CN109962292B - Lithium ion battery electrolyte and lithium ion battery comprising same - Google Patents
Lithium ion battery electrolyte and lithium ion battery comprising same Download PDFInfo
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- CN109962292B CN109962292B CN201910101491.1A CN201910101491A CN109962292B CN 109962292 B CN109962292 B CN 109962292B CN 201910101491 A CN201910101491 A CN 201910101491A CN 109962292 B CN109962292 B CN 109962292B
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- 239000000654 additive Substances 0.000 claims abstract description 48
- 230000000996 additive effect Effects 0.000 claims abstract description 43
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- -1 lithium hexafluorophosphate Chemical group 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 229910013872 LiPF Inorganic materials 0.000 claims description 4
- 101150058243 Lipf gene Proteins 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-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
- 238000000034 method Methods 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-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
- 229910015013 LiAsF Inorganic materials 0.000 claims description 2
- 229910013075 LiBF Inorganic materials 0.000 claims description 2
- 229910012258 LiPO Inorganic materials 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 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
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000007600 charging Methods 0.000 abstract description 7
- 239000010405 anode material Substances 0.000 abstract description 4
- 238000006864 oxidative decomposition reaction Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 34
- 230000014759 maintenance of location Effects 0.000 description 34
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- GWQOOADXMVQEFT-UHFFFAOYSA-N 2,5-Dimethylthiophene Chemical compound CC1=CC=C(C)S1 GWQOOADXMVQEFT-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910004761 HSV 900 Inorganic materials 0.000 description 2
- 229910012820 LiCoO Inorganic materials 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
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- KXSFECAJUBPPFE-UHFFFAOYSA-N 2,2':5',2''-terthiophene Chemical compound C1=CSC(C=2SC(=CC=2)C=2SC=CC=2)=C1 KXSFECAJUBPPFE-UHFFFAOYSA-N 0.000 description 1
- YGFLYIFQVUCTCU-UHFFFAOYSA-N 2-ethylhexoxy 2-methylbutan-2-yl carbonate Chemical compound CCCCC(CC)COOC(=O)OC(C)(C)CC YGFLYIFQVUCTCU-UHFFFAOYSA-N 0.000 description 1
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000012496 blank sample Substances 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
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- LRVBJNJRKRPPCI-UHFFFAOYSA-K lithium;nickel(2+);phosphate Chemical compound [Li+].[Ni+2].[O-]P([O-])([O-])=O LRVBJNJRKRPPCI-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- H01M10/05—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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides an electrolyte of a lithium ion battery, a preparation method thereof and the lithium ion battery comprising the electrolyte. The electrolyte of the lithium ion battery comprises: a lithium salt, an organic solvent, and an additive having the following structure. The electrolyte disclosed by the invention enables the additive to preferentially form a layer of interface film with uniform thickness on the surface of the anode during charging, protects the surface of the anode material, reduces oxidative decomposition caused by direct contact of the electrolyte and the surface of the anode, maintains the structure of the anode material, and improves the cycle performance of the battery under high voltage.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery electrolyte and a high-voltage lithium ion battery containing the electrolyte.
Background
Lithium ion batteries are widely used in portable electronic devices due to their high energy density, high voltage, long life, no memory effect, no pollution, etc. Development of high voltage positive electrode materials, and obtaining higher energy output by increasing the cut-off voltage of batteries is an effective method for developing high energy density lithium ion batteries. However, under high voltage, the conventional electrolyte is continuously oxidized and decomposed at high potential on the positive electrode side, a layer of interface film with uneven thickness and high impedance is generated, and side reaction occurs on the surface of the positive electrode, so that a series of problems of gas generation, electrolyte drying, rapid battery capacity attenuation and the like on the positive electrode side of the battery are caused, and the performance of the battery is difficult to effectively exert. And a certain amount of additive is designed and used, so that the additive preferentially forms an interface film with uniform thickness on the surface of the anode during charging, the surface of the anode material is protected, the oxidative decomposition caused by direct contact of electrolyte and the surface of the anode is reduced, the structure of the anode material is maintained, and the cycle performance of the battery under high voltage is improved.
At present, the development of high-voltage electrolyte becomes a hotspot in the field of current high-voltage lithium ion battery electrolyte, and the use of a novel additive can effectively improve the performance of the battery under high voltage. When the charging voltage of the conventional electrolyte is higher than or equal to 4.4V, the electrolyte can undergo obvious oxidative decomposition, so that the cycle performance is rapidly attenuated, the use of the battery is influenced, and the development of a high-energy-density lithium ion battery is hindered. Therefore, it is highly desirable to develop an electrolyte solution that can allow a battery to stably operate at a high voltage.
Disclosure of Invention
Technical problem
In view of the above, the present invention provides a novel lithium ion battery electrolyte, which can improve the cycle performance of the battery. The electrolyte is particularly preferably used for a high-voltage lithium ion battery, can be preferentially oxidized into a film at high voltage to form a stable interface film, and thus improves the electrochemical performance of the battery at high voltage. The electrolyte can improve the electrochemical performance under high voltage and improve the cycling stability.
Technical scheme
In order to achieve the object of the present invention, the present invention provides an electrolyte for a lithium ion battery, comprising: a lithium salt, an organic solvent and an additive having the following structure,
wherein R is1、R2And R4Each independently selected from hydrogen or alkyl of 1 to 8 carbon atoms, preferably each independently selected from hydrogen or alkyl of 1 to 4 carbon atoms, more preferably H, methyl, ethyl, propyl, butyl or isobutyl; and R3Is a direct bond or an alkylene group having 1 to 8 carbon atoms, preferably a direct bond or an alkylene group having 1 to 4 carbon atoms, for example, a direct bond, methylene, ethylene, propylene or butylene. Further, the concentration of the additive is 0.03 wt% -3 wt%, preferably 0.05 wt% -2 wt%, more preferably 0.1wt% -1 wt%, and even more preferably 0.1wt% -E, based on the weight of the battery electrolyte0.5 wt%, most preferably 0.3 wt%.
Further, the organic solvent is selected from one or a mixture of several of Propylene Carbonate (PC), Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), Tetrahydrofuran (THF), γ -butyrolactone (γ BL), Methyl Propionate (MP), Ethyl Propionate (EP), 1, 3-Dioxolane (DOL), Dimethoxymethane (DMM), 1, 2-Dimethoxyethane (DME), 1, 2-Dimethoxypropane (DMP), or tetraethylene glycol dimethyl ether (TEGDME).
Further, the lithium salt is selected from lithium hexafluorophosphate (LiPF)6) Lithium hexafluoroarsenate (LiAsF)6) Lithium tetrafluoroborate (LiBF)4) Lithium difluorophosphate (LiPO)4F2) Lithium perchlorate (LiClO)4) Lithium fluorosulfonylimide (LiFSI), lithium bistrifluoromethylsulfonyl imide (LiTFSI) or lithium bisoxalato borate (LiBOB).
Further, the concentration of the lithium salt is 0.5-3.5 mol/L.
Further, the additive is preferably 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylic acid ethyl ester.
Preferably, the electrolyte is composed of the lithium salt, the organic solvent, and the additive.
According to another aspect of the present invention, there is provided a method for preparing the electrolyte for a lithium ion battery, comprising the steps of:
purifying the organic solvent by using a molecular sieve in a glove box filled with inert atmosphere;
then dissolving the lithium salt in the organic solvent;
and adding the additive into the obtained solution, and stirring until the additive is completely dissolved, wherein the concentration of the additive is 0.03-3 wt% based on the weight of the battery electrolyte.
According to another aspect of the invention, a lithium ion battery is also provided, which comprises the lithium ion battery electrolyte.
Preferably, the lithium ion battery is a high voltage lithium ion battery. The high-voltage lithium ion battery refers to a lithium ion battery with a charge cut-off voltage of 4.4V or more, and particularly relates to a lithium ion battery using high-voltage lithium cobaltate and high-voltage ternary cathode materials, lithium-rich manganese-based cathode materials, spinel lithium nickel manganese oxide, cobalt lithium phosphate, vanadium lithium phosphate, nickel lithium phosphate and other high-voltage cathode materials.
Advantageous effects
The invention has the advantages that: by designing and using a specific amount of the additive, the additive preferentially forms an interface film with uniform thickness on the surface of the positive electrode during charging, so that the surface of the positive electrode material is protected, the oxidative decomposition caused by direct contact of electrolyte and the surface of the positive electrode is reduced, the structure of the positive electrode material is maintained, and the cycle performance of the battery under high voltage is improved.
Drawings
Fig. 1 is a graph showing ac impedance spectra measured on an electrochemical workstation after 100 cycles of a battery prepared according to example 1 of the present invention.
Detailed Description
In order to clearly, completely and clearly describe the technical solution of the present invention, the following embodiments are provided. It is to be understood that the illustrated embodiments are only a few, and not all, of the present invention.
Example 1
1) Electrolyte preparation
And (3) preparing the lithium ion battery electrolyte in a glove box protected by inert gas (wherein the water content is less than 0.1ppm, and the oxygen content is less than 0.1 ppm). The treated EC-DEC was mixed in a mass ratio of 1:1, after which a certain amount of lithium hexafluorophosphate (LiPF) was added6) So that LiPF6The final concentration of (3) is 1 mol/L. Dividing the electrolyte into ten parts, wherein nine parts are respectively added with 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophene ethyl formate (TAEC) accounting for 0.03%, 0.1%, 0.2%, 0.3%, 0.5%, 0.75%, 1%, 2% and 3% of the total mass of the electrolyte and shaken up to be completely dissolved, and the other part is not added with an additive, so that 1.0M LiPF is respectively obtained6/EC-DEC(1:1,wt％)，1.0M LiPF6/EC-DEC(1:1,wt％)+0.03wt% of ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate, 1.0M LiPF6EC-DEC (1:1, wt%) +0.1 wt% of ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate, 1.0M LiPF6EC-DEC (1:1, wt%) +0.2 wt% of ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate, 1.0M LiPF6EC-DEC (1:1, wt%) +0.3 wt% of ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate, 1.0M LiPF6EC-DEC (1:1, wt%) +0.5 wt% of ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate, 1.0M LiPF6EC-DEC (1:1, wt%) +0.75 wt% of ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate, 1.0M LiPF6EC-DEC (1:1, wt%) + 1wt% ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate, 1.0M LiPF6EC-DEC (1:1, wt%) +2 wt% ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate, 1.0M LiPF6EC-DEC (1:1, wt%) +3 wt% of ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate. The ten electrolytes were used for battery preparation, respectively.
2) Electrochemical performance test
And (3) positive electrode: the active material is LiCoO2The conductive agent is conductive carbon black (Super P, Timcal Ltd.), the binder is polyvinylidene fluoride (PVDF, HSV 900, Arkema), the dispersant is N-methyl-2-pyrrolidone (NMP), and the conductive agent is LiCoO2: super P: mixing PVDF (84: 8: 8) in a mass ratio, coating the mixture on an aluminum foil, drying, rolling, punching to prepare an electrode plate, and preparing an active material LiCoO on the surface of the electrode2Controlling at 5mg/cm2。
And (3) manufacturing a button type half cell in a glove box filled with argon, wherein the negative electrode is a lithium sheet, and the polypropylene microporous membrane is a diaphragm. And activating the half cell twice by C/10 circulation, circulating for 100 times by adopting the current density of 1C, and charging at constant voltage for half an hour after each constant current charging, wherein the charging and discharging voltage range is 3.0-4.5V. After the electrochemical performance test is completed, the battery is measured on an electrochemical workstation for alternating current impedance spectroscopy, and the spectrogram test result is shown in fig. 1. The battery discharge capacity and capacity retention rate are shown in table 1 below.
TABLE 1
| Additive content | First discharge capacity (mAh g)-1) | Capacity retention after 100 cycles |
| 0wt％ | 186 | 27％ |
| 0.03wt％ | 188 | 60％ |
| 0.1wt％ | 187 | 79％ |
| 0.2wt％ | 191 | 80％ |
| 0.3wt％ | 191 | 81％ |
| 0.5wt％ | 188 | 79％ |
| 0.75wt％ | 185 | 73％ |
| 1wt％ | 180 | 68％ |
| 2wt％ | 175 | 65％ |
| 3wt％ | 171 | 60％ |
By comparison, the addition of ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate in the range of the present invention can improve the capacity retention of the 4.5V high voltage positive electrode material compared to the blank without the addition of the ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate additive, wherein the capacity retention of the battery is the highest at 0.3 wt%, and the cycle is the most stable. From the comparison of impedance spectra after the cycle, it was found that the addition of 0.3 wt% of ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate was effective in reducing the interfacial film between the electrode and the electrolyte, thereby reducing the interfacial impedance.
Example 2
Example 1 was repeated except that the active material of step 2) was LiCoO2The conductive agent is conductive carbon black (Super P, Timcal Ltd.), the binder is polyvinylidene fluoride (PVDF, HSV 900, Arkema), the dispersant is N-methyl-2-pyrrolidone (NMP), and the conductive agent is LiCoO2: super P: mixing PVDF (84: 8: 8) in a mass ratio, coating the mixture on an aluminum foil, drying, rolling, punching to prepare an electrode plate, wherein an active material LiCoO is arranged on the surface of the electrode2Controlling at 5mg/cm2。
Preparation method of the productA negative electrode with MAG10 graphite (Hitachi Powdered Metals co. ltd.), PVDF as binder, N-methyl-2-pyrrolidone (NMP) as dispersant, MAG 10: PVDF (polyvinylidene fluoride) is mixed into slurry according to the mass ratio of 92:8, the slurry is coated on a copper foil, and then the copper foil is dried, rolled and stamped to prepare an electrode sheet, wherein MAG10 serving as an active substance on the surface of the electrode is controlled to be 2.5mg/cm2。
And manufacturing the button full cell in a glove box filled with argon. The prepared full cell is stood for 2 hours, activated by two cycles of C/20 circulation, and then circulated for 100 cycles by adopting the current density of 1C, and the charging and discharging voltage range is 3.0-4.4V. The discharge capacity and capacity retention rate of the full cell after electrochemical test are shown in table 2 below.
TABLE 2
| Additive content | First discharge capacity (mAh) | Capacity retention after 100 cycles |
| 0wt％ | 2.92 | 43％ |
| 0.03wt％ | 2.84 | 63％ |
| 0.1wt％ | 2.86 | 71％ |
| 0.2wt％ | 2.81 | 84％ |
| 0.3wt％ | 2.72 | 91％ |
| 0.5wt％ | 2.70 | 80％ |
| 1wt％ | 2.68 | 73％ |
Through comparison, compared with a blank sample without the 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophene ethyl formate additive, the capacity retention rate of the 4.4V high-voltage positive electrode material can be improved by adding the 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophene ethyl formate in the content of the invention, wherein the capacity retention rate of the battery is the highest under the condition of 0.3 wt%, and the cycle is the most stable.
Example 3
Example 1 was repeated except that the electrolyte prepared in step 1) was 1.0M LiPF6[ 0.3% by weight of ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate, [ 1.0% by weight of ethyl 5-amino-4-cyano- ] -EC-DEC-EMC (3:3:4, wt%) + 1.0M LiPF6[ EC-DEC-EMC (3:3:4, wt%). The discharge capacity and capacity retention after electrochemical testing are shown in table 3 below.
TABLE 3
| Additive content | First discharge capacity (mAh g)-1) | Capacity retention after 100 cycles |
| 0wt％ | 191 | 30％ |
| 0.3wt％ | 190 | 82％ |
Through comparison of the results, the capacity retention ratio of the lithium ion battery added with 0.3 wt% of the electrolyte of 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylic acid ethyl ester is improved from 30% to 82% after 100 cycles, compared with the lithium ion battery using the electrolyte without the additive. The capacity retention ratio of the high-voltage positive electrode material is the highest under the condition that the additive amount of the high-voltage positive electrode material is 0.3 wt%, and the cycle is the most stable.
Example 4
Example 1 was repeated except that the electrolyte prepared in step 1) was 0.6M LiPF6+0.5M LiTFSI/EC-DEC (1:1, wt%) +0.3 wt% of ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate, 0.6M LiPF6+0.5M LiTFSI/EC-DEC (1:1, wt%). The discharge capacity and capacity retention after electrochemical testing are shown in table 4 below.
TABLE 4
| Additive content | First discharge capacity (mAh g)-1) | Capacity retention after 100 cycles |
| 0wt％ | 195 | 40％ |
| 0.3wt％ | 193 | 86％ |
Through comparison of the results, the capacity retention of the lithium ion battery added with 0.3 wt% of the electrolyte of 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylic acid ethyl ester is improved from 40% to 86% after 100 cycles, compared with the lithium ion battery using the electrolyte without the additive.
Example 5
Example 1 was repeated except that the electrolyte prepared in step 1) was 1.0M LiPF6/EC-DEC(1:1,wt％)，1.0M LiPF6EC-DEC (1:1, wt%) +0.1 wt% of ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate, 1.0M LiPF6EC-DEC (1:1, wt%) +0.3 wt% of ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate, 1.0M LiPF6EC-DEC (1:1, wt%) +0.5 wt% of ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate. The discharge capacity and capacity retention after electrochemical testing are shown in table 5 below.
TABLE 5
| Additive content | First discharge capacity (mAh g)-1) | Capacity retention after 100 cycles |
| 0wt％ | 190 | 28％ |
| 0.1wt％ | 189 | 78％ |
| 0.3wt％ | 186 | 82％ |
| 0.5wt％ | 187 | 76％ |
The comparison of the results shows that compared with a lithium ion battery using an electrolyte without an additive, the capacity retention rate of the battery after the battery is subjected to 100 cycles is improved by adding the formula containing 0.3% of the additive, and the capacity retention rate of the battery can reach 82% under the addition of 0.3 wt%.
Comparative example 1
Example 1 was repeated except that the electrolyte prepared in step 1) was 1.0M LiPF6EC-DEC (1:1, wt%) +0.5 wt% VC (vinylene carbonate), 1.0M LiPF6EC-DEC (1:1, wt%) + 1wt% VC, 1.0M LiPF6EC-DEC (1:1, wt%) +0.5 wt% FEC (fluoroethylene carbonate), 1.0M LiPF6EC-DEC (1:1, wt%) + 1wt% FEC. The discharge capacity and capacity retention after electrochemical testing are shown in table 6 below.
TABLE 6
| Types and contents of additives | First discharge capacity (mAh g)-1) | Capacity retention after 100 cycles |
| 0.3wt％VC | 184 | 32％ |
| 0.5wt％VC | 182 | 35％ |
| 0.3wt％FEC | 187 | 45％ |
| 0.5wt％FEC | 189 | 42％ |
Through comparison of results, the capacity retention rate of a formula containing 0.3% of VC and 0.5% of FEC additive after 100 cycles of battery cycle is relatively low compared with a lithium ion battery added with electrolyte of 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylic acid ethyl ester additive, and the capacity retention rate of the battery can reach 82% under the condition of 0.3 wt% of 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylic acid ethyl ester additive.
Comparative example 2
Example 1 was repeated except that the electrolyte prepared in step 1) was 1.0M LiPF6EC-DEC (1:1, wt%) +0.3 wt% TH (thiophene), 1.0M LiPF6EC-DEC (1:1, wt%) +0.5 wt% TH, 1.0M LiPF6EC-DEC (1:1, wt%) +0.3 wt% of 2TH (2,2' -bithiophene), 1.0M LiPF6EC-DEC (1:1, wt%) +0.5 wt% of 2TH, 1.0M LiPF6EC-DEC (1:1, wt%) +0.3 wt% of 3TH (terthiophene), 1.0M LiPF6/EC-DEC (1:1, wt%) +0.5 wt% of 3 TH. The discharge capacity and capacity retention after electrochemical testing are shown in table 7 below.
TABLE 7
| Types and contents of additives | First discharge capacity (mAh g)-1) | Capacity retention after 100 cycles |
| 0.3wt％TH | 184 | 35％ |
| 0.5wt％TH | 182 | 46％ |
| 0.3wt％2TH | 187 | 41％ |
| 0.5wt％2TH | 189 | 53％ |
| 0.3wt％3TH | 189 | 48％ |
| 0.5wt％3TH | 190 | 61％ |
Through comparison of results, compared with a lithium ion battery added with an electrolyte of a 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylic acid ethyl ester additive, the capacity retention rate of the battery after 100 cycles of battery cycle is relatively low by adding a formula containing 0.3% and 0.5% of TH, 2TH and 3TH additives, the capacity retention rate of 0.5 wt% of 3TH added additive is 61% at the highest, and the capacity retention rate of the battery can reach 82% under the condition of 0.3 wt% of 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylic acid ethyl ester additive.
Comparative example 3
Example 1 was repeated except that the electrolyte prepared in step 1) was 1.0M LiPF6EC-DEC (1:1, wt%) +0.3 wt% TH (thiophene), 1.0M LiPF6EC-DEC (1:1, wt%) +0.5 wt% TH, 1.0M LiPF6EC-DEC (1:1, wt%) +0.3 wt% MTH (2-methylthiophene), 1.0M LiPF6EC-DEC (1:1, wt%) +0.5 wt% MTH, 1.0M LiPF6EC-DEC (1:1, wt%) +0.3 wt% DMTH (2, 5-dimethylthiophene), 1.0M LiPF6EC-DEC (1:1, wt%) +0.5 wt% of DMTH. The discharge capacity and capacity retention after electrochemical testing are shown in table 8 below.
TABLE 8
| Types and contents of additives | First discharge capacity (mAh g)-1) | Content after 100 cyclesAmount retention ratio |
| 0.3wt％TH | 183 | 33％ |
| 0.5wt％TH | 185 | 46％ |
| 0.3wt％MTH | 188 | 45％ |
| 0.5wt％MTH | 188 | 57％ |
| 0.3wt％DMTH | 193 | 52％ |
| 0.5wt％DMTH | 191 | 69％ |
Through comparison of results, compared with a lithium ion battery added with an electrolyte of a 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylic acid ethyl ester additive, the capacity retention rate of the battery after 100 cycles of battery cycle is relatively low by adding a formula containing 0.3% and 0.5% of TH, MTH and DMTH additives, the capacity retention rate of 0.5 wt% of DMTH additive is 69% at the highest, and the capacity retention rate of the battery can reach 82% under the condition of 0.3 wt% of 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylic acid ethyl ester additive.
As can be seen from the above examples and comparative examples, by adding 0.03 wt% to 3 wt% of the additive according to the present invention to the electrolyte, the capacity retention rate can be significantly improved. The illustrated embodiments are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (9)
1. An electrolyte for a lithium ion battery, comprising: a lithium salt, an organic solvent and an additive having the following structure,
wherein R is1And R4Each independently selected from alkyl with 1-8 carbon atoms, R2Selected from hydrogen or alkyl with 1-8 carbon atoms, and R3Is a direct bond or an alkylene group having 1 to 8 carbon atoms,
wherein the concentration of the additive is 0.1wt% to 1wt% based on the weight of the electrolyte.
2. The electrolyte of claim 1, wherein R1And R4Each independently selected from hydrogen or alkyl with 1-4 carbon atoms, R2Selected from hydrogen or alkyl with 1-4 carbon atoms, and R3Is a direct bond or an alkylene group having 1 to 4 carbon atoms.
3. The electrolyte of claim 1, wherein the organic solvent is selected from one or more of propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, tetrahydrofuran, gamma-butyrolactone, methyl propionate, ethyl propionate, 1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane, 1, 2-dimethoxypropane, or tetraethylene glycol dimethyl ether.
4. Root of herbaceous plantThe electrolyte of claim 1, wherein the lithium salt is selected from lithium hexafluorophosphate (LiPF)6) Lithium hexafluoroarsenate (LiAsF)6) Lithium tetrafluoroborate (LiBF)4) Lithium difluorophosphate (LiPO)4F2) Lithium perchlorate (LiClO)4) Lithium fluorosulfonylimide (LiFSI), lithium bistrifluoromethylsulfonyl imide (LiTFSI) or lithium bisoxalato borate (LiBOB).
5. The electrolyte of claim 1, wherein the lithium salt has a concentration of 0.5 to 3.5 mol/L.
6. The electrolyte of any one of claims 1 to 5, wherein the additive is ethyl 5-amino-4-cyano-3- (2-ethoxy-2-carboxymethyl) -2-thiophenecarboxylate.
7. A method of preparing the electrolyte of any one of claims 1 to 6, comprising the steps of:
purifying the organic solvent by using a molecular sieve in a glove box filled with inert atmosphere;
then dissolving the lithium salt in the organic solvent;
and adding the additive into the organic solvent in which the lithium salt is dissolved, and stirring until the additive is completely dissolved, wherein the concentration of the additive is 0.1-1 wt% based on the weight of the battery electrolyte.
8. A lithium ion battery comprising the electrolyte of any one of claims 1 to 6.
9. The lithium ion battery of claim 8, wherein the lithium ion battery is a high voltage lithium ion battery.
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