5-5% of the total mass of the electrolyte.
As an improvement of the high-voltage lithium ion battery electrolyte, the addition amount of the anhydride additive accounts for 0.2-0.5% of the total mass of the electrolyte.
As an improvement of the high-voltage lithium ion battery electrolyte, the addition amount of the nitrile additive accounts for 0.2-6% of the total mass of the electrolyte.
As an improvement of the high-voltage lithium ion battery electrolyte, the acid anhydride additive comprises at least one of phthalic anhydride, 2-methyl maleic anhydride, succinic anhydride, 1-propyl phosphoric anhydride and citric anhydride.
As an improvement of the high-voltage lithium ion battery electrolyte, the nitrile additive comprises at least one of ethylene glycol dipropionitrile ether, 1,3, 6-hexanetricarbonitrile, adiponitrile, succinonitrile, pentafluoroalkoxy cyclotriphosphazene and 1, 4-dicyano-2-butene.
As an improvement of the high voltage lithium ion battery electrolyte according to the present invention, the additive further includes at least one of 1, 3-propane sultone, fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1, 3-propylene sultone, 1, 4-butane sultone, triallyl isocyanurate, tripentyl phosphate, triallyl phosphate, ethyl 4,4, 4-trifluorobutyrate, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, fluorobenzene, boron trifluoride tetrahydrofuran, tris (trimethylsilane) phosphate, tris (trimethylsilane) borate, and methane disulfonate.
As an improvement of the high-voltage lithium ion battery electrolyte, the total mass of the additive accounts for 5-15% of the total mass of the electrolyte.
As an improvement of the high voltage lithium ion battery electrolyte according to the present invention, the lithium salt is lithium hexafluorophosphate or a mixed salt of lithium hexafluorophosphate and a doped lithium salt, and the doped lithium salt includes at least one of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium difluoro (oxalato) borate, lithium difluoro (oxalato) phosphate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, lithium perfluoroalkyl sulfonyl imide, lithium perfluoroalkyl sulfonyl methyl, lithium difluoro (oxalato) phosphate, and lithium tetrafluoro (oxalato) phosphate.
As an improvement of the high-voltage lithium ion battery electrolyte, the addition amount of the organic solvent accounts for 60-85% of the total mass of the electrolyte, and the organic solvent comprises diethyl carbonate and at least one of ethylene carbonate and propylene carbonate.
As an improvement of the high voltage lithium ion battery electrolyte, the organic solvent further includes at least one of ethyl methyl carbonate, dimethyl carbonate, propyl propionate, ethyl propionate, propyl acetate, butyl butyrate, ethyl butyrate, γ -butyrolactone, γ -valerolactone, δ -valerolactone, ethyl acetate, dipropyl carbonate, and dibutyl carbonate.
The second purpose of the invention is: the high-voltage lithium ion battery is provided, the charge cut-off voltage is 4.4V-5.0V, and the high-voltage lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is the high-voltage lithium ion battery electrolyte disclosed by any one of claims 1-11.
As an improvement of the high-voltage lithium ion battery, the active material of the positive electrode is LiCowL1-wO2Wherein L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0<w≤1。
As an improvement of the high-voltage lithium ion battery, the active material of the positive electrode is LiNixCoyMnzM1-x-y-zO2Or LiNiaCobAlcN1-a-b-cO2Wherein M and N are respectively and independently selected from any one of Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, and y is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than 1, z is more than or equal to 0 and less than or equal to 1, x + y + z is less than or equal to 1, a is more than or equal to 0 and less than or equal to 1<1，0≤b≤1，0≤c≤1，a+b+c≤1。
Compared with the prior art, the beneficial effects of the invention include but are not limited to:
1) the additive contains low-impedance anhydride, on one hand, the additive can neutralize the alkalinity of the surface of a positive electrode and inhibit the decomposition effect of the alkalinity of metal oxide on carbonic ester, and on the other hand, the anhydride can react with water in a pole piece or electrolyte to generate organic acid and reduce the dissolution of materials. In addition, the acid anhydride can form a film on the surface of the positive electrode at a high potential, so that the cycle performance of the battery under a high-voltage condition is obviously improved.
2) The additive contains nitrile additive, can generate complexation with metal ions, reduces the decomposition of electrolyte, inhibits the dissolution of metal ions, protects the positive electrode and improves the high-temperature performance of the battery.
3) The additive contains the phosphate additive with the structure shown in the formula I, and a stable protective film can be formed on an electrode by consuming a small amount of charges, so that the circulation and the multiplying power of a battery can be improved, and the expansion of a pole piece after the battery is circulated can be inhibited. Moreover, the phosphate additive also has a certain flame retardant effect.
4) The additive contains sulfite additives with a structure shown in a formula II, can be preferentially reduced at a negative electrode to generate a protective film, can be further combined with a reduced solvent to generate a more compact solid interfacial film, and can inhibit the thickening of the negative electrode after high-temperature circulation, so that the electrolyte presents excellent storage stability, and the low-temperature performance of the electrolyte can be improved. But it also prevents PC molecules from intercalating into the graphite electrode. In addition to this, it is a biphenyl group-containing sulfate compound, which has an effect of preventing overcharge.
5) The electrolyte of the high-voltage lithium ion battery adopts at least one of the additives, so that the high-temperature storage performance and the cycle performance of the high-voltage lithium ion battery are effectively improved. Particularly, when a plurality of types are used in combination, the high-temperature storage and cycle performance of the high-voltage lithium ion battery can be more remarkably improved.
Detailed Description
Embodiments of the present application will be described in detail below. The examples of the present application should not be construed as limiting the present application.
The following terms as used herein have the meanings indicated below, unless otherwise explicitly indicated.
The term "alkyl" is intended to be a straight-chain saturated hydrocarbon structure having 1 to 20, 1 to 15, 1 to 10, 1 to 5, or 3 to 5 carbon atoms. "alkyl" is also contemplated to be a branched or cyclic hydrocarbon structure having 3 to 20, 3 to 15, 3 to 10, or 3 to 5 carbon atoms. When alkyl groups having a particular carbon number are specified, all geometric isomers having that carbon number are intended to be encompassed; thus, for example, "butyl" is meant to include n-butyl, sec-butyl, isobutyl, tert-butyl, and cyclobutyl; "propyl" includes n-propyl, isopropyl and cyclopropyl. Examples of 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, and the like.
The term "alkenyl" refers to a monovalent unsaturated hydrocarbon group that can be straight or branched chain and has at least one and typically 1,2, or 3 carbon-carbon double bonds. Unless otherwise defined, the alkenyl group typically contains 2 to 20, 2 to 15, 2 to 10, 2 to 6, or 2 to 4 carbon atoms and includes, for example, -C2-4Alkenyl, -C2-6Alkenyl and-C2-10An alkenyl group. Representative alkenyl groups include, by way of example, ethenyl, n-propenyl, isopropenyl, n-but-2-enyl, but-3-enyl, n-hex-3-enyl, and the like.
The term "alkynyl" refers to a monovalent unsaturated hydrocarbon group that can be straight-chain or branched and has at least one, and typically 1,2, or 3 carbon-carbon triple bonds. Unless otherwise defined, the alkynyl group typically contains 2 to 20, 2 to 15, 2 to 10, 3 to 6, or 2 to 4 carbon atoms and includes, for example, -C2-4Alkynyl, -C3-6Alkynyl and-C3-10Alkynyl. Representative alkynyl groups include, for example, ethynyl, prop-2-ynyl (n-propynyl), n-but-2-ynyl, n-hex-3-ynyl, and the like.
The term "fluoroalkyl" means an alkyl group in which one or more hydrogen atoms are replaced with a fluorine atom.
The term "fluorophenyl" means a phenyl group in which one or more hydrogen atoms are replaced by a fluorine atom.
The term "monofluorobiphenyl" means that one hydrogen atom in a biphenyl group is replaced with a fluorine atom.
1. Electrolyte solution
The first aspect of the present application provides a high voltage lithium ion battery electrolyte, which includes a lithium salt, an organic solvent and an additive, wherein the additive includes at least one of an anhydride additive, a nitrile additive, a phosphate additive having a structure shown in formula I and a sulfite additive having a structure shown in formula II,
wherein R0 and R are independently selected from alkyl, fluoroalkyl, alkenyl, alkynyl, phenyl, fluorophenyl, biphenyl or monofluorobiphenyl; R1-R5 are independently selected from fluorine atom or hydrogen atom; one of R6-R14 is fluorine atom or-CF3And the balance being hydrogen atoms; r15 is phenyl or fluorophenyl.
The inventor of the application unexpectedly finds that the high-temperature storage and cycle performance of the high-voltage lithium ion battery can be remarkably improved by adding at least one of an anhydride additive, a nitrile additive, a phosphate additive with a structure shown in formula I and a sulfite additive with a structure shown in formula II into the high-voltage lithium ion battery electrolyte.
Additive agent
In some embodiments, the high voltage lithium ion battery electrolyte of the present application includes an anhydride-based additive. In some embodiments, the high voltage lithium ion battery electrolyte of the present application includes additives that are nitrile based. In some embodiments, the additive of the electrolyte for high voltage lithium ion batteries of the present application comprises a phosphate additive having a structure represented by formula i. In some embodiments, the additive of the electrolyte for high voltage lithium ion batteries of the present application comprises a sulfite additive having a structure represented by formula ii. In some embodiments, the additives of the high voltage lithium ion battery electrolyte of the present application include anhydride-based additives and nitrile-based additives. In some embodiments, the additives of the electrolyte for high voltage lithium ion batteries of the present application include an acid anhydride additive and a phosphate additive having a structure represented by formula i. In some embodiments, the additives of the electrolyte for high voltage lithium ion batteries of the present application include an anhydride additive and a sulfite additive having a structure represented by formula ii. In some embodiments, the additives of the electrolyte for the high-voltage lithium ion battery comprise a nitrile additive and a phosphate additive with a structure shown in formula I. In some embodiments, the additives of the high voltage lithium ion battery electrolyte of the present application include a nitrile additive and a sulfite additive having a structure represented by formula ii. In some embodiments, the additives of the electrolyte for high voltage lithium ion batteries of the present application include phosphate additives having a structure represented by formula i and sulfite additives having a structure represented by formula ii. In some embodiments, the additives of the electrolyte for the high-voltage lithium ion battery comprise an acid anhydride additive, a nitrile additive and a phosphate additive with a structure shown in formula I. In some embodiments, the additives of the high voltage lithium ion battery electrolyte comprise an anhydride additive, a nitrile additive and a sulfite additive having a structure shown in formula II. In some embodiments, the additives of the electrolyte for high voltage lithium ion batteries of the present application include an acid anhydride additive, a phosphate additive having a structure represented by formula i, and a sulfite additive having a structure represented by formula ii. In some embodiments, the additives of the electrolyte for high voltage lithium ion batteries of the present application include nitrile additives, phosphate additives having a structure represented by formula i, and sulfite additives having a structure represented by formula ii. In some embodiments, the additives of the electrolyte for high voltage lithium ion batteries of the present application include acid anhydride additives, nitrile additives, phosphate additives having a structure represented by formula i, and sulfite additives having a structure represented by formula ii.
In some embodiments, the phosphate additive with the structure shown in formula I is added in an amount of 0.5-5% of the total mass of the electrolyte. In some embodiments, the sulfite additive with the structure shown in the formula II is added in an amount of 0.5-5% of the total mass of the electrolyte. In some embodiments, the total addition amount of the phosphate additive with the structure shown in the formula I and the sulfite additive with the structure shown in the formula II accounts for 0.5-5% of the total mass of the electrolyte. The content of the additives is not suitable to be excessive, so that the impedance of the battery is increased too obviously, and the comprehensive performance of the battery is influenced.
In some embodiments, the anhydride-based additive includes, but is not limited to, at least one of phthalic anhydride, 2-methyl maleic anhydride, succinic anhydride, 1-propyl phosphoric anhydride, and citric anhydride.
In some embodiments, the addition amount of the anhydride additive accounts for 0.2-0.5% of the total mass of the electrolyte. The content of the additives is not suitable to be excessive, so that the impedance of the battery is increased too obviously, and the comprehensive performance of the battery is influenced.
In some embodiments, the nitrile additives include, but are not limited to, at least one of ethylene glycol dipropionitrile ether, 1,3, 6-hexanetricarbonitrile, adiponitrile, succinonitrile, pentafluoroalkoxycyclotriphosphazene, and 1, 4-dicyano-2-butene.
In some embodiments, the nitrile additive is added in an amount of 0.2-6% by mass based on the total mass of the electrolyte. The content of the additives is not suitable to be excessive, so that the impedance of the battery is increased too obviously, and the comprehensive performance of the battery is influenced.
In some embodiments, the additive further comprises at least one of 1, 3-propane sultone, fluoroethylene carbonate, vinylene carbonate, vinylethylene carbonate, 1, 3-propene sultone, 1, 4-butanesultone, triallyl isocyanurate, triallyl phosphate, ethyl 4,4, 4-trifluorobutyrate, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, fluorobenzene, boron trifluoride tetrahydrofuran, tris (trimethylsilane) phosphate, tris (trimethylsilane) borate, and methylene methanedisulfonate.
In some embodiments, the total mass of all additives accounts for 5-15% of the total mass of the electrolyte. The contents of all the additives mentioned in the above examples are controlled within this range, and excessive total contents result in a significant increase in battery impedance, affecting battery performance. Furthermore, each type of additive needs to be controlled within a reasonable content range, and increasing the content of one type alone while decreasing the content of the other type also increases the battery impedance. That is, if and only if the additives are controlled within their reasonable ranges, the additives of the various types can exert their optimal effects, and the overall performance of the battery can be improved by the synergistic effect.
Lithium salt
In some embodiments, the lithium salt is lithium hexafluorophosphate. In some embodiments, the lithium salt is a mixed salt of lithium hexafluorophosphate and a doped lithium salt comprising at least one of lithium bis-fluorosulfonylimide, lithium bis-trifluoromethylsulfonyl imide, lithium difluoro-oxalato-borate, lithium difluorophosphate, lithium tetrafluoroborate, lithium bis-oxalato-borate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, lithium perfluoroalkyl sulfonyl imide, lithium perfluoroalkyl sulfonyl methide, lithium difluoro-oxalato-phosphate, and lithium tetrafluorooxalato-phosphate.
Organic solvent
In some embodiments, the organic solvent comprises ethylene carbonate and diethyl carbonate. In some embodiments, the organic solvent comprises propylene carbonate and diethyl carbonate. In some embodiments, the organic solvent comprises ethylene carbonate, propylene carbonate, and diethyl carbonate.
In some embodiments, the organic solvent comprises at least one of ethyl methyl carbonate, dimethyl carbonate, propyl propionate, ethyl propionate, propyl acetate, butyl butyrate, ethyl butyrate, gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, ethyl acetate, dipropyl carbonate, and dibutyl carbonate, in addition to the organic solvents listed above.
In some embodiments, the addition amount of the organic solvent accounts for 60-85% of the total mass of the electrolyte,
2. high voltage lithium ion battery
The second aspect of the application provides a high voltage lithium ion battery, and the cut-off voltage of charging is 4.4V ~ 5.0V, including positive pole, negative pole, set up the diaphragm between positive pole and negative pole to and electrolyte, electrolyte be this application high voltage lithium ion battery electrolyte.
Positive electrode
In the high voltage lithium ion battery described herein, the positive electrode includes a positive current collector and a positive active material layer disposed on the positive current collector.
In some embodiments, the positive electrode active material is LiCowL1-wO2Wherein L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0<w≤1。
In some embodiments, the positive active material is LiNixCoyMnzM1-x-y-zO2Wherein M is selected from any one of Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, y is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is less than or equal to 1.
In some embodiments, the positive active material is LiNiaCobAlcN1-a-b-cO2Wherein N is selected from any one of Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, and a is more than or equal to 0<1，0≤b≤1，0≤c≤1，a+b+c≤1。
In some embodiments, the positive active material layer further comprises a binder. The binder improves the binding of the positive electrode active material particles to each other, and also improves the binding of the positive electrode active material to the current collector. Non-limiting examples of binders include polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoride, polyethylene, polypropylene, styrene butadiene rubber, acrylated styrene butadiene rubber, epoxy, nylon, and the like.
In some embodiments, the positive active material layer further includes a conductive material, thereby imparting conductivity to the electrode. The conductive material may include any conductive material as long as it does not cause a chemical change. Non-limiting examples of the conductive material include carbon-based materials (e.g., natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, etc.), metal-based materials (e.g., metal powder, metal fiber, etc., including, for example, copper, nickel, aluminum, silver, etc.), conductive polymers (e.g., polyphenylene derivatives), and mixtures thereof.
The positive electrode current collector for the high voltage lithium ion battery of the present application may be aluminum, but is not limited thereto.
Negative electrode
In the high voltage lithium ion battery described herein, the negative electrode includes a negative current collector and a negative active material layer disposed on the negative current collector. The specific kind of the negative electrode active material is not particularly limited and may be selected as desired.
In some embodiments, the negative active material is selected from natural graphite, artificial graphite, mesophase micro carbon spheres (abbreviated as MCMB), hard carbon, soft carbon, silicon-carbon composite, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO2Spinel-structured lithiated TiO2-Li4Ti5O12And one or more of Li-Al alloy. Non-limiting examples of carbon materials include crystalline carbon, amorphous carbon, and mixtures thereof. The crystalline carbon may be natural graphite or artificial graphite in an amorphous form or in a form of a flake, a platelet, a sphere or a fiber. The amorphous carbon may be soft carbon, hard carbon, mesophase pitch carbide, calcined coke, or the like.
In some embodiments, the negative active material layer may include a binder. The binder improves the binding of the negative active material particles to each other and the binding of the negative active material to the current collector. Non-limiting examples of binders include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy, nylon, and the like.
In some embodiments, the negative active material layer further includes a conductive material, thereby imparting conductivity to the electrode. The conductive material may include any conductive material as long as it does not cause a chemical change. Non-limiting examples of the conductive material include carbon-based materials (e.g., natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, etc.), metal-based materials (e.g., metal powder, metal fiber, etc., such as copper, nickel, aluminum, silver, etc.), conductive polymers (e.g., polyphenylene derivatives), and mixtures thereof.
The negative current collector for use herein may be selected from the group consisting of copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, polymer substrates coated with conductive metals, and combinations thereof.
Diaphragm
In some embodiments, the high voltage lithium ion batteries of the present application are provided with a separator between the positive and negative electrodes to prevent short circuits.
The material and shape of the separator used in the high voltage lithium ion battery of the present application are not particularly limited, and may be any of the techniques disclosed in the prior art.
In some embodiments, the separator includes a polymer or inorganic substance or the like formed of a material stable to the electrolyte of the present application. For example, the separator may include a substrate layer and a surface treatment layer. The substrate layer is a non-woven fabric, a film or a composite film with a porous structure, and the material of the substrate layer is at least one selected from polyethylene, polypropylene, polyethylene terephthalate and polyimide. Specifically, a polypropylene porous film, a polyethylene porous film, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric, or a polypropylene-polyethylene-polypropylene porous composite film can be used. At least one surface of the substrate layer is provided with a surface treatment layer, and the surface treatment layer can be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic substance. The inorganic layer comprises inorganic particles and a binder, wherein the inorganic particles are selected from one or more of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium oxide, tin oxide, cerium dioxide, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and barium sulfate. The binder is selected from one or a combination of more of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene. The polymer layer comprises a polymer, and the material of the polymer is selected from at least one of polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride and poly (vinylidene fluoride-hexafluoropropylene).
Embodiments of the present application are illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the claims herein.
Comparative example 1
1) Preparation of the Positive electrode
A positive electrode active material LCO (4.48V), conductive carbon black Super-P and a binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 93:4:3, and then dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a positive electrode slurry. And uniformly coating the slurry on two sides of the aluminum foil, drying, rolling and vacuum drying, and welding an aluminum outgoing line by using an ultrasonic welding machine to obtain the positive plate, wherein the thickness of the pole piece is 120-150 mu m.
2) Preparation of the negative electrode
Mixing artificial graphite serving as a negative electrode active material, conductive carbon black Super-P, Styrene Butadiene Rubber (SBR) serving as a binder and carboxymethyl cellulose (CMC) according to a mass ratio of 94:1:2.5:2.5, and dispersing the materials in ionized water to obtain negative electrode slurry. Coating the slurry on two sides of the copper foil, drying, rolling and vacuum drying, and welding a nickel outgoing line by using an ultrasonic welding machine to obtain the negative plate, wherein the thickness of the pole piece is 120-150 mu m.
3) Preparation of the electrolyte
Ethylene Carbonate (EC), diethyl carbonate (DEC) and Propylene Carbonate (PC) were mixed in a mass ratio of EC: DEC: PC: 2:6:2, and then 0.2 wt% VC, 5.0 wt% FEC, 2% wtPS, 1.0% wtADN, 1.0% wtEGBE and 1.0% wtHTCN were added, respectively, followed by 14.0 wt% lithium hexafluorophosphate (LiPF)6) Fully mixing and dissolving for later use.
4) Preparation of the separator
A16 μm thick Polyethylene (PE) barrier film was used.
5) Preparation of high-voltage lithium ion battery
Winding a sandwich structure consisting of the positive plate, the negative plate and the diaphragm, flattening the wound body, putting the flattened wound body into an aluminum-plastic film packaging bag, and baking the flattened wound body in vacuum at 80 ℃ for 48 hours to obtain an electric core to be injected with liquid; respectively injecting the prepared electrolyte into a battery cell in a glove box with the dew point controlled below-40 ℃, carrying out vacuum packaging, standing for 24h, and then carrying out conventional formation and capacity grading according to the following steps: charging at 0.05C for 180min, charging at 0.2C to 4.0V, and vacuum sealing twice; further charging to 4.48V at a constant current of 0.2C, standing at normal temperature for 24h, and discharging to 3.0V at a constant current of 0.2C; and finally, charging the battery to 4.48V at a constant current of 1C for standby.
Examples 1 to 15
In contrast to the comparative examples, the preparation of the electrolyte was:
at least one of additives a to d is further added to the electrolyte in the embodiments 1 to 15, the specific structural formulas of the additives a to d are shown in table 1, and the specific compositions of the additives a to d in each embodiment are shown in table 2.
The rest is the same as comparative example 1 and will not be described again.
TABLE 1 specific structural formulas of additives
Performance testing
The performance of the high voltage lithium ion batteries prepared in comparative example 1 and examples 1 to 15 was tested.
1) EIS Performance test
Taking the cell after grading of comparative example 1 and examples 1-15, and carrying out EIS test under the following test conditions: the frequency range is 100 kHz-0.01 Hz, and the amplitude is 10 mV; the tested data were subjected to circuit fitting to obtain SEI impedance, the results of which are shown in table 1.
2) High temperature cycle performance test
The batteries prepared in comparative example 1 and examples 1 to 15 were placed in an oven at a constant temperature of 45 ℃, and were charged to 4.48V at a constant current of 0.7C and then the constant voltage charging current was decreased to 0.02C, and then discharged to 3.0V at a constant current of 0.7C, and the cycle was repeated for 300 weeks, and the discharge capacity per week was recorded, and the capacity retention rate in the high-temperature cycle was calculated according to the following formula: the n-week capacity retention rate is 100% of the n-week discharge capacity/1-week discharge capacity.
3) Test of ordinary temperature cycle Performance
Taking the batteries prepared in the comparative example 1 and the examples 1 to 15, charging the batteries to 4.48V at room temperature by a constant current of 0.7C, then charging the batteries at constant voltage until the current is reduced to 0.02C, then discharging the batteries to 3.0V at a constant current of 0.7C, cycling the batteries for 300 weeks, recording the discharge capacity of each week, and calculating the capacity retention rate of the batteries in normal-temperature cycling according to the following formula: capacity retention rate at m weeks was 100% of discharge capacity at m weeks/discharge capacity at 1 week.
4) High temperature storage Performance test
The batteries prepared in comparative example 1 and examples 1 to 15 were used, and the 0.7C discharge capacity C was measured at room temperature0And initial thickness T in full electric state0Then fully charged, stored in an oven at 85 ℃ for 12 hours and measured for thickness T1And standing at room temperature for 2h, and measuring the residual capacity C1And recovery capacity C2. Thickness expansion ratio ═ T1/T0-1) 100%, capacity remaining rate C1/C0100%, capacity recovery rate ═ C2/C0Specific results of performance tests of 100% or more are shown in tables 2 to 3.
TABLE 2 EIS test results
TABLE 3 test results of cycle capacity retention rate and high-temperature storage performance
As can be seen from the data in tables 2-3:
1) by adding the four additives a, b, c and d independently, the film forming resistance of the added compounds b and d under high voltage is relatively large, and the film forming resistance of the added compounds a and c is small; and the four compounds all improve the cycle performance and the high-temperature storage performance of the battery to a certain extent.
2) When the additives a, b, c and d are combined, the cycle performance is slightly deteriorated, but the high-temperature storage performance is further improved.
3) When more than three compounds of the additives a, b, c and d are combined, the cycle performance and the high-temperature storage performance are obviously improved, which also shows that the combination of more than three compounds improves the comprehensive performance of the battery through synergistic action, wherein the combination effect of four compounds is obvious.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (14)
1. A high voltage lithium ion battery electrolyte is characterized in that: comprises lithium salt, organic solvent and additive, wherein the additive comprises at least one of anhydride additive, nitrile additive, phosphate additive with a structure shown in formula I and sulfite additive with a structure shown in formula II,
wherein R0 and R are independently selected from alkyl, fluoroalkyl, alkenyl, alkynyl, phenyl, fluorophenyl, biphenyl or monofluorobiphenyl; R1-R5 are independently selected from fluorine atom or hydrogen atom; one of R6-R14 is fluorine atom or-CF3And the balance being hydrogen atoms; r15 is phenyl or fluorophenyl;
the high voltage is 4.4-5.0V.
2. The high voltage lithium ion battery electrolyte of claim 1, wherein: the addition amount of the phosphate additive with the structure shown in the formula I and/or the sulfite additive with the structure shown in the formula II accounts for 0.5-5% of the total mass of the electrolyte.
3. The high voltage lithium ion battery electrolyte of claim 1, wherein: the addition amount of the anhydride additive accounts for 0.2-0.5% of the total mass of the electrolyte.
4. The high voltage lithium ion battery electrolyte of claim 1, wherein: the addition amount of the nitrile additive accounts for 0.2-6% of the total mass of the electrolyte.
5. The high voltage lithium ion battery electrolyte of claim 1, wherein: the anhydride additive comprises at least one of phthalic anhydride, 2-methyl maleic anhydride, succinic anhydride, 1-propyl phosphoric anhydride and citric anhydride.
6. The high voltage lithium ion battery electrolyte of claim 1, wherein: the nitrile additive comprises at least one of ethylene glycol dipropionitrile ether, 1,3, 6-hexanetricarbonitrile, adiponitrile, succinonitrile, pentafluoroalkoxy cyclotriphosphazene and 1, 4-dicyano-2-butene.
7. The high voltage lithium ion battery electrolyte of claim 1, wherein: the additive further comprises at least one of 1, 3-propane sultone, fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1, 3-propylene sultone, 1, 4-butane sultone, triallyl isocyanurate, triallyl phosphate, ethyl 4,4, 4-trifluorobutyrate, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, fluorobenzene, boron trifluoride tetrahydrofuran, tris (trimethylsilane) phosphate, tris (trimethylsilane) borate, and methylene methanedisulfonate.
8. The high voltage lithium ion battery electrolyte of claim 7, wherein: the total mass of the additive accounts for 5-15% of the total mass of the electrolyte.
9. The high voltage lithium ion battery electrolyte of claim 1, wherein: the lithium salt is lithium hexafluorophosphate or a mixed salt composed of lithium hexafluorophosphate and a doped lithium salt, and the doped lithium salt comprises at least one of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium difluoro (oxalato) borate, lithium difluoro (phosphorato) phosphate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, lithium perfluoroalkyl sulfonyl imide, lithium perfluoroalkyl sulfonyl methyl, lithium difluoro (oxalato) phosphate and lithium tetrafluorooxalato phosphate.
10. The high voltage lithium ion battery electrolyte of claim 1, wherein: the addition amount of the organic solvent accounts for 60-85% of the total mass of the electrolyte, and the organic solvent comprises diethyl carbonate and at least one of ethylene carbonate and propylene carbonate.
11. The high voltage lithium ion battery electrolyte of claim 10, wherein: the organic solvent also comprises at least one of methyl ethyl carbonate, dimethyl carbonate, propyl propionate, ethyl propionate, propyl acetate, butyl butyrate, ethyl butyrate, gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, ethyl acetate, dipropyl carbonate and dibutyl carbonate.
12. A high-voltage lithium ion battery, the cut-off voltage of charging is 4.4V ~ 5.0V, including positive pole, negative pole, set up in anodal with the diaphragm between the negative pole, and electrolyte, its characterized in that: the electrolyte is the electrolyte for the high-voltage lithium ion battery as defined in any one of claims 1 to 11.
13. The high voltage lithium ion battery of claim 12, wherein: the active material of the positive electrode is LiCowL1-wO2Wherein L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0<w≤1。
14. The high voltage lithium ion battery of claim 12, wherein: the active material of the positive electrode is LiNixCoyMnzM1-x-y-zO2Or LiNiaCobAlcN1-a-b-cO2Wherein M and N are respectively and independently selected from any one of Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, and y is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than 1, z is more than or equal to 0 and less than or equal to 1, x + y + z is less than or equal to 1, a is more than or equal to 0 and less than or equal to 1<1，0≤b≤1，0≤c≤1，a+b+c≤1。
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| CN114447431A (en) * | 2020-11-03 | 2022-05-06 | 浙江中蓝新能源材料有限公司 | Electrolyte containing phthalic anhydride compound and lithium ion battery |
| CN114597488B (en) * | 2020-12-04 | 2024-12-13 | 深圳新宙邦科技股份有限公司 | A non-aqueous electrolyte and lithium ion battery |
| CN112768767B (en) * | 2020-12-30 | 2022-11-04 | 广东国光电子有限公司 | Electrolyte and lithium secondary battery using same |
| CN112786965B (en) * | 2020-12-30 | 2022-06-24 | 广东国光电子有限公司 | A kind of electrolyte and lithium secondary battery using the electrolyte |
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| CN118516052B (en) * | 2024-07-22 | 2024-10-29 | 深圳市豪鹏科技股份有限公司 | Battery finishing tape, winding core assembly and secondary battery |
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