CN103456991B - Lithium ion battery and gel electrolyte and preparation method thereof - Google Patents
Lithium ion battery and gel electrolyte and preparation method thereof Download PDFInfo
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- CN103456991B CN103456991B CN201310391965.3A CN201310391965A CN103456991B CN 103456991 B CN103456991 B CN 103456991B CN 201310391965 A CN201310391965 A CN 201310391965A CN 103456991 B CN103456991 B CN 103456991B
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- gel electrolyte
- electrolyte layer
- lithium ion
- positive electrode
- ion battery
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- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 162
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 135
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000007773 negative electrode material Substances 0.000 claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 39
- 229920000642 polymer Polymers 0.000 claims description 38
- -1 Polytetrafluoroethylene Polymers 0.000 claims description 25
- 239000004014 plasticizer Substances 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 239000002608 ionic liquid Substances 0.000 claims description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 238000005098 hot rolling Methods 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 7
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 6
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 4
- 229920005646 polycarboxylate Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920005554 polynitrile Polymers 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920006295 polythiol Polymers 0.000 claims description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- 229910013164 LiN(FSO2)2 Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007770 graphite material Substances 0.000 claims description 2
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000733 Li alloy Inorganic materials 0.000 claims 1
- 239000001989 lithium alloy Substances 0.000 claims 1
- DGCPSAFMAXHHDM-UHFFFAOYSA-N sulfuric acid;hydrofluoride Chemical compound F.OS(O)(=O)=O DGCPSAFMAXHHDM-UHFFFAOYSA-N 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 56
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 239000011267 electrode slurry Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- UIOWFYDMDBRHLM-UHFFFAOYSA-N 2-butyl-3-methylpyridine Chemical compound CCCCC1=NC=CC=C1C UIOWFYDMDBRHLM-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical group [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- LRVBJNJRKRPPCI-UHFFFAOYSA-K lithium;nickel(2+);phosphate Chemical compound [Li+].[Ni+2].[O-]P([O-])([O-])=O LRVBJNJRKRPPCI-UHFFFAOYSA-K 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HVSAUQKNIJRYSR-UHFFFAOYSA-N 3-methyl-5-propylpyridine Chemical compound CCCC1=CN=CC(C)=C1 HVSAUQKNIJRYSR-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000681 Silicon-tin Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 description 1
- IEFJDZJERJLOEW-UHFFFAOYSA-L lithium cobalt(2+) sulfate Chemical class S(=O)(=O)([O-])[O-].[Co+2].[Li+] IEFJDZJERJLOEW-UHFFFAOYSA-L 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-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
- 239000011572 manganese Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium ion battery and gel electrolyte and a preparation method of the lithium ion battery. The gel electrolyte of the lithium ion battery is arranged between a positive electrode piece and a negative electrode piece and comprises a positive electrode gel electrolyte layer and a negative electrode gel electrolyte layer, wherein one side of the positive electrode gel electrolyte layer is adjacently connected with the positive electrode piece, the positive electrode piece is provided with a high-potential positive electrode active material, and the oxidation potential of the positive electrode gel electrolyte layer is above 4.5V (vs Li/Li+); one side of the negative electrode gel electrolyte layer is adjacently connected with the negative electrode piece, and the other side of the negative electrode gel electrolyte layer is adjacently connected with the other side of the positive electrode gel electrolyte layer; the negative electrode piece has a low-potential negative electrode active material, and the reduction potential of the negative electrode gel electrolyte layer is below 0.2V (vs Li/Li+). The gel electrolyte of the lithium ion battery can improve the compatibility of the gel electrolyte and the positive and negative electrode pieces, can effectively improve the working voltage and can prolong the cycle life of the lithium ion battery.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium ion battery, a gel electrolyte thereof and a preparation method thereof.
Background
Due to its long service life and high energy density and operating voltage, lithium ion batteries have been widely used in recent years in consumer electronics products such as notebook computers, smart phones, digital cameras, and the like. However, with the miniaturization and intelligence development of these electronic products, the energy density of the lithium ion battery is more demanding.
Improving the working voltage of the lithium ion battery is one of the most effective ways to improve the energy density of the lithium ion battery. However, the traditional carbonate electrolyte has a low oxidative decomposition potential (about 4V), so that the operating voltage of the lithium ion battery assembled by the carbonate electrolyte is strictly limited. Even though some electrolyte additives can slow the oxidative decomposition of such electrolytes and increase the operating voltage of the battery to about 4.4V to some extent, the battery assembled therewith is often unsatisfactory in cycle performance due to the electrochemical instability of the electrolyte itself. In addition, the increase of the operating voltage also puts higher requirements on the safety and reliability of the lithium ion battery. The common carbonate electrolyte becomes the biggest potential safety hazard of the lithium ion battery due to higher vapor pressure and inflammability.
Patents US20060088767a1 and US2011212359a1 propose the use of ionic liquids as electrolytes for lithium ion batteries to increase their operating voltage. The electrolyte has high decomposition potential (> 4.5V), and has good compatibility with a high-potential anode. And due to the lower vapor pressure and the non-inflammability, the safety performance of the lithium ion battery can be greatly improved. However, according to the research of the inventor, due to the fact that the reduction potential of the ionic liquid is high, the ionic liquid can generate violent reduction reaction on the surface of the low-potential negative electrode, and the reduction product can greatly increase the internal resistance of the battery so as to reduce the rate and the cycle performance of the battery. Patent US2005196676a1 proposes that an ionic liquid is gelled with an organic high molecular polymer to further improve the safety of the ionic liquid used as an electrolyte in a lithium ion secondary battery. However, also due to the high reduction potential of the ionic liquid, this gel electrolyte is poorly compatible with low potential negative electrode materials.
Disclosure of Invention
In view of the problems in the background art, an object of the present invention is to provide a lithium ion battery, a gel electrolyte thereof, and a preparation method thereof, which can improve the compatibility of the gel electrolyte with positive and negative electrode plates, and can effectively improve the working voltage, energy density, and cycle life of the lithium ion battery.
In order to achieve the above object, in a first aspect of the present invention, there is provided a lithium ion battery gel electrolyte for spacing between a positive electrode sheet and a negative electrode sheet, the lithium ion battery gel electrolyte comprising: a positive electrode gel electrolyte layer, one side of which is adjacent to a positive electrode plate, the positive electrode plate is provided with a high-potential positive electrode active material, and the oxidation potential of the positive electrode gel electrolyte layer is 4.5V (vs Li/Li)+) The above; a negative electrode gel electrolyte layer, one side of which is adjacent to the negative electrode plate and the other side is connected with the other side of the positive electrode gel electrolyte layer, the negative electrode plate is provided with a low-potential negative electrode active material, and the reduction potential of the negative electrode gel electrolyte layer is 0.2V (vs Li/Li)+) The following.
In order to achieve the above object, in a second aspect of the present invention, there is provided a lithium ion battery comprising: a positive electrode sheet having a high potential positive active material; a negative electrode sheet having a low potential negative electrode active material; and a gel electrolyte, which is spaced between the negative pole piece and the positive pole piece, wherein the gel electrolyte is the lithium ion battery gel electrolyte according to the first aspect of the invention.
In order to achieve the above object, in a third aspect of the present invention, there is provided a method for manufacturing a lithium ion battery according to the second aspect of the present invention, comprising the steps of: respectively dissolving corresponding polymers and lithium salts in organic solvent solutions of plasticizers to prepare slurry for the positive gel electrolyte layer; coating the slurry for the positive electrode gel electrolyte layer on a positive electrode sheet containing a positive electrode active material to form a positive electrode gel electrolyte layer, and then drying under a protective atmosphere to obtain a composite of the positive electrode gel electrolyte layer and the positive electrode sheet; respectively dissolving corresponding polymers and lithium salts in organic solvent solutions of plasticizers to prepare slurry for the negative electrode gel electrolyte layer; coating the slurry for the negative electrode gel electrolyte layer on a negative electrode plate containing a negative electrode active material to form a negative electrode gel electrolyte layer, and then drying under a protective atmosphere to obtain a composite of the negative electrode gel electrolyte layer and the negative electrode plate; compounding a composite of the positive gel electrolyte layer and the positive pole piece with a composite of the negative gel electrolyte layer and the negative pole piece through hot rolling, and then cutting the composite into a battery cell unit; superposing a plurality of cell units to form a cell; and packaging the battery cell to form the lithium ion battery.
The invention has the following beneficial effects:
the gel electrolyte has good compatibility with a high-potential positive electrode active material and a low-potential negative electrode active material, and a battery using the gel electrolyte can effectively improve the working voltage, the energy density and the cycle life of a lithium ion battery by using the gel electrolyte and simultaneously using the high-potential positive electrode material and the low-potential negative electrode material.
Drawings
Fig. 1 is a schematic structural diagram of an arrangement mode of a gel electrolyte of a lithium ion battery according to the invention.
Wherein the reference numerals are as follows:
1 positive pole piece
2 negative pole piece
3 lithium ion battery gel electrolyte
31 positive electrode gel electrolyte layer
32 negative electrode gel electrolyte layer
Detailed Description
The following describes in detail embodiments according to the present invention.
First, the gel electrolyte of the lithium ion battery according to the first aspect of the present invention is explained.
Referring to fig. 1, a lithium ion battery gel electrolyte according to a first aspect of the present invention is used to be spaced between a positive electrode tab 1 and a negative electrode tab 2, and a lithium ion battery gel electrolyte 3 includes: a positive electrode gel electrolyte layer 31, one side of which is adjacent to the positive electrode pole piece 1, the positive electrode pole piece 1 is provided with a high-potential positive electrode active material, and the oxidation potential of the positive electrode gel electrolyte layer 31 is 4.5V (vs Li/Li)+) The above; a negative electrode gel electrolyte layer 32, one side of which is adjacent to the negative electrode plate 2 and the other side of which is additionally connected with the other side of the positive electrode gel electrolyte layer 31, wherein the negative electrode plate 2 is provided with a low-potential negative electrode active material, and the reduction potential of the negative electrode gel electrolyte layer 32 is 0.2V (vs Li/Li)+) The following. Therefore, the working voltage of the lithium ion battery can be greatly widened, so that the lithium ion battery has higher energy density and cycle life.
In the lithium ion battery gel electrolyte according to the first aspect of the invention, both the positive electrode gel electrolyte layer 31 and the negative electrode gel electrolyte layer 32 may contain a polymer and a plasticizer.
In the lithium ion battery gel electrolyte according to the first aspect of the present invention, the plasticizer contained in the positive electrode gel electrolyte layer 31 and the plasticizer contained in the negative electrode gel electrolyte layer 32 have a solubility of less than 1000ppm with respect to each other.
In the lithium ion battery gel electrolyte according to the first aspect of the present invention, the polymer contained in the positive electrode gel electrolyte layer 31 may be selected from one or more of fluorine-containing olefin polymers, polynitrile polymers, and polycarboxylate polymers; the plasticizer contained in the positive electrode gel electrolyte layer 31 may be an ionic liquid containing a lithium salt. The fluorine-containing olefin polymer can be selected from one or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and polyvinylidene fluoride hexafluoropropylene copolymer (PVDF-HFP); the polynitrile polymer is selected from Polyacrylonitrile (PAN); the polycarboxylate polymer is selected from Polymethylmethacrylate (PMMA). The cation in the ionic liquid can be one or more of quaternary ammonium type cation, quaternary phosphine type cation, imidazole type cation and pyridine type cation; the anion in the ionic liquid can be selected from one or more of halogen ion, fluorine-containing inorganic ion and fluorine-containing organic ion. The halogen ion can be selected from one of bromide ion and chloride ion; the fluorine-containing inorganic ion may be selected from BF4 -、PF6 -Bis (fluorosulfonyl) imide ion (FSI)-) One of (1); the fluorine-containing organic ion may be selected from the group consisting of trifluoromethanesulfonic acid ion (OTF)-) Bis (trifluoromethyl) sulfonimide ion (TFSI)-) One kind of (1).
In the lithium ion battery gel electrolyte according to the first aspect of the present invention, the polymer contained in the negative electrode gel electrolyte layer 32 may be selected from one or more of a polyether-based polymer, a halogen-free polyolefin-based polymer, a polythioether-based polymer, and a polyurethane-based polymer; the plasticizer contained in the negative electrode gel electrolyte layer 32 may be a low reduction potential liquid polymer containing a lithium salt. The polyether polymer can be selected from at least one of polyethylene oxide (PEO) and polypropylene oxide (PPO); the halogen-free polyolefin polymer may be selected from at least one of Polyethylene (PE) and polypropylene (PP); the polythioether-based polymer can be selected from polyphenylene sulfide (PPS); the polyurethane-based polymer may be selected from Polyurethanes (PU). The low reduction potential liquid polymer can be at least one selected from polyethylene glycol (PEG), polyethylene glycol dimethyl ether (PEGDME) and polysiloxane.
In the lithium ion battery gel electrolyte according to the first aspect of the present invention, the lithium salt may be selected from LiPF6、LiBF4、LiCl、LiAlCl4、LiSbF6、LiSCN、LiCl、LiCF3SO3、LiCF3CO2、LiN(CF3SO2)2、LiAsF6、LiBC4O8、LiN(FSO2)2And mixtures thereof.
In the gel electrolyte for a lithium ion battery according to the first aspect of the present invention, the high potential positive active material may be selected from at least one of layered lithium metal oxide, spinel-structured lithium metal oxide, lithium metal phosphate, lithium metal fluorosulfate, and lithium metal vanadate. The layered lithium metal oxide may be selected from at least one of Lithium Cobaltate (LCO), Lithium Nickelate (LNO), nickel cobalt manganese ternary material (NMC); the spinel-structured lithium metal oxide is selected from lithium manganate (LiMn)2O4) (ii) a The lithium metal phosphate may be selected from at least one of cobalt lithium phosphate (LCP), nickel lithium phosphate (LNP); the lithium metal fluorinated sulfate may be selected from the group consisting of fluorinated lithium cobalt sulfate (LiCoFSO)4) (ii) a The lithium metal vanadate may be selected from nickel lithium vanadate (LiNiVO)4）。
In the lithium ion battery gel electrolyte according to the first aspect of the present invention, the negative active material may be selected from at least one of a graphite-based material, an alloy-based material, a lithium metal, and an alloy thereof. The graphite material can be at least one of artificial graphite and natural graphite; the alloy material can be at least one selected from silicon, silicon oxide, tin and titanium sulfide.
In the lithium ion battery gel electrolyte according to the first aspect of the present invention, the thickness of the positive electrode gel electrolyte layer 31 is 1 to 100 μm, preferably 5 to 25 μm; the thickness of the negative electrode gel electrolyte layer 32 is 1 to 100 μm, preferably 5 to 25 μm. The energy density of the finished battery can be greatly reduced due to the fact that the gel electrolyte layer is too thick; an excessively thin gel electrolyte layer increases the risk of short circuits within the battery.
A lithium ion battery according to a second aspect of the present invention is explained below.
Referring to fig. 1, a lithium ion battery according to a second aspect of the present invention includes: the positive pole piece 1 is provided with a high-potential positive active material; a negative electrode sheet 2 having a low potential negative electrode active material; the gel electrolyte is spaced between the negative pole piece 2 and the positive pole piece 1; wherein the gel electrolyte is the lithium ion battery gel electrolyte according to the first aspect of the invention.
Next, a method for producing a lithium ion battery according to the third aspect of the invention will be described.
The method for manufacturing a lithium ion battery according to the third aspect of the present invention is used for manufacturing a lithium ion battery according to the second aspect of the present invention, and includes the steps of: respectively dissolving corresponding polymers and lithium salts in organic solvent solutions of plasticizers to prepare slurry for the positive gel electrolyte layer; coating the slurry for the positive electrode gel electrolyte layer on a positive electrode plate 1 containing a positive electrode active material to form a positive electrode gel electrolyte layer 31, and then drying under a protective atmosphere to obtain a composite of the positive electrode gel electrolyte layer 31 and the positive electrode plate 1; respectively dissolving corresponding polymers and lithium salts in organic solvent solutions of plasticizers to prepare slurry for the negative electrode gel electrolyte layer; coating the slurry for the negative electrode gel electrolyte layer on a negative electrode plate 2 containing a negative electrode active material to form a negative electrode gel electrolyte layer 32, and then drying under a protective atmosphere to obtain a composite of the negative electrode gel electrolyte layer 32 and the negative electrode plate 2; the composite of the positive gel electrolyte layer 31 and the positive pole piece 1 and the composite of the negative gel electrolyte layer 32 and the negative pole piece 2 are compounded together by hot rolling, and then the composite is cut into a cell unit; superposing a plurality of cell units to form a cell; and packaging the battery cell to form the lithium ion battery.
In the method for manufacturing a lithium ion battery according to the third aspect of the present invention, the organic solvent may be at least one selected from the group consisting of an ether organic solvent, an ester organic solvent, a nitrile organic solvent, an amide organic solvent, an alcohol organic solvent, and a halogenated organic solvent. The ether organic solvent can be at least one selected from diethyl ether and tetrahydrofuran; the ester organic solvent can be at least one selected from ethyl acetate, methyl formate and dimethyl phthalate; the nitrile organic solvent may be selected from acetonitrile; the amide organic solvent can be at least one of N-methyl pyrrolidone (NMP) and N, N-Dimethylformamide (DMF); the alcohol organic solvent can be selected from ethanol; the halogenated organic solvent may be selected from dichloromethane.
In the method of manufacturing a lithium ion battery according to the third aspect of the invention, the viscosity of the slurry for a positive electrode gel electrolyte layer may be 5000 to 200000mpa.s, preferably 10000 to 50000 mpa.s; the viscosity of the slurry for the negative electrode gel electrolyte layer may be 5000 to 200000mPa.s, preferably 10000 to 50000 mPa.s. The viscosity outside the range can bring adverse effects to the coating of the slurry on the surface of the pole piece; the thickness of the gel electrolyte coating layer is not uniform due to permeation of the slurry into the pole piece when the viscosity is too low, and the difficulty of slurry coating is increased due to too high viscosity.
In the method of manufacturing a lithium ion battery according to the third aspect of the invention, the protective atmosphere is an argon protective atmosphere.
In the method for manufacturing a lithium ion battery according to the third aspect of the present invention, the temperature of the drying treatment may be 50 to 200 ℃.
Finally, examples according to the present invention, comparative examples and test results are explained.
Example 1
Preparing a positive pole piece of the lithium ion battery: lithium cobaltate (30 g) as a positive electrode active material, acetylene black (1 g) as a conductive agent, polyvinylidene fluoride (PVDF, 3 g), and methylpropylpyridinedifluorosulfonyl bisimide salt (PP 13-FSI,10 mL) were thoroughly dispersed in N-methylpyrrolidone (NMP, 100 mL) to prepare a positive electrode slurry. The slurry was applied to both sides of a 15 μm thick aluminum foil, and the solvent was removed by air blast treatment at 80 ℃ for 5h to obtain a positive electrode sheet coated with 80 μm thick active material. Polyvinylidene fluoride (PVDF, 3 g) was dissolved in the plasticizers methylpropylpyridinedifluorosulfimide (PP 13-FSI,10 mL) and lithium hexafluorophosphate (LiPF)610 g) of tetrahydrofuran (100 mL) to prepare a positive electrode gel electrolyte slurry with the viscosity of 30000 mPa.s; coating the positive electrode gel electrolyte slurry on the surface of the dried positive electrode piece; and drying the mixture in an argon atmosphere at 70 ℃ to remove tetrahydrofuran, and then obtaining the positive pole piece covered with the positive pole gel electrolyte layer with the thickness of 12 mu m.
Preparing a lithium ion battery negative pole piece: graphite (20 g) used as a negative active material, acetylene black (1 g) used as a conductive agent, polyethylene oxide (PEO, 2 g), and polyethylene glycol (PEG, 10 mL) were thoroughly dispersed in deionized water (100 mL) to prepare a negative electrode slurry. The slurry was applied to both sides of a 12 μm thick copper foil, and the solvent was removed by air blast treatment at 70 ℃ for 5h to obtain a negative electrode sheet coated with 75 μm thick active material. Polyethylene oxide (PEO, 2 g) was dissolved in polyethylene glycol (PEG, 10 mL) as plasticizer and lithium hexafluorophosphate (LiPF)60.8 g) in acetonitrile (20 mL) to prepare negative electrode gel electrolyte slurry with the viscosity of 25000mPa.s, and coating the negative electrode gel electrolyte slurry on the surface of the dried negative electrode piece; drying the negative pole piece coated with the negative gel electrolyte in an argon atmosphere at 50 ℃ to remove acetonitrile, and then obtaining a negative pole with the thickness of 10 mu mAnd the negative pole piece of the gel electrolyte layer.
Preparing a lithium ion battery: and compounding the prepared positive pole piece and the prepared negative pole piece together through hot rolling, cutting into lithium ion battery units, overlapping 8 lithium ion battery units and packaging into a lithium ion battery to obtain the lithium ion battery A.
Comparative example 1
Preparing a positive pole piece of the lithium ion battery: same as example 1
Preparing a lithium ion battery negative pole piece: the negative electrode tab is only the negative electrode tab not coated with the negative gel electrolyte, and the rest is the same as example 1.
Preparing a lithium ion battery: lithium ion battery B was obtained in the same manner as in example 1.
Example 2
Preparing a positive pole piece of the lithium ion battery: LiNi to be used as a positive electrode active material1/3Co1/3Mn1/3O2(25g) Acetylene black (1 g), polyacrylonitrile (PAN, 1.8 g) and methylpropylpyridinbistrifluoromethylsulfonyl imide salt (PP 13-TFSI,10 mL) used as a conductive agent were well dispersed in N-methylpyrrolidone (NMP, 80 mL) to prepare a positive electrode slurry. The slurry was applied to both sides of a 15 μm thick aluminum foil, and the solvent was removed by air blast treatment at 80 ℃ for 5h to obtain a positive electrode sheet coated with 70 μm thick active material. Polyacrylonitrile (PAN, 1.8 g) was dissolved in the plasticizers methylpropylpyridine bistrifluoromethylsulfonyl imide salt (PP 13-TFSI,10 mL) and lithium salt lithium bistrifluoromethylsulfonyl imide (LiN (CF)3SO2)27.2 g) of the electrolyte solution in 70mL of ethyl acetate to prepare anode gel electrolyte slurry with the viscosity of 40000 mPa.s; coating the positive electrode gel electrolyte slurry on the surface of the dried positive electrode piece; drying in an argon atmosphere at 50 ℃ to remove ethyl acetate, and then obtaining the positive pole piece covered with the positive pole gel electrolyte layer with the thickness of 15 mu m.
Preparing a lithium ion battery negative pole piece: polypropylene oxide (PPO, 2.5 g) was dissolved in the plasticizers polyethylene glycol dimethyl ether (PEGDME, 10 mL) and lithium salt lithium bistrifluoromethylsulfonyl imide (LiN (CF)3SO2)212 g) of N, N-dimethylformamide (DMF, 160 mL) to prepare a negative electrode gel electrolyte slurry with the viscosity of 12000mPa.s, and coating the negative electrode gel electrolyte slurry on the surface of a lithium sheet (65 μm) serving as a negative electrode; and drying the negative pole piece coated with the negative gel electrolyte in an argon atmosphere at 90 ℃ to remove DMF, and then obtaining the negative pole piece coated with the negative gel electrolyte layer with the thickness of 20 mu m.
Preparing a lithium ion battery: and compounding the prepared positive pole piece and the prepared negative pole piece together through hot rolling, cutting into lithium ion battery units, overlapping 8 lithium ion battery units and packaging into a lithium ion battery to obtain a lithium ion battery C.
Comparative example 2
Preparing a positive pole piece of the lithium ion battery: same as example 2
Preparing a lithium ion battery negative pole piece: the negative electrode sheet is a negative electrode sheet not coated with the negative gel electrolyte, and the rest is the same as example 2.
Preparing a lithium ion battery: in the same manner as in example 2, a lithium ion battery D was obtained.
Example 3
Preparing a positive pole piece of the lithium ion battery: lithium manganate LiMn to be used as positive electrode active material2O4(40g) Acetylene black (1 g), polymethyl methacrylate (PMMA, 3.2 g) and methylbutyl pyridine bistrifluoromethylsulfonyl imide salt (PP 14-TFSI,10 mL) used as a conductive agent were thoroughly dispersed in N-methylpyrrolidone (NMP, 100 mL) to prepare a positive electrode slurry. The slurry was applied to both sides of a 15 μm thick aluminum foil, and the solvent was removed by air blast treatment at 80 ℃ for 5h to obtain a positive electrode sheet coated with 85 μm thick active material. A mixture of polymethyl methacrylate (PMMA,3.2 g) dissolved in the plasticizers methylbutylpyridine bistrifluoromethylsulfonyl imide salt (PP 14-TFSI,10 mL) and lithium salt lithium bis-fluorosulfonimide (LiN (FSO)2)29 g) in dichloromethane (100 mL) to prepare positive gel electrolyte slurry with viscosity of 20000 mPa.s; coating the positive electrode gel electrolyte slurry on the surface of the dried positive electrode piece; drying in an argon atmosphere at 40 ℃ to remove dichloromethane, and then obtaining the positive pole piece covered with the positive pole gel electrolyte layer with the thickness of 18 mu m.
Preparing a lithium ion battery negative pole piece: silicon powder (25 g) serving as a negative electrode active material, acetylene black (1 g) serving as a conductive agent, polymethyl methacrylate (PMMA, 1.6 g), and polysiloxane (10 mL) were thoroughly dispersed in nitrogen methyl pyrrolidone (NMP, 100 mL) to prepare a negative electrode slurry. The slurry was applied to both sides of a 12 μm thick copper foil, and the solvent was removed by air blast treatment at 80 ℃ for 5h to obtain a negative electrode sheet coated with 75 μm thick active material. Polyphenylene sulfide (PPS, 1.6 g) was dissolved in a plasticizer polysiloxane (10 mL) and lithium salt lithium bis-fluorosulfonylimide (LiN (FSO)2)20.9 g) in acetonitrile (20 mL) to prepare negative electrode gel electrolyte slurry with the viscosity of 25000mPa.s, and coating the negative electrode gel electrolyte slurry on the surface of the dried negative electrode piece; and drying the negative pole piece coated with the negative gel electrolyte in an argon atmosphere at 50 ℃ to remove acetonitrile, and then obtaining the negative pole piece coated with the negative gel electrolyte layer with the thickness of 8 mu m.
Preparing a lithium ion battery: and compounding the prepared positive pole piece and the prepared negative pole piece together through hot rolling, cutting into lithium ion battery units, overlapping 8 lithium ion battery units and packaging into a lithium ion battery to obtain a lithium ion battery E.
Comparative example 3
Preparing a positive pole piece of the lithium ion battery: same as example 3
Preparing a lithium ion battery negative pole piece: the negative electrode sheet is a negative electrode sheet not coated with the negative gel electrolyte, and the rest is the same as example 3.
Preparing a lithium ion battery: in the same manner as in example 3, a lithium ion battery F was obtained.
Example 4
Preparing a positive pole piece of the lithium ion battery: LiCoFSO to be used as a cathode active material4(45g) Acetylene black (1 g), polyacrylonitrile (PAN, 2.2 g) and methylbutylpyridine bistrifluoromethylsulfonyl imide salt (PP 14-TFSI,10 mL) used as a conductive agent were well dispersed in N-methylpyrrolidone (NMP, 100 mL) to prepare a positive electrode slurry. The slurry was applied to both sides of a 15 μm thick aluminum foil, and the solvent was removed by air blast treatment at 80 ℃ for 5h to obtain a positive electrode sheet coated with 65 μm thick active material. Polyacrylonitrile (PAN, 2.2 g) was dissolved in the plasticizers methylbutylpyridine bistrifluoromethylsulfonyl imide salt (PP 14-TFSI,10 mL) and lithium salt lithium bis-fluorosulfonimide (LiN (FSO)2)29 g) of N, N-dimethylformamide (DMF, 100 mL) to prepare positive gel electrolyte slurry with the viscosity of 22000 mPa.s; coating the positive electrode gel electrolyte slurry on the surface of the dried positive electrode piece; drying at 150 ℃ in an argon atmosphere to remove DMF, and then obtaining the positive pole piece covered with the positive pole gel electrolyte layer with the thickness of 18 mu m.
Preparing a lithium ion battery negative pole piece: natural graphite (35 g) used as a negative active material, acetylene black (1 g) used as a conductive agent, polyethylene oxide (PEO, 1.6 g), and polyethylene glycol (PEG, 10 mL) were thoroughly dispersed in deionized water (100 mL) to prepare a negative electrode slurry. The slurry was applied to both sides of a 12 μm thick copper foil, and the solvent was removed by air blast treatment at 70 ℃ for 5h to obtain a negative electrode sheet coated with 95 μm thick active material. Polyethylene oxide (PEO, 1.6 g) was dissolved in polyethylene glycol (PEG, 10 mL) as plasticizer and lithium salt lithium bis-fluorosulfonylimide (LiN (FSO)2)20.9 g) of azomethidone (NMP, 20 mL) to prepare a negative electrode gel electrolyte slurry having a viscosity of 25000mpa.s, and coating the negative electrode gel electrolyte slurry on the dried negative electrode sheetA surface of (a); and drying the negative pole piece coated with the negative gel electrolyte in an argon atmosphere at 80 ℃ to remove NMP, and then obtaining the negative pole piece coated with the negative gel electrolyte layer with the thickness of 5 mu m.
Preparing a lithium ion battery: preparing a lithium ion battery: and compounding the prepared positive pole piece and the prepared negative pole piece together through hot rolling, cutting into lithium ion battery units, overlapping 8 lithium ion battery units and packaging into a lithium ion battery to obtain a lithium ion battery G.
Comparative example 4
Preparing a positive pole piece of the lithium ion battery: same as example 4
Preparing a lithium ion battery negative pole piece: the negative electrode sheet is a negative electrode sheet not coated with the negative gel electrolyte, and the rest is the same as example 4.
Preparing a lithium ion battery: in the same manner as in example 4, a lithium ion battery H was obtained.
Finally, the lithium ion battery detection and results of the examples 1 to 4 and the comparative examples 1 to 4 of the invention are given.
Capacity retention rate test: the lithium ion batteries (4 lithium ion batteries) of examples 1 to 4 and comparative examples 1 to 4 were charged at a constant current of 1C at normal temperature, and the charge cut-off voltages of the lithium ion battery a and the lithium ion battery B were 4.5V; the charge cut-off voltage of the lithium ion battery C and the lithium ion battery D is 4.8V; the charge cut-off voltage of the lithium ion battery E and the lithium ion battery F is 4.9V; the charge cut-off voltage of the lithium ion battery G and the lithium ion battery H is 5.1V; after charging to 0.05 ℃ at constant voltage, standing for 30min, and then discharging at a constant current of 1C, wherein the discharge cut-off voltage of the lithium ion batteries A, B, C, D, E and F is 3V; the discharge cut-off voltage of the lithium ion battery G and the lithium ion battery H is 3.5V; and standing for 30min, and performing 500-time cyclic charge and discharge tests on the lithium ion battery according to the mode, and taking the discharge capacity of the 500 th cycle.
The capacity retention (%) at week N = [ discharge capacity at week N/discharge capacity at week N ]. 100%, and the results are shown in table 1.
TABLE 1 Capacity Retention rates after cycling of lithium ion batteries of examples 1-4 and comparative examples 1-4
As can be seen from table 1, the capacity retention rates of the lithium ion batteries A, C, E and G with the double-layer gel electrolyte in examples 1 to 4 after 500 cycles under high voltage are both above 85%, which indicates that the double-layer gel electrolyte has good compatibility with both the high-potential positive electrode and the low-potential negative electrode, thereby significantly improving the cycle performance of the lithium ion batteries. However, the lithium ion batteries B, D, F and H of comparative examples 1-4 with a single layer of positive gel electrolyte decayed rapidly in capacity during cycling and the lithium ion batteries failed rapidly. The performance decay of the lithium ion batteries is closely related to the incompatibility of the ionic liquid to a low-potential negative electrode. Ionic liquids are reduced at the negative terminal as plasticizers for gel electrolytes, leading to increased polarization and eventual failure of lithium ion batteries.
Claims (9)
1. A lithium ion battery gel electrolyte for spacing between a positive electrode sheet (1) and a negative electrode sheet (2), characterized in that the lithium ion battery gel electrolyte (3) comprises:
a positive electrode gel electrolyte layer (31), one side of which is adjacent to the positive electrode plate (1), wherein the positive electrode plate (1) is provided with a high-potential positive electrode active material, and the oxidation potential of the positive electrode gel electrolyte layer (31) is 4.5V (vsLi/Li)+) The above;
a negative electrode gel electrolyte layer (32) having one side adjacent to the negative electrode sheet (2) and the other side adjacent to the positive electrode gel electrolyte layer (31)The negative pole piece (2) is provided with a low-potential negative pole active material, and the reduction potential of the negative pole gel electrolyte layer (32) is 0.2V (vs Li/Li)+) The following;
wherein,
the positive electrode gel electrolyte layer (31) and the negative electrode gel electrolyte layer (32) both contain a polymer and a plasticizer;
the plasticizer contained in the positive electrode gel electrolyte layer (31) and the plasticizer contained in the negative electrode gel electrolyte layer (32) have a solubility of less than 1000ppm with respect to each other;
the high-potential positive electrode active material is selected from at least one of layered lithium metal oxide, spinel-structured lithium metal oxide, lithium metal phosphate, lithium metal fluoride sulfate and lithium metal vanadate;
the low-potential negative electrode active material is selected from at least one of graphite materials, silicon oxide, tin, titanium sulfide, lithium metal and lithium alloy.
2. The lithium ion battery gel electrolyte of claim 1,
the polymer contained in the positive electrode gel electrolyte layer (31) is one or more selected from fluorine-containing olefin polymers, polynitrile polymers and polycarboxylate polymers;
the plasticizer contained in the positive electrode gel electrolyte layer (31) is an ionic liquid containing lithium salt;
the polymer contained in the negative electrode gel electrolyte layer (32) is selected from one or more of polyether polymer, halogen-free polyolefin polymer, polythioether polymer and polyurethane polymer;
the plasticizer contained in the negative electrode gel electrolyte layer (32) is a low reduction potential liquid polymer containing a lithium salt.
3. The lithium ion battery gel electrolyte of claim 2,
the fluorine-containing olefin polymer is at least one selected from Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinylidene fluoride hexafluoropropylene copolymer (PVDF-HFP);
the polynitrile polymer is selected from Polyacrylonitrile (PAN);
the polycarboxylate polymer is selected from Polymethylmethacrylate (PMMA);
the polyether polymer is selected from at least one of polyethylene oxide (PEO) and polypropylene oxide (PPO);
the halogen-free polyolefin polymer is selected from at least one of Polyethylene (PE) and polypropylene (PP);
the polythioether polymer is selected from polyphenylene sulfide (PPS);
the polyurethane-based polymer is selected from the group consisting of Polyurethanes (PU);
the low reduction potential liquid polymer is at least one selected from polyethylene glycol (PEG), polyethylene glycol dimethyl ether (PEGDME) and polysiloxane.
4. The lithium ion battery gel electrolyte of claim 2, wherein the lithium salt is selected from LiPF6、LiBF4、LiCl、LiAlCl4、LiSbF6、LiSCN、LiCl、LiCF3SO3、LiCF3CO2、LiN(CF3SO2)2、LiAsF6、LiBC4O8、LiN(FSO2)2And mixtures thereof.
5. The lithium ion battery gel electrolyte of claim 1,
the thickness of the positive electrode gel electrolyte layer (31) is 1-100 μm;
the thickness of the negative electrode gel electrolyte layer (32) is 1 to 100 μm.
6. The lithium ion battery gel electrolyte of claim 5,
the thickness of the positive electrode gel electrolyte layer (31) is 5-25 μm;
the thickness of the negative electrode gel electrolyte layer (32) is 5 to 25 μm.
7. A lithium ion battery comprising:
a positive electrode sheet (1) having a high-potential positive electrode active material;
a negative electrode sheet (2) having a low potential negative electrode active material; and
the gel electrolyte is spaced between the negative pole piece (2) and the positive pole piece (1);
characterized in that the gel electrolyte is a lithium ion battery gel electrolyte according to any one of claims 1 to 6.
8. A method for manufacturing a lithium ion battery according to claim 7, comprising the steps of:
respectively dissolving corresponding polymers and lithium salts in organic solvent solutions of plasticizers to prepare slurry for the positive gel electrolyte layer;
coating the slurry for the positive electrode gel electrolyte layer on a positive electrode plate (1) containing a positive electrode active material to form a positive electrode gel electrolyte layer (31), and then drying under a protective atmosphere to obtain a composite of the positive electrode gel electrolyte layer (31) and the positive electrode plate (1);
respectively dissolving corresponding polymers and lithium salts in organic solvent solutions of plasticizers to prepare slurry for the negative electrode gel electrolyte layer;
coating the slurry for the negative electrode gel electrolyte layer on a negative electrode pole piece (2) containing a negative electrode active material to form a negative electrode gel electrolyte layer (32), and then drying under a protective atmosphere to obtain a composite of the negative electrode gel electrolyte layer (32) and the negative electrode pole piece (2);
the composite of the positive gel electrolyte layer (31) and the positive pole piece (1) and the composite of the negative gel electrolyte layer (32) and the negative pole piece (2) are compounded together by hot rolling, and then the battery cell unit is cut;
superposing a plurality of cell units to form a cell; and
and packaging the battery cell to form the lithium ion battery.
9. The method for manufacturing a lithium ion battery according to claim 8, wherein the temperature of the drying treatment is 50 to 200 ℃.
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| CN111613830B (en) * | 2020-07-09 | 2021-08-17 | 常州赛得能源科技有限公司 | Composite electrolyte and application thereof |
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| JP4014816B2 (en) * | 2001-04-13 | 2007-11-28 | シャープ株式会社 | Lithium polymer secondary battery |
| JP4032931B2 (en) * | 2002-11-06 | 2008-01-16 | 日産自動車株式会社 | Bipolar battery |
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Address after: 352100 Jiaocheng District of Ningde City, Fujian Province Zhang Wan Zhen Xingang Road No. 1 Patentee after: Contemporary Amperex Technology Co.,Ltd. Patentee after: NINGDE AMPEREX TECHNOLOGY Ltd. Address before: 352100 Jiaocheng District of Ningde City, Fujian Province Zhang Wan Zhen Xingang Road No. 1 West Building 1F- research Patentee before: CONTEMPORARY AMPEREX TECHNOLOGY Ltd. Patentee before: Ningde Amperex Technology Ltd. |