CN116315091A - Electrolyte and lithium ion battery comprising same - Google Patents
Electrolyte and lithium ion battery comprising same Download PDFInfo
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- CN116315091A CN116315091A CN202310138086.3A CN202310138086A CN116315091A CN 116315091 A CN116315091 A CN 116315091A CN 202310138086 A CN202310138086 A CN 202310138086A CN 116315091 A CN116315091 A CN 116315091A
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- electrolyte
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- lithium
- lithium ion
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- 239000000654 additive Substances 0.000 claims abstract description 30
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims abstract description 3
- 125000006725 C1-C10 alkenyl group Chemical group 0.000 claims abstract description 3
- 125000005103 alkyl silyl group Chemical group 0.000 claims abstract description 3
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims abstract description 3
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- 150000005678 chain carbonates Chemical class 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 claims 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002000 Electrolyte additive Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000007784 solid electrolyte Substances 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 229940125904 compound 1 Drugs 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000005457 optimization Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 description 2
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910013825 LiNi0.33Co0.33Mn0.33O2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- DFFDSQBEGQFJJU-UHFFFAOYSA-N butyl hydrogen carbonate Chemical compound CCCCOC(O)=O DFFDSQBEGQFJJU-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000006258 conductive agent Substances 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
- 238000004807 desolvation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical group [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method 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 an electrolyte and a lithium ion battery comprising the same, wherein the electrolyte comprises lithium salt, an organic solvent and a multifunctional six-membered heterocyclic compound additive shown in the following formula:
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to electrolyte and a lithium ion battery comprising the same.
Background
Lithium ion batteries are widely used by people due to the characteristics of high working voltage, large specific energy, long cycle life, no memory effect and the like, such as the current lithium ion batteries are widely applied to the field of 3C consumer electronic products, and with the development of new energy automobiles, the lithium ion batteries are widely used in the fields of power and energy storage, so that higher demands are put forward on various performances of the lithium ion batteries.
The lithium ion battery electrolyte belongs to one of four main materials of the lithium ion battery, and plays a role in lithium ion transmission when existing between the positive plate material and the negative plate material and in the pores of the diaphragm, and has important influence on various performances of the lithium ion battery, such as circulation, multiplying power, safety and the like. The electrolyte used commercially at present consists of lithium salt, solvent and additive, wherein the additive has relatively small addition amount, but can form a solid electrolyte interface film on the surface of the electrode material, thereby playing an important role in inhibiting continuous side reaction of the electrode material and the electrolyte, helping desolvation of lithium ions and the like. The electrolyte additives currently being researched are various in variety, including phosphate additives containing phosphorus, borate additives containing boron, sulfate additives containing sulfur and the like, in order to improve the comprehensive performance of the lithium ion battery, various additives with different functional groups are generally required to be added into the electrolyte, so that the use cost of the additives is high, the optimization screening and optimization work is complex, and the coordination between different functional groups is difficult to play, therefore, the exploration of novel multifunctional electrolyte additives is more beneficial to realizing the synergistic effect between different functional groups, the additive combination screening efficiency is improved, and the comprehensive electrochemical performance of the lithium ion battery is further improved.
Disclosure of Invention
Based on the technical problems in the background art, the invention aims to provide an electrolyte and a lithium ion battery comprising the same, wherein the electrolyte uses a multifunctional group six-membered heterocyclic compound as an electrolyte additive of the lithium ion battery, so that the combination optimization efficiency of the electrolyte additive can be improved, and the normal, high-cycle, low-temperature discharge performance and other comprehensive electrochemical performances of the lithium ion battery are improved.
The aim of the invention is realized by the following technical scheme:
an electrolyte comprising a lithium salt, an organic solvent, and a multi-functional six-membered heterocyclic compound additive having the chemical structural formula:
wherein: r1 and R2 are each independently selected from any one of substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkenyl, substituted or unsubstituted C1-C10 alkynyl, substituted or unsubstituted phenyl, substituted or unsubstituted carbonyl, substituted or unsubstituted carboxylate, substituted or unsubstituted alkylsilyl, cyano, isocyano or isothiocyanato.
Further, the multifunctional six-membered heterocyclic compound additive comprises at least one of compounds represented by the following formulas (1) to (6):
preferably, the organic solvent is at least one selected from the group consisting of cyclic or chain carbonates, cyclic or linear carboxylates, and cyclic or linear ethers. Further preferably, the organic solvent is selected from one or more of dimethyl carbonate, diethyl carbonate, methylethyl carbonate, propylmethyl carbonate, ethylene carbonate, propylene carbonate, gamma-butyrolactone, ethyl propionate, methyl butyrate, butyl acetate, methyl propionate, propyl butyrate, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane.
Preferably, the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium bisfluorosulfonyl imide and lithium bistrifluoromethane sulfonyl imide.
Preferably, the lithium salt content in the electrolyte is 5-30wt%; the content of the multifunctional six-membered heterocyclic compound additive in the electrolyte is 0.5-20%; the content of the organic solvent in the electrolyte is 60-85%.
The invention also discloses a lithium ion battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the electrolyte is the electrolyte
Compared with the prior art, the invention has the beneficial effects that:
1) The multifunctional six-membered heterocyclic compound additive provided by the invention can participate in film forming reaction on the surface of an electrode material of a lithium ion battery, is decomposed to generate various film forming products containing silicon, sulfur and phosphorus, and promotes the formation of a solid electrolyte interface film with compactness, stability and low impedance, thereby simultaneously improving the normal and high cycle and low-temperature discharge performance of the lithium ion battery.
2) The multifunctional six-membered heterocyclic compound additive provided by the invention contains multiple functional groups such as phosphate, borate, sulfonate and the like, so that complex screening work for carrying out combination optimization on multiple single-functional group-containing additives is avoided, and coordination among different functional groups can be better realized.
Detailed Description
The invention will be further illustrated with reference to examples. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The raw materials, reagents and the like used in the following examples and comparative examples are commercially available products.
Example 1
A lithium ion battery electrolyte comprises lithium salt, an organic solvent and an additive, wherein the additive is a multi-functional six-membered heterocyclic compound of a compound 1 shown in the following formula (1).
The preparation method of the electrolyte comprises the following steps: liPF is carried out in an inert atmosphere glove box having water/oxygen index of < 0.1ppm 6 Dissolving in organic solvents of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a mass ratio of 3:2:5, and LiPF 6 The concentration is 1.0mol/L, and the LiPF is to be used 6 After complete dissolution, adding a compound 1 accounting for 4 percent of the total mass of the electrolyte as an additive, and uniformly mixing and stirring to obtain the lithium ion battery electrolysisLiquid sample
A lithium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the electrolyte is the prepared lithium ion battery electrolyte sample.
The preparation method of the lithium ion battery comprises the following steps: artificial graphite as a cathode material, a conductive base SP, a binder CMC and a dispersing agent SBR according to the following weight percentage of 96:1:1.5:1.5, adding a proper amount of deionized water, mixing into uniform paste, uniformly coating on copper foil serving as a 12 mu m negative electrode current collector, and baking at 100 ℃ for 12 hours to obtain a negative electrode plate. The anode material LiNi 0.33 Co 0.33 Mn 0.33 O 2 Conductive agent SP, binder PVDF according to 96:2:2, adding an appropriate amount of NMP solvent, mixing into uniform paste, uniformly coating on 15 mu m aluminum foil serving as a positive electrode current collector, and baking at 110 ℃ for 12 hours to obtain the positive electrode plate. And sequentially laminating the positive plate, the diaphragm and the negative plate to obtain the lithium ion battery cell, wherein the battery prepared by the experiment is a 2Ah soft package battery. The cells were dried and then injected with 8g of electrolyte samples to obtain corresponding battery samples.
Example 2
The manufacturing method and steps of the lithium ion battery electrolyte and the battery are the same as those of the embodiment 1, except that the compound 2 shown in the following formula (2) is used for replacing the compound 1, and the rest is the same as the embodiment 1, and the details are not repeated.
Example 3
The manufacturing method and steps of the lithium ion battery electrolyte and the battery are the same as those of the embodiment 1, except that the compound 3 shown in the following formula (3) is used for replacing the compound 1, and the rest is the same as the embodiment 1, and is not repeated.
Example 4
The lithium ion battery electrolyte and the battery are the same as in example 1 in the manufacturing method and steps, except that the compound 4 shown in the following formula (4) is used for replacing the compound 1, and the rest is the same as in example 1, and is not repeated.
Example 5
The lithium ion battery electrolyte and the battery are the same as in example 1 in the manufacturing method and steps, except that the compound 5 shown in the following formula (5) is used for replacing the compound 1, and the rest is the same as in example 1, and is not repeated.
Example 6
The lithium ion battery electrolyte and the battery are the same as in example 1 in the manufacturing method and steps, except that the compound 6 shown in the following formula (6) is used for replacing the compound 1, and the rest is the same as in example 1, and is not repeated.
Example 7
The manufacturing method and steps of the lithium ion battery electrolyte and the battery are the same as those of the embodiment 1, except that 2% of the compound 1 and 2% of the compound 2 are used for replacing 4% of the compound 1, and the rest is the same as the embodiment 1, and the details are not repeated.
Comparative example 1
The lithium ion battery electrolyte and the battery are the same as in the embodiment 1 in the manufacturing method and the steps, the only difference is that the additive only comprises 4% of vinylene carbonate, and the rest is the same as in the embodiment 1, and the details are not repeated.
Comparative example 2
The method for manufacturing the lithium ion battery electrolyte and the lithium ion battery are the same as in the embodiment 1, except that 4% of the compound 1 in the embodiment 1 is replaced by a mixture of 1% of vinylene carbonate, 1% of vinyl sulfate, 1% of tri (trimethylsilyl) phosphate and 1% of tri (trimethylsilyl) borate, and the rest of the method is the same as in the embodiment 1, and is not repeated.
The testing method comprises the following steps: the batteries prepared in the above examples and comparative examples were subjected to a normal temperature cycle test, a high temperature cycle test, and a low temperature discharge performance test, respectively.
(one) normal temperature cycle test
The batteries of examples 1 to 7 and comparative examples 1 to 2 were charged to 4.2V at 25℃with a constant current and a constant voltage of 0.2C, respectively, and the off-current was 0.05C; then 0.2C constant current discharge is carried out to 2.5V, and the discharge capacity Q is recorded 0 Initially as discharge initial capacity. After the environment temperature is kept unchanged and the charge and discharge system is cycled for 100 times according to the same charge and discharge system, the 300 th discharge capacity Q is recorded 300 Room temperature discharge capacity retention rate=q 300 /Q 0 *100％。
(II) high temperature cycle Performance test
The high-temperature cycle performance test method is the same as the normal-temperature cycle test method, and the only difference is that the environment temperature of the cycle test is set to 45 DEG C
(III) -20 ℃ low-temperature discharge Performance test
The lithium ion batteries of examples 1 to 7 and comparative examples 1 to 2 were charged to 4.2V with a constant current and constant voltage of 0.2C, and an off current of 0.05C, respectively, at 25 ℃; then 0.2C constant current discharge is carried out to 2.0V, and the discharge capacity Q is recorded 0 As the initial discharge capacity. Charging the battery to 4.2V with a constant current and a constant voltage of 0.2C, and stopping the current at 0.05C; then placing the sample at-20deg.C for 3h to reach temperature balance, then discharging the experimental cell to 2.0V with 0.2C constant current, and recording its discharge capacity Q 1 Thus, when three experimental batteries are tested in parallel to average, the low-temperature discharge capacity retention rate=q 1 /Q 0 *100％。
The results of the above test are shown in Table 1.
Table 1 test results for examples and comparative examples battery samples
The test data of comparative examples 1-2 show that only ethylene carbonate additive is used, the electrolyte has poor low-temperature performance, the low-temperature discharge capacity retention rate of minus 20 ℃ is less than 60 percent, even if various additives such as ethylene sulfate, tri (trimethylsilyl) phosphate, tri (trimethylsilyl) borate and the like are used in combination in comparative example 2, the improvement effect of each electrochemical performance is poorer than that of the multifunctional six-membered heterocyclic compound additive in the examples, and the main reason is that the synergy of different additives cannot be exerted, the film forming stability is poorer, and the side reaction of the electrolyte and the electrode material is serious.
In contrast, the test data of examples 1 to 7 show that the use of one or a combination of the multifunctional six-membered heterocyclic compounds of compounds 1 to 7 as additives can exert the synergistic effect of different functional groups, promote the formation of a compact and stable solid electrolyte interface film, remarkably improve cycle performance, ensure that the capacity retention rate at normal temperature cycle for 300 weeks is more than 94%, ensure that the capacity retention rate at normal temperature cycle for 300 weeks is more than 85.9%, and simultaneously ensure that the low-temperature discharge performance is remarkably improved, and ensure that the low-temperature discharge capacity retention rate at-20 ℃ is more than 70.9%. Therefore, the multifunctional six-membered heterocyclic compound additive provided by the invention avoids complex screening work for carrying out combination optimization on various additives containing single functional groups, and can better realize the synergistic effect between different functional groups.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (9)
1. An electrolyte, characterized in that: the electrolyte comprises lithium salt, an organic solvent and a multifunctional six-membered heterocyclic compound additive, wherein the chemical structural formula of the multifunctional six-membered heterocyclic compound additive is as follows:
wherein: r1 and R2 are each independently selected from any one of substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkenyl, substituted or unsubstituted C1-C10 alkynyl, substituted or unsubstituted phenyl, substituted or unsubstituted carbonyl, substituted or unsubstituted carboxylate, substituted or unsubstituted alkylsilyl, cyano, isocyano or isothiocyanato.
2. The electrolyte of claim 1, wherein: the multifunctional six-membered heterocyclic compound additive comprises at least one of compounds shown in the following formulas (1) to (6):
3. the electrolyte of claim 1, wherein: the organic solvent is at least one selected from cyclic or chain carbonates, cyclic or linear carboxylic acid esters, and cyclic or linear ethers.
4. The electrolyte according to claim 3, wherein: the organic solvent is selected from one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propyl methyl carbonate, ethylene carbonate, propylene carbonate, gamma-butyrolactone, ethyl propionate, methyl butyrate, butyl acetate, methyl propionate, propyl butyrate, tetrahydrofuran, 2-methyltetrahydrofuran and 1, 3-dioxolane.
5. The electrolyte of claim 1, wherein: the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium bisfluorosulfonyl imide and lithium bistrifluoromethane sulfonyl imide.
6. The electrolyte according to any one of claims 1 to 5, wherein: the lithium salt content in the electrolyte is 5-30wt%.
7. The electrolyte according to any one of claims 1 to 5, wherein: the content of the multifunctional six-membered heterocyclic compound additive in the electrolyte is 0.5-20%.
8. The electrolyte according to any one of claims 1 to 5, wherein: the content of the organic solvent in the electrolyte is 60-85%.
9. A lithium ion battery, characterized in that: comprising a positive electrode sheet, a negative electrode sheet, a separator, and an electrolyte as claimed in any one of claims 1 to 8.
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| CN116730880A (en) * | 2023-08-14 | 2023-09-12 | 江苏天合储能有限公司 | Electrolyte water removal additive, electrolyte and lithium ion battery |
| CN116730880B (en) * | 2023-08-14 | 2023-10-27 | 江苏天合储能有限公司 | Electrolyte water removal additive, electrolyte and lithium ion battery |
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