CN114079083A - Lithium ion battery electrolyte and additive thereof, lithium ion battery cell, lithium ion battery pack and application thereof - Google Patents
Lithium ion battery electrolyte and additive thereof, lithium ion battery cell, lithium ion battery pack and application thereof Download PDFInfo
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- CN114079083A CN114079083A CN202010835594.3A CN202010835594A CN114079083A CN 114079083 A CN114079083 A CN 114079083A CN 202010835594 A CN202010835594 A CN 202010835594A CN 114079083 A CN114079083 A CN 114079083A
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- Prior art keywords
- ion battery
- lithium ion
- electrolyte
- anhydride
- lithium
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 77
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000003792 electrolyte Substances 0.000 title claims abstract description 47
- 239000000654 additive Substances 0.000 title claims abstract description 34
- 230000000996 additive effect Effects 0.000 title claims abstract description 30
- -1 fluorinated benzene ring acid anhydride Chemical class 0.000 claims abstract description 20
- 238000003860 storage Methods 0.000 claims abstract description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 239000002000 Electrolyte additive Substances 0.000 claims description 15
- 230000014759 maintenance of location Effects 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- BJDDKZDZTHIIJB-UHFFFAOYSA-N 4,5,6,7-tetrafluoro-2-benzofuran-1,3-dione Chemical compound FC1=C(F)C(F)=C2C(=O)OC(=O)C2=C1F BJDDKZDZTHIIJB-UHFFFAOYSA-N 0.000 claims description 6
- AVLRPSLTCCWJKC-UHFFFAOYSA-N 4,7-difluoro-2-benzofuran-1,3-dione Chemical compound FC1=CC=C(F)C2=C1C(=O)OC2=O AVLRPSLTCCWJKC-UHFFFAOYSA-N 0.000 claims description 6
- WWJAZKZLSDRAIV-UHFFFAOYSA-N 4-fluoro-2-benzofuran-1,3-dione Chemical compound FC1=CC=CC2=C1C(=O)OC2=O WWJAZKZLSDRAIV-UHFFFAOYSA-N 0.000 claims description 6
- UATBWQQFLABWKR-UHFFFAOYSA-N 5,6-difluoro-2-benzofuran-1,3-dione Chemical compound C1=C(F)C(F)=CC2=C1C(=O)OC2=O UATBWQQFLABWKR-UHFFFAOYSA-N 0.000 claims description 6
- XVMKZAAFVWXIII-UHFFFAOYSA-N 5-fluoro-2-benzofuran-1,3-dione Chemical compound FC1=CC=C2C(=O)OC(=O)C2=C1 XVMKZAAFVWXIII-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 239000003125 aqueous solvent Substances 0.000 claims description 5
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 5
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 5
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical group 0.000 claims description 4
- 150000005678 chain carbonates Chemical class 0.000 claims description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910013872 LiPF Inorganic materials 0.000 claims description 3
- 101150058243 Lipf gene Proteins 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical compound B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910013075 LiBF Inorganic materials 0.000 claims description 2
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 2
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 abstract description 11
- 150000008065 acid anhydrides Chemical class 0.000 abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 230000009044 synergistic interaction Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229910001428 transition metal ion Inorganic materials 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
The invention discloses a lithium ion battery pack, a lithium ion battery core, a lithium ion battery electrolyte and an additive thereof. Specifically, the fluorinated benzene ring acid anhydride additive has three functional groups of fluorine, benzene ring and acid anhydride, wherein the benzene ring can be electropolymerized to form a film at the positive electrode, the acid anhydride is easy to generate a reduction film-forming reaction at the negative electrode interface, the fluorine atom can be combined with lithium in the electrolyte to form LiF to increase the stability of the interface film, the synergistic interaction of the three is beneficial to the protection of the positive electrode interface and the negative electrode interface, the direct contact between the electrolyte and the electrode interface is effectively isolated, and the electrochemical performance of the battery under different working conditions is improved. The additive effectively improves the high-voltage cycling stability of the battery, the storage and cycling performance under the high-temperature condition, and can also take the safety characteristic of the lithium ion battery into consideration.
Description
Technical Field
The invention relates to the field of energy storage, in particular to a lithium ion battery electrolyte and an additive thereof, a lithium ion battery cell, a lithium ion battery pack and application thereof.
Background
With the rapid development of new energy automobiles, the market puts higher requirements on the safety and the endurance mileage of electric automobiles. The lithium ion battery is widely applied to the field of new energy automobiles due to the characteristics of high energy density, no memory effect, environmental friendliness and the like. The lithium ion battery serving as a core power component of the electric automobile mainly comprises four major parts, namely a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the capacity of the battery is mainly determined by positive and negative electrode materials. The method is characterized in that the transition metal ions are transferred and deposited in the battery to accelerate the oxidation and reduction decomposition of the electrolyte on the positive and negative electrode interfaces, so that a large amount of electrolyte decomposition products are accumulated on the electrode interfaces, and the impedance of the battery is increased and the performance of the battery is deteriorated. Meanwhile, under the high-temperature condition, the interface film of the negative electrode is unstable, and under the lithium intercalation state, the self-repairing process of the interface film can occur on the interface of the negative electrode, which can cause the irreversible consumption of active lithium in the electrolyte, and finally cause the loss of the battery capacity. Therefore, improving the stability of the interface films of the positive and negative electrodes of the battery is an effective method for improving the performance of the battery.
The electrolyte serves as a transmission medium for lithium ions inside the battery and mainly consists of a solvent, a lithium salt and an additive, and the selectivity of the solvent and the lithium salt is relatively low. The development of new additives to improve certain electrochemical properties of batteries is considered to be an economically efficient approach. The additive generally generates a passivation film with specific properties on positive and negative electrode interfaces through oxidation or reduction reactions respectively, the passivation film formed by the participation of specific additive substances has good stability, can inhibit transition metal ions dissolved out from a positive electrode from migrating to a negative electrode through electrolyte, isolates the direct contact of the electrolyte and the electrode interface, relieves the irreversible consumption of the electrolyte on the electrode interface, and further improves the high-voltage cycling stability of the battery and the high-temperature performance of the battery. Then most of the additives can only carry out single protection on the positive electrode or the negative electrode, and can not simultaneously protect the positive electrode interface and the negative electrode interface, and two or more additives are required to be added for compounding in practical application. Most of the additives are generally expensive and harmful to human body, and easily cause increase of battery cost and environmental pollution. Therefore, the development of an electrolyte additive capable of simultaneously protecting the positive and negative electrode interfaces is of great significance for the development of high-performance low-cost batteries.
Disclosure of Invention
The first purpose of the invention is to provide an electrolyte additive, which can protect both the positive and negative electrode interfaces and improve the electrochemical performance of a lithium ion battery cell under high voltage and high temperature conditions.
The second purpose of the invention is to provide a lithium ion battery electrolyte, wherein the additive in the electrolyte can protect the positive and negative electrode interfaces, and the electrochemical performance of the lithium ion battery cell under high voltage and high temperature conditions is improved.
A third object of the present invention is to provide a lithium ion battery cell having improved electrochemical performance under high voltage and high temperature conditions.
A fourth object of the present invention is to provide a lithium ion battery pack including a lithium ion battery cell excellent in electrochemical performance under high voltage and high temperature conditions.
A fifth object of the present invention is to apply a lithium ion battery pack including a lithium ion battery cell having excellent electrochemical properties under high voltage and high temperature conditions to digital 3C, automobiles, motorcycles, or bicycles.
In order to achieve the above object, the present invention provides an electrolyte additive comprising a fluorinated benzene ring anhydride-based additive, wherein an acid anhydride functional group in the fluorinated benzene ring anhydride-based additive is a cyclic acid anhydride functional group.
Further, the structural formula of the fluorinated benzene ring anhydride additive is as follows:
Wherein R is1，R2，R3And R4Are each any one of a hydrogen atom and a fluorine atom, and R1，R2，R3And R4At least one of which is a fluorine atom. Preferably, the fluorine atoms contained may be 1, 2 or 4. The fluorine atom-containing compound is preferably selected from the group consisting of fluorine atom-containing compounds, fluorine atoms, and fluorine atoms. The fluorinated cyclic anhydride additive of the present invention is preferably at least one of 3-fluorophthalic anhydride, 4-fluorophthalic anhydride, 3, 6-difluorophthalic anhydride, 4, 5-difluorophthalic anhydride, tetrafluorophthalic anhydride and 4,4 '- (hexafluoroisopropylidene) phthalic anhydride, wherein the structural formulas of the 3-fluorophthalic anhydride, 4-fluorophthalic anhydride, 3, 6-difluorophthalic anhydride, 4, 5-difluorophthalic anhydride, tetrafluorophthalic anhydride and 4, 4' - (hexafluoroisopropylidene) phthalic anhydride are respectively:
further, the lithium ion battery electrolyte comprises the electrolyte additive, and the content of the electrolyte additive accounts for 0.01-5% of the total mass of the lithium ion battery electrolyte.
Further, the lithium ion battery electrolyte also comprises a non-aqueous solvent and a conductive lithium salt, wherein the non-aqueous solvent accounts for 80.0-90.0% of the total mass of the lithium ion battery electrolyte, and the conductive lithium salt accounts for 9.0-15% of the total mass of the lithium ion battery electrolyte.
Further, the nonaqueous solvent is a mixed solvent of at least one of cyclic carbonates including Ethylene Carbonate (EC), Propylene Carbonate (PC) and Butylene Carbonate (BC), and at least one of chain carbonates including dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC) and propyl methyl carbonate (MPC). The cyclic carbonate has a high dielectric constant but a high viscosity, while the chain carbonate has a relatively low viscosity but a dielectric constant lower than that of the cyclic carbonate, and the nonaqueous solvent is a mixed solvent of at least one of the cyclic carbonates and at least one of the chain carbonates, so that the dielectric constant and the viscosity are both satisfied.
Further, the conductive lithium salt includes lithium hexafluorophosphate (LiPF)6) Lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium difluorophosphate (LiDFP), lithium bis (oxalato) borate (LiBOB), lithium tetrafluoroborate (LiBF)4) And lithium difluoroborate (LiODFB).
The invention also provides a lithium ion battery cell, which comprises the lithium ion battery electrolyte.
Furthermore, the lithium ion cell has a capacity retention rate of 78.3-91.3% after 200 weeks of normal-temperature high-voltage cycling, a capacity retention rate of 79.2-91.9% after 200 weeks of 45 ℃ cycling, an expansion rate of 2.2-8.7% after 14 days of high-temperature 60 ℃ storage, a capacity retention rate of 78.2-91.3% and a capacity recovery rate of 87.3-96.8%.
Further, the lithium ion battery cell also comprises a positive electrode, a negative electrode and a diaphragm, wherein the positive electrode material of the positive electrode comprises LiFePO4、LiCO2And LiNixCoyMn1-x-yO2The negative electrode material of the negative electrode comprises a graphite base and a silicon-containing material.
The invention also provides a lithium ion battery pack which comprises the lithium ion battery cell.
The lithium ion battery pack is also applied to digital 3C, automobiles, motorcycles or bicycles.
Compared with the prior art, the invention provides a lithium ion battery pack, a lithium ion battery cell, a lithium ion battery electrolyte and an additive thereof. Specifically, the fluorinated benzene ring acid anhydride additive has three functional groups of fluorine, benzene ring and acid anhydride simultaneously, wherein, benzene ring can generate electropolymerization film at the anode, which can effectively protect the anode interface, inhibit the migration of transition metal ions of the anode and the direct contact between the electrode interface and electrolyte under the condition of high voltage, anhydride is easy to generate reduction film-forming reaction at the cathode interface, a stable SEI film is formed on the interface of the negative electrode, the direct contact between the electrolyte and the interface of the electrode is isolated, the consumption of the electrolyte is relieved, the irreversible loss of active lithium on the interface of the negative electrode of the battery under the high-temperature condition can be reduced, the high-temperature performance of the battery is improved, the fluorine atoms can be combined with the lithium in the electrolyte to form LiF to increase the stability of the interface film, the synergistic interaction of the three components is favorable for protecting the interfaces of the positive electrode and the negative electrode, thereby effectively isolating the direct contact between the electrolyte and the electrode interface and improving the electrochemical performance of the battery under different working conditions. The additive effectively improves the high-voltage cycling stability of the battery, the storage and cycling performance under the high-temperature condition, can also take the safety characteristic of the lithium ion battery into account, and shows excellent market application prospect.
Detailed Description
The "ranges" disclosed herein are in the form of lower and upper limits. There may be one or more lower limits, and one or more upper limits, respectively. The given range is defined by the selection of a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges that can be defined in this manner are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for particular parameters, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present invention, all embodiments and preferred embodiments mentioned herein may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the steps mentioned herein may be performed sequentially or randomly, if not specifically stated, but preferably sequentially.
The invention provides a lithium ion battery pack, which comprises a battery module, a circuit board, a shell and the like, wherein the battery module, the circuit board and the like are assembled in the shell to form the lithium ion battery pack, the lithium ion battery pack has various specifications, can be adjusted and designed according to needs, and is not limited in the process, and the assembly mode of the lithium ion battery pack in the prior art can be applied to the invention.
The battery module is composed of a plurality of lithium ion battery cells connected in series and in parallel, and similarly, the battery module has various specifications and can be adjusted and designed according to needs.
The lithium ion battery pack can be applied to digital 3C, automobiles, motorcycles or bicycles. The steps of the lithium ion cell preparation and the battery performance test according to the present invention are described below.
1. Preparing lithium ion battery electrolyte: mixing Ethylene Carbonate (EC), Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), Propyl Propionate (PP) and other solvents according to a certain mass ratio in a glove box protected by argon or nitrogen atmosphere, and then adding a certain mass percent of electrolyte additive (the electrolyte additive is at least one of 3-fluorophthalic anhydride, 4-fluorophthalic anhydride, 3, 6-difluorophthalic anhydride, 4, 5-difluorophthalic anhydride, tetrafluorophthalic anhydride and 4, 4' - (hexafluoroisopropylidene) phthalic anhydride) and conductive lithium salt lithium hexafluorophosphate (LiPF)6) (occupy ratio 9% >. E15%), and the like, and the electrolyte of the lithium ion battery is obtained. Wherein the structural formulas of the 3-fluorophthalic anhydride, the 4-fluorophthalic anhydride, the 3, 6-difluorophthalic anhydride, the 4, 5-difluorophthalic anhydride, the tetrafluorophthalic anhydride and the 4, 4' - (hexafluoroisopropylidene) phthalic anhydride are shown as A to E and II:
2. preparing a lithium ion battery cell:
1) preparing a positive pole piece: the positive electrode slurry is respectively made of LiNi0.6Co0.2Mn0.2O2PVDF, NMP and a conductive agent are uniformly mixed and stirred according to a certain proportion, the anode slurry is uniformly coated on two surfaces of an aluminum foil, the processes of drying, rolling and vacuum drying are carried out, then rolling and cutting are carried out, and an aluminum outgoing line is welded by an ultrasonic welding machine to obtain an anode plate.
2) Preparing a negative pole piece: the negative electrode slurry takes SiO-C mixed material of graphite and silica as a negative electrode active material, and is uniformly mixed with CMC, deionized water, conductive agent and SBR according to a certain proportion by stirring, the negative electrode slurry is coated on two sides of copper foil, and is subjected to the processes of drying, rolling and vacuum drying, rolling and cutting, and an ultrasonic welding machine is used for welding a nickel outgoing line to obtain the negative electrode sheet.
3) Preparing a diaphragm: the diaphragm adopts a PP/PE/PP three-layer composite diaphragm.
4) Assembling the lithium ion battery cell: stacking the prepared positive plate, the diaphragm and the negative plate in sequence, enabling the diaphragm to be positioned between the positive plate and the negative plate, and winding to obtain a bare cell; placing the bare cell in an outer package, baking to remove moisture, transferring to a glove box for liquid injection, injecting the prepared electrolyte into the dried outer package, packaging, standing, pre-charging, aging, shaping, testing capacity and the like, and completing the preparation of the lithium secondary soft package battery.
Experimental information on the electrolyte additives, the electrolyte and the lithium ion battery cell of comparative examples 1 to 5 and examples 1 to 12 in the present invention is shown in tables 1 and 2.
Table 1 comparative example experimental information
Table 2 example experimental information
3. Testing of the lithium ion cell: the lithium ion cells in the examples and comparative examples were subjected to high voltage and high temperature performance tests under the following specific test conditions.
1) And (3) normal-temperature high-voltage cycle test: the battery is placed at 25 ℃, the battery is subjected to charge-discharge circulation by using 1C current in a charge-discharge voltage interval of 3.0-4.5V, the initial capacity is recorded as Q, and the capacity of the battery which is circulated to 200 weeks is selected as Q1The capacity retention rate of the battery at normal temperature for 200 weeks is calculated by the following formula:
2) and (3) high-temperature storage test: the method comprises the steps of cycling a battery at a rate of 1C at normal temperature for 5 weeks, standing the fully charged battery in a constant-temperature explosion-proof oven at 60 ℃ for 14 days, calculating the expansion rate of the battery before and after high-temperature storage (the expansion rate is (the thickness of the battery after the high-temperature storage-the thickness of the battery before the high-temperature storage)/the thickness of the battery before the high-temperature storage is multiplied by 100%), cycling the battery at the normal temperature for 5 weeks after the high-temperature storage, and performing a capacity recovery test, and calculating the capacity retention rate and the recovery rate of the battery (the capacity retention rate is 1-week-discharge capacity at normal temperature/discharge capacity of the battery before storage, and the capacity recovery rate is 5-week-discharge capacity at normal temperature/discharge capacity of the battery before storage).
3) High temperature cycle test at 45 ℃: the battery is placed at 45 ℃, a 1C current is used for carrying out charge-discharge circulation in a charge-discharge voltage interval of 3.0-4.3V, the initial capacity is recorded as Q, the capacity selected from the circulation to 200 weeks is recorded as Q2, and the capacity retention ratio of the battery in 200 weeks of high-temperature circulation is calculated by the following formula:
the test results of the batteries of comparative examples 1 to 5 and examples 1 to 12 in the present invention are shown in tables 3 and 4.
Table 3: comparative examples 1 to 5 Experimental test results
TABLE 4 test results of examples 1 to 12
As can be seen from the test results of tables 3 and 4, when the fluorinated benzene cyclic acid anhydride additive is added to the electrolyte as the electrolyte additive, the high voltage cycle stability of the lithium ion battery cell can be significantly improved. Meanwhile, under high-temperature storage, the lithium ion battery cell using the fluorinated benzene ring acid anhydride additive as the electrolyte additive shows lower volume expansion rate and higher capacity retention rate and recovery rate, and the cycle stability under the condition of 45 ℃ can be obviously improved. As can be seen from the examples and the comparative examples, compared with the high-temperature additive DTD and the high-voltage additive LiDFP which are commonly used at present, the fluorinated benzene ring acid anhydride additive can simultaneously give consideration to the high-voltage and high-temperature performances of the battery, and has good application prospect and economic benefit.
In the embodiment, as shown in comparative example 5, the acid anhydride functional group in the fluorinated benzene ring acid anhydride additive of the present invention is a cyclic acid anhydride functional group, that is, a ring-closed acid anhydride functional group, and compared with the ring-opened acid anhydride functional group of comparative example 5, the film formation of the negative electrode is more significant, the interfacial film of the negative electrode is stable at high temperature, and the generated lithium carbonate has a large amount of lithium carbonate components and better high-temperature performance.
The invention provides a lithium ion battery pack, a lithium ion battery core, a lithium ion battery electrolyte and an additive thereof. Specifically, the fluorinated benzene ring acid anhydride additive has three functional groups of fluorine, benzene ring and acid anhydride simultaneously, wherein, benzene ring can generate electropolymerization film at the anode, which can effectively protect the anode interface, inhibit the migration of transition metal ions of the anode and the direct contact between the electrode interface and electrolyte under the condition of high voltage, anhydride is easy to generate reduction film-forming reaction at the cathode interface, a stable SEI film is formed on the interface of the negative electrode, the direct contact between the electrolyte and the interface of the electrode is isolated, the consumption of the electrolyte is relieved, the irreversible loss of active lithium on the interface of the negative electrode of the battery under the high-temperature condition can be reduced, the high-temperature performance of the battery is improved, the fluorine atoms can be combined with the lithium in the electrolyte to form LiF to increase the stability of the interface film, the synergistic interaction of the three components is favorable for protecting the interfaces of the positive electrode and the negative electrode, thereby effectively isolating the direct contact between the electrolyte and the electrode interface and improving the electrochemical performance of the battery under different working conditions. The additive effectively improves the high-voltage cycling stability of the battery, the storage and cycling performance under the high-temperature condition, can also take the safety characteristic of the lithium ion battery into account, and shows excellent market application prospect.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, therefore, the present invention is not limited by the appended claims.
Claims (12)
1. The electrolyte additive is characterized by comprising a fluorinated benzene ring anhydride additive, wherein an anhydride functional group in the fluorinated benzene ring anhydride additive is a cyclic anhydride functional group.
2. The electrolyte additive of claim 1 wherein the fluorinated benzene ring anhydride additive has the formula:
Wherein R is1，R2，R3And R4Are each any one of a hydrogen atom and a fluorine atom, and R1，R2，R3And R4At least one of which is a fluorine atom.
3. The electrolyte additive according to claim 1, wherein the fluorinated cyclic anhydride additive is at least one of 3-fluorophthalic anhydride, 4-fluorophthalic anhydride, 3, 6-difluorophthalic anhydride, 4, 5-difluorophthalic anhydride, tetrafluorophthalic anhydride and 4,4 '- (hexafluoroisopropylidene) phthalic anhydride, and wherein the structural formulas of the 3-fluorophthalic anhydride, 4-fluorophthalic anhydride, 3, 6-difluorophthalic anhydride, 4, 5-difluorophthalic anhydride, tetrafluorophthalic anhydride and 4, 4' - (hexafluoroisopropylidene) phthalic anhydride are respectively:
4. the electrolyte of the lithium ion battery is characterized by comprising the electrolyte additive according to any one of claims 1 to 3, wherein the content of the electrolyte additive accounts for 0.01-5% of the total mass of the electrolyte of the lithium ion battery.
5. The lithium ion battery electrolyte of claim 4 further comprising a non-aqueous solvent and a conductive lithium salt, wherein the non-aqueous solvent comprises 80.0% to 90.0% of the total mass of the lithium ion battery electrolyte, and the conductive lithium salt comprises 9.0% to 15% of the total mass of the lithium ion battery electrolyte.
6. The lithium ion battery electrolyte of claim 5 wherein the non-aqueous solvent is a mixed solvent of at least one of cyclic carbonates including Ethylene Carbonate (EC), Propylene Carbonate (PC) and Butylene Carbonate (BC) and at least one of chain carbonates including dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC) and propyl methyl carbonate (MPC).
7. The lithium ion battery electrolyte of claim 5 wherein the conductive lithium salt comprises lithium hexafluorophosphate (LiPF)6) Lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium difluorophosphate (LiDFP), lithium bis (oxalato) borate (LiBOB), lithium tetrafluoroborate (LiBF)4) And lithium difluoroborate (LiODFB).
8. A lithium ion battery cell, characterized in that the lithium ion battery cell comprises the lithium ion battery electrolyte according to any one of claims 4 to 7.
9. The lithium ion battery cell of claim 8, wherein the lithium ion battery cell has a capacity retention ratio of 78.3-91.3% after 200 cycles at room temperature and high voltage, a capacity retention ratio of 79.2-91.9% after 200 cycles at 45 ℃, an expansion ratio of 2.2-8.7% after 14 days of high temperature storage at 60 ℃, a capacity retention ratio of 78.2-91.3%, and a capacity recovery ratio of 87.3-96.8%.
10. The lithium ion battery cell of claim 8, further comprising a positive electrode, a negative electrode, and a separator, wherein the positive electrode material of the positive electrode comprisesLiFePO4、LiCO2And LiNixCoyMn1-x-yO2The negative electrode material of the negative electrode comprises a graphite base and a silicon-containing material.
11. A lithium ion battery pack, characterized in that the lithium ion battery pack comprises the lithium ion battery cell according to any one of claims 8 to 10.
12. The lithium ion battery pack of claim 11 applied to a digital 3C, an automobile, a motorcycle, or a bicycle.
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