CN114188599A - High-energy-density dual-electrolyte lithium ion battery and preparation method and application thereof - Google Patents
High-energy-density dual-electrolyte lithium ion battery and preparation method and application thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 252
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 91
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title abstract description 7
- -1 perfluoro Chemical group 0.000 claims abstract description 46
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 150000003457 sulfones Chemical class 0.000 claims abstract description 16
- 239000002608 ionic liquid Substances 0.000 claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 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 32
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 30
- 239000012528 membrane Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims description 22
- 159000000002 lithium salts Chemical class 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 230000009977 dual effect Effects 0.000 claims description 16
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 15
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 12
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000009830 intercalation Methods 0.000 claims description 9
- 230000002687 intercalation Effects 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical class FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910013716 LiNi Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000006182 cathode active material Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000011241 protective layer Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims description 2
- 229920001774 Perfluoroether Polymers 0.000 claims 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims 1
- 230000007849 functional defect Effects 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 229920000557 Nafion® Polymers 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 238000003411 electrode reaction Methods 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 14
- 229910013872 LiPF Inorganic materials 0.000 description 14
- 101150058243 Lipf gene Proteins 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 10
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 8
- 230000003044 adaptive effect Effects 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 230000016507 interphase Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001520299 Phascolarctos cinereus Species 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- MJIULRNAOLSIHL-UHFFFAOYSA-N carbonic acid;fluoroethene Chemical compound FC=C.OC(O)=O MJIULRNAOLSIHL-UHFFFAOYSA-N 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
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- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
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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
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
Abstract
The invention discloses a high-energy-density double-electrolyte lithium ion battery and a preparation method and application thereof. The double-electrolyte lithium ion battery comprises an anode, an anode reaction chamber, a diaphragm, a cathode and a cathode reaction chamber; a positive electrolyte channel is arranged above the positive reaction chamber, and a negative electrolyte channel is arranged above the negative reaction chamber; the anode is contacted with the anode electrolyte, and the cathode is contacted with the cathode electrolyte; the positive electrolyte and the negative electrolyte are separated by a diaphragm; the positive electrolyte is one of perfluoro-based electrolyte, sulfone-based electrolyte and ionic liquid electrolyte; the negative electrode electrolyte is one of an ether-based electrolyte, a fluorine ether-based electrolyte and a local high-concentration ether-based electrolyte. The invention combines the advantages of the positive electrolyte and the negative electrolyte, makes up the functional defects of the traditional single electrolyte, improves the cycle life of the lithium ion battery and obviously improves the cycle performance of the lithium ion battery.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a high-energy-density dual-electrolyte lithium ion battery and a preparation method and application thereof.
Background
In order to meet the rapidly increasing demand of electric transportation and large-scale energy grid systems, it is required to develop a battery having high energy density and long cycle life. The reliability of high energy density long cycle lithium ion batteries can ultimately be achieved through structurally optimized electrode materials and tailored electrolyte systems. Silicon-based composites are considered to be one of the most viable anode candidates for lithium ion batteries because of their high capacity and durability. However, during the continuous cycling, the extreme volume fluctuations can lead to fatal mechanical cracking of the Si, resulting in repeated damage to the surface. The formation of a stable Solid Electrolyte Interphase (SEI) can tolerate the volume strain of silicon, which is critical to extending the cycle life of a lithium ion battery without further electrolyte decomposition. Although vinyl fluoride carbonate (FEC) was used as a standard additive for anodic protection, its role in reversibility of silicon-containing anodes remains controversial. In this regard, the discovery of new electrolytes that can compensate for the shortcomings of conventional electrolytes, such as reduced battery cycle life, will help in the development of robust silicon-based anode materials.
To achieve high energy density lithium ion batteries, reliable cathode technology must be achieved at the same time. Although high pressure/high capacity intercalation nickel-rich cathode NCM (LiNi)0.8Mn0.1Co0.1O2NCM811), but practical application thereof is hindered due to problems of irreversible phase transition and particle cracking during charging. Furthermore, at high pressures above 4.3V, conventional carbonate electrolytes are compatible with Li/Li+Leads to a thickening of the catholyte interphase (CEI). In contrast, the use of electrolytes based on a perfluoro-based electrolyte, a sulfone-based electrolyte, and an Ionic Liquid (IL) can satisfy the high pressure resistance required for the positive electrode reaction, can improve the electrochemical performance of the nickel cathode, and simultaneously alleviate the adverse phase change that occurs continuously by reconstructing the cathode surface. However, despite extensive research on such high voltage electrolytes, there has not been a high voltage electrolyte that achieves both desirable high and low potential stability. Therefore, full cell lithium ion batteries based on high voltage electrolytes typically use electrodes of moderate potential, limiting operating voltage and energy density. Although mixed ionic liquids have been usedSynergistic effects are proposed, but this approach does not fully broaden the operating voltage of full-cell lithium-ion batteries. In addition, organic carbonates have been added to ionic liquid electrolytes to enhance cathode stability, but at the expense of safety. Therefore, it is desirable to find a simple electrolyte design method for achieving high energy density, long cycle lithium ion batteries.
The full battery assembled based on the high-capacity high-voltage intercalation positive electrode NCM and the high-capacity low-voltage silicon-based negative electrode can provide the highest theoretical energy density in all electrochemistry, but has some defects in the practical application process, and at present, any electrolyte thermodynamic window can simultaneously meet the requirements of the high-voltage positive electrode and the low-voltage negative electrode, so that the energy density of the full battery based on the NCM-Si base is limited. The use of conventional commercial electrolytes results in excessively low energy density and poor cycle life based on NCM811-Si/C full cells.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a dual-electrolyte lithium ion battery with high energy density.
The invention also aims to provide a preparation method of the dual-electrolyte lithium ion battery with high energy density.
It is a further object of the present invention to provide the use of the high energy density dual electrolyte lithium ion battery.
The purpose of the invention is realized by the following technical scheme:
a high energy density double electrolyte lithium ion battery comprises an anode, an anode reaction chamber, a diaphragm, a cathode and a cathode reaction chamber;
a positive electrolyte channel is arranged above the positive reaction chamber, and a negative electrolyte channel is arranged above the negative reaction chamber;
the anode is contacted with the anode electrolyte, and the cathode is contacted with the cathode electrolyte;
the positive electrolyte and the negative electrolyte are separated by a diaphragm;
the positive electrolyte is one of perfluoro-based electrolyte, sulfone-based electrolyte and ionic liquid electrolyte;
the negative electrode electrolyte is one of an ether-based electrolyte, a fluorine ether-based electrolyte and a local high-concentration ether-based electrolyte.
The anode is a high-capacity high-voltage intercalation cathode (contacted with a cathode electrolyte); further preferably a positive electrode made of a high-voltage high-capacity nickel-rich NCM positive electrode material; still more preferably a positive electrode made of a nickel-rich ternary NCM811 material; more preferably, the compound is prepared by the following method: LiNi as cathode active material0.8Co0.1Mn0.1O2Acetylene black and polyvinylidene fluoride according to a mass ratio of 95: 2: 3, uniformly mixing, adding N-methyl pyrrolidone (NMP) as a solvent to prepare slurry, uniformly coating the slurry on an aluminum foil, and performing vacuum drying, rolling and slicing to obtain a high-capacity high-voltage intercalation cathode which is used as the anode of the dual-electrolyte lithium ion battery.
The diameter of the high-capacity high-voltage intercalation cathode is about 1.4 cm, and the surface density is 7.7mg/cm–2。
The negative electrode is a high-capacity low-voltage silicon-based anode (in contact with an anolyte); preferably a negative electrode made of a silicon carbon material; more preferably, the preparation method comprises the following steps: mixing a negative electrode active material Si/C-650, acetylene black, a binder Styrene Butadiene Rubber (SBR) and carboxymethyl cellulose (CMC) according to a mass ratio of 95: 1: 2:2, adding deionized water serving as a solvent to prepare slurry, uniformly coating the slurry on an aluminum foil, and performing vacuum drying, rolling and slicing to obtain a high-capacity low-voltage anode serving as a cathode of the dual-electrolyte lithium ion battery.
The diameter of the high-capacity low-voltage anode is about 1.6 cm, and the surface density is 3mg/cm–2。
The positive and negative electrolytes in the invention are composed of lithium salt and organic solvent; the positive electrolyte is high-voltage-resistant electrolyte, and the negative electrolyte is low-voltage-resistant electrolyte.
The lithium salt is lithium hexafluorophosphate (LiPF)6) Lithium bis (fluorosulfonyl) imide (LiFSI) and bis (trifluoromethylsulfonyl) imideOne or more of Lithium (LiTFSI);
the organic solvent is fluoroethyl carbonate (FEMC), fluoroethylene carbonate (FEC), Hydrofluoroether (HFE), ethylene glycol dimethyl ether (DME), beta-fluorinated sulfone (TFPMS), Tetrahydrofuran (THF), dimethyl tetrahydrofuran (MTHF) and 1-methyl-1-propyl pyrrolidine bis (trifluoromethanesulfonyl) imide salt (Pyr)13TFSI) is used.
The concentration of the positive electrolyte is 14-28% by mass (namely, the lithium salt of the positive electrolyte accounts for 14-28% of the total mass of the positive electrolyte).
The concentration of the negative electrode electrolyte is 14-28% by mass (namely, the lithium salt of the negative electrode electrolyte accounts for 14-28% of the total mass of the negative electrode electrolyte).
The lithium salt in the perfluoro-based electrolyte is lithium hexafluorophosphate (LiPF)6) One or more of lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (preferably lithium bis (fluorosulfonyl) imide); the organic solvent is one or more of fluoroethyl methyl carbonate (FEMC), fluoroethylene carbonate (FEC) and Hydrofluoroether (HFE) (preferably an organic solvent obtained by mixing fluoroethyl methyl carbonate, fluoroethylene carbonate and hydrofluoroether in a mass ratio of 2:2: 6).
The concentration of the perfluoro-based electrolyte is preferably 14% by mass.
The lithium salt in the sulfone-based electrolyte is lithium hexafluorophosphate (LiPF)6) One or more of lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (preferably lithium hexafluorophosphate); the organic solvent is beta-fluorinated sulfone (TFPMS).
The concentration of the sulfone-based electrolyte is preferably 28% by mass.
The lithium salt in the ionic liquid electrolyte is lithium hexafluorophosphate (LiPF)6) One or more of lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (preferably lithium bis (trifluoromethylsulfonyl) imide); the organic solvent is 1-methyl-1-propyl pyrrolidine bis (trifluoromethanesulfonyl) imide salt (Pyr13 TFSI).
The concentration of the ionic liquid electrolyte is preferably 14% by mass.
The lithium salt in the ether electrolyte is lithium hexafluorophosphate (LiPF)6) One or more of lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (preferably lithium bis (fluorosulfonyl) imide); the organic solvent is one or more of ethylene glycol dimethyl ether (DME), fluoroethylene carbonate (FEC) and Hydrofluoroether (HFE) (preferably an organic solvent obtained by mixing ethylene glycol dimethyl ether, fluoroethylene carbonate and hydrofluoroether according to the mass ratio of 2:2: 6).
The concentration of the ether electrolyte is preferably 14% by mass.
The lithium salt in the fluorine ether-based electrolyte is lithium hexafluorophosphate (LiPF)6) One or more of lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (preferably lithium hexafluorophosphate); the organic solvent is one or two of Tetrahydrofuran (THF) and dimethyl tetrahydrofuran (MTHF) (preferably an organic solvent obtained by mixing tetrahydrofuran and dimethyl tetrahydrofuran in a volume ratio of 1: 1).
The concentration of the fluorine ether-based electrolyte is preferably 28% by mass.
The lithium salt in the local high-concentration ether-based electrolyte is lithium hexafluorophosphate (LiPF)6) One or more of lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (preferably lithium bis (trifluoromethylsulfonyl) imide); the organic solvent is one or two of ethylene glycol dimethyl ether (DME) and Hydrofluoroether (HFE) (preferably an organic solvent obtained by mixing ethylene glycol dimethyl ether and hydrofluoroether in a volume ratio of 1: 3).
The concentration of the local high-concentration ether-based electrolyte is preferably 14% by mass.
And diaphragm protective layers are arranged at two ends of the diaphragm, which are in contact with the positive electrolyte and the negative electrolyte.
The diaphragm is a perfluorinated sulfonic acid proton exchange membrane (Nafion-based diaphragm); preferably a lithiated perfluorosulfonic acid proton exchange membrane (lithiated Nafion-based membrane).
The lithiated perfluorosulfonic acid proton exchange membrane (lithiated Nafion-based membrane) is preferably prepared by the following method:
putting the perfluorinated sulfonic acid proton exchange membrane into deionized water, boiling for 3-5 hours for pretreatment, then transferring the perfluorinated sulfonic acid proton exchange membrane into a hydrogen peroxide water solution with the concentration of 5% by volume, treating for 3-5 hours at 60 ℃, then putting the perfluorinated sulfonic acid proton exchange membrane into a dilute sulfuric acid solution, boiling for 2 hours, and cleaning with boiling deionized water; and then boiling the cleaned perfluorinated sulfonic acid proton exchange membrane in LiOH solution for 2 hours, cleaning, drying and punching to form a diaphragm to obtain the lithiated perfluorinated sulfonic acid proton exchange membrane (lithiated Nafion-based diaphragm).
The concentration of the dilute sulfuric acid solution is preferably 5 mol/L.
The concentration of the LiOH solution is preferably 1 mol/L.
The LiOH solution is preferably prepared by the following method: adding LiOH into a mixture of ethanol and deionized water in a volume ratio of 1: 2, mixing the obtained solution to prepare a LiOH solution.
The drying conditions are preferably as follows: vacuum drying at 80 deg.C for more than 5 days.
The diameter of the diaphragm is about 19 mm.
The preparation method of the double-electrolyte lithium ion battery with high energy density comprises the following steps: preparing the positive electrolyte and the negative electrolyte, and then assembling according to the assembling sequence of the lithium ion battery to obtain the dual-electrolyte lithium ion battery.
The high-energy-density double-electrolyte lithium ion battery is applied to the field of lithium ion batteries.
Compared with the prior art, the invention has the following advantages and effects:
(1) compared with the traditional single electrolyte, the method for realizing the high-energy-density long-cycle lithium ion battery based on the double-electrolyte battery technology has the advantages that the thermodynamic window of the single electrolyte cannot simultaneously meet the requirements of a high-voltage positive electrode and a low-voltage negative electrode, the functional defects of the traditional single electrolyte are overcome by combining the advantages of the positive electrolyte and the negative electrolyte, the cycle life of the lithium ion battery based on a high-voltage ternary positive electrode material and a silicon-carbon negative electrode system is prolonged, and the cycle performance of the lithium ion battery is remarkably improved.
(2) The double-electrolyte battery system with the high-energy-density lithium ion battery electrode compatible with the electrolyte consists of positive and negative electrolytes, positive and negative reaction chambers, positive and negative materials and a diaphragm; the lithium ion battery electrolyte comprises a positive electrode electrolyte, a negative electrode electrolyte, a positive electrode reaction chamber and a negative electrode reaction chamber, wherein the positive electrode electrolyte is a high-voltage resistant electrolyte, the negative electrode electrolyte is a low-voltage resistant electrolyte, the positive electrode material is a high-capacity high-voltage intercalation nickel-rich cathode, the negative electrode material is a high-capacity low-voltage silicon-based anode, and a diaphragm is a lithiated perfluorinated sulfonic acid proton exchange membrane (Nafion-based diaphragm), the positive electrode reaction chamber and the negative electrode reaction chamber are separated by the lithiated perfluorinated sulfonic acid proton exchange membrane, and an independent electrolyte environment is established by measuring the positive electrode and the negative electrode, so that a good reaction environment corresponding to the positive electrode and the negative electrode is realized, and the electrochemical window of the lithium ion battery is further widened.
Drawings
FIG. 1 is a structural diagram of a dual electrolyte lithium ion battery of the present invention (in the figure, 1: positive electrode; 2: negative electrode; 3: positive electrode reaction chamber; 4: positive electrode electrolyte; 5: negative electrode reaction chamber; 6: negative electrode electrolyte; 7: separator; 8: separator protective layer).
FIG. 2 is a graph showing the results of cycle tests at 25 ℃ at room temperature in examples 1 to 3 and comparative examples 1 to 7.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. The following examples are given without reference to specific experimental conditions, and are generally in accordance with conventional experimental conditions. Unless otherwise specified, reagents and starting materials for use in the present invention are commercially available.
The structure of the dual-electrolyte lithium ion battery in the embodiment of the invention is shown in fig. 1, and the dual-electrolyte lithium ion battery comprises a positive electrode 1, a negative electrode 2, a positive electrode reaction chamber 3, a positive electrode electrolyte 4, a negative electrode reaction chamber 5, a negative electrode electrolyte 6, a diaphragm 7 and a diaphragm protection layer 8;
the anode reaction chamber 3 is provided with an anode electrolyte channel, and the cathode reaction chamber 5 is provided with a cathode electrolyte channel; electrolyte channels are designed on the anode reaction chamber 3 and the cathode reaction chamber 5, and liquid can be injected from the outside, namely, the anode electrolyte 4 enters the anode reaction chamber 3 through the anode electrolyte channel to participate in the reaction, and the cathode electrolyte 6 enters the cathode reaction chamber 5 through the cathode electrolyte channel to participate in the reaction;
the positive electrode reaction chamber 3 is internally provided with a positive electrode electrolyte 4, and the negative electrode reaction chamber 5 is provided with a negative electrode electrolyte 6;
the positive electrode reaction chamber 3 and the negative electrode reaction chamber 5 are separated by a diaphragm 7, namely the positive electrode electrolyte 4 and the negative electrode electrolyte 6 are separated by the diaphragm 7;
two ends of the diaphragm 7, which are in contact with the positive electrolyte 4 and the negative electrolyte 6, are provided with diaphragm protection layers 8;
the membrane 7 can be a lithiated perfluorosulfonic acid proton exchange membrane (lithiated Nafion-based membrane) and is prepared by the following method:
the method comprises the following steps of pretreating a commercial perfluorosulfonic acid proton exchange membrane: first, in order to convert the Nafion membrane into-SO3H form, boiling a perfluorinated sulfonic acid proton exchange membrane (Nafion membrane) in deionized water for 3-5 hours for pretreatment, and then transferring to another membrane containing 5% (v/v) hydrogen peroxide (H)2O2) Treating the mixture for 3 to 5 hours at the temperature of 60 ℃ in the aqueous solution; then boiling the Nafion membrane in a dilute sulfuric acid (0.5M) solution for 2 hours, and then cleaning with boiling deionized water; subsequent Li+Exchange process under strong stirring, the Nafion membrane is boiled in 1M LiOH solution (the volume ratio of ethanol to deionized water is 1: 2 solution) for 2 hours; rinsing the Nafion membrane and washing again in boiling deionized water to remove residual salts and ethanol; finally, after vacuum drying at 80 ℃ for 5 days, the lithiated Nafion membrane was transferred into a glove box filled with argon and punched into a separator (diameter 19 mm) to obtain a lithiated Nafion-based separator. The separator used in the following examples was a lithiated Nafion-based separator.
During the experiment, after the parts are sealed and fixed by the clamping device, positive electrolyte and negative electrolyte are respectively injected into the lithium ion battery shell, the positive electrode is contacted with the positive electrolyte, and the negative electrode is contacted with the negative electrolyte; because the positive electrode reaction chamber and the negative electrode reaction chamber are separated by the diaphragm, the situation that the positive electrolyte and the negative electrolyte are mixed does not occur, and the concentration of the electrolytes in the positive electrode reaction chamber and the negative electrode reaction chamber on the two sides of the diaphragm can be respectively and freely adjusted.
(II) the anode (the negative electrode material is a high-capacity low-voltage anode) of the lithium ion battery in the embodiment of the invention is prepared by the following method: mixing a negative electrode active material Si/C-650 (China colored Guilin mineral research institute), acetylene black, a binder Styrene Butadiene Rubber (SBR) and carboxymethyl cellulose (CMC) (purchased from Korea company, China) according to a mass ratio of 95: 1: 2:2, taking deionized water as a solvent, mixing into slurry, uniformly coating the anode slurry on a copper foil, performing vacuum drying, rolling and slicing to prepare a cathode with the diameter of 1.6 cm, namely the anode of the double-electrolyte lithium ion battery, wherein the areal density is 3mg/cm–2。
And thirdly, the cathode (the anode material is a high-capacity high-voltage intercalation cathode) of the lithium ion battery in the embodiment of the invention is prepared by the following method: LiNi as cathode active material0.8Co0.1Mn0.1O2(purchased from china koala corporation), acetylene black and polyvinylidene fluoride in a mass ratio of 95: 2: 3 mixing evenly, taking N-methyl pyrrolidone (NMP) as a solvent, preparing slurry, evenly coating the cathode slurry on an aluminum foil, and preparing an anode with the diameter of 1.4 cm through vacuum drying, rolling and slicing, namely the cathode of the double electrolyte lithium ion battery, wherein the surface density is 7.7mg/cm–2。
(IV) the test method of the double-electrolyte lithium ion battery in the embodiment of the invention and the test method of the single-electrolyte lithium ion battery in the comparative example are as follows: the battery new power tester is adopted to perform constant current charging and discharging tests on the double-electrolyte lithium ion battery, the charging and discharging current density is at least one of 20mA/g, 100mA/g or 200mA/g, and the charging and discharging voltage interval is 3.0V-4.35V. The capacity retention rate of the 200 th cycle was calculated after 200 cycles of charge and discharge. The calculation formula is as follows: the 200 th cycle capacity retention (%) was (200 th cycle discharge capacity/1 st cycle discharge capacity) × 100%. Wherein the content of the first and second substances,
the assembling method of the double-electric-liquid lithium ion battery comprises the following steps: the bi-electrolyte lithium ion battery was assembled in an argon filled glove box (moisture < 1ppm, oxygen < 1ppm) using a homemade H-cell as shown in fig. 1. Firstly, a lithiated Nafion-based diaphragm is fixed in the middle of an H-shaped battery jar and then is protected by a diaphragm protection layer to prevent liquid leakage. Injecting positive electrolyte into the positive reaction chamber, injecting negative electrolyte into the negative reaction chamber, fixing the positive plate and the negative plate by the polytetrafluoroethylene conductive clip, immersing the positive plate and the negative plate into the corresponding electrolytes, and sealing the cover to prevent moisture and air from entering.
The anode and the cathode of the lithium ion battery prepared in the way and the electrolyte in the comparative example are assembled by adopting a traditional 2032 button cell.
(V) fluoroethyl methyl carbonate (FEMC), fluoroethylene carbonate (FEC), beta-fluorinated sulfone (TFPMS) in the examples of the present invention were purchased from Dooduo chemical technology, Inc., Suzhou, China.
Example 1 Dual electrolyte lithium ion Battery
In an argon-filled glove box (moisture < 1ppm, oxygen < 1ppm), fluoroethyl carbonate (FEMC), fluoroethylene carbonate (FEC), and Hydrofluoroether (HFE) were uniformly mixed at a mass ratio of 2:2:6, and then 14.0 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the positive electrode electrolyte was slowly added to the mixed solution6) Stirring until the nickel ions are completely dissolved to obtain the high-nickel-content ternary NCM811 positive electrolyte. Uniformly mixing ethylene glycol dimethyl ether (DME), fluoroethylene carbonate (FEC) and Hydrofluoroether (HFE) in a mass ratio of 2:2:6, and then slowly adding 14.0 wt% of lithium bis (fluorosulfonyl) imide (LiFSI) based on the total weight of the cathode electrolyte into the mixed solution, and stirring until the lithium bis (fluorosulfonyl) imide (LiFSI) is completely dissolved to obtain the cathode electrolyte adaptive to the silicon-carbon cathode material. And (3) assembling the double-electrolyte lithium ion battery by using a lithiated Nafion-based diaphragm according to the method.
EXAMPLE 2 Dual electrolyte lithium ion Battery
Under chargingIn an argon-filled glove box (moisture < 1ppm, oxygen < 1ppm), 28.0 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the positive electrode electrolyte was added6) Adding the solution into a beta-fluorinated sulfone (TFPMS) solvent, and stirring until the solution is completely dissolved to obtain the adaptive high-nickel ternary NCM811 positive electrolyte. Tetrahydrofuran (THF) and dimethyltetrahydrofuran (MTHF) were uniformly mixed in a mass ratio of 1:1, and then 28.0 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the negative electrode electrolyte was slowly added to the mixed solvent6) Stirring until the solution is completely dissolved to obtain the anode electrolyte adaptive to the silicon-carbon anode material. And (3) assembling the double-electrolyte lithium ion battery by using a lithiated Nafion-based diaphragm according to the method.
EXAMPLE 3 Dual electrolyte lithium ion Battery
In an argon-filled glove box (moisture < 1ppm, oxygen < 1ppm), 14.0 wt% of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) based on the total weight of the positive electrode electrolyte was dissolved in 1-methyl-1-propylpyrrolidine bis (trifluoromethylsulfonyl) imide salt (Pyr13TFSI) and stirred until it was completely dissolved, to obtain a compatible high-nickel ternary NCM811 positive electrode electrolyte. Uniformly mixing ethylene glycol dimethyl ether (DME) and Hydrofluoroether (HFE) in a mass ratio of 1:3, slowly adding 14.0 wt% of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) based on the total weight of the cathode electrolyte into the mixed solvent, and stirring until the lithium bis (trifluoromethylsulfonyl) imide is completely dissolved to obtain the cathode electrolyte matched with the silicon-carbon cathode material. And (3) assembling the double-electrolyte lithium ion battery by using a lithiated Nafion-based diaphragm according to the method.
Comparative example 1 Single electrolyte lithium ion Battery
Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) were uniformly mixed in a 3:2:5 mass ratio in an argon-filled glove box (moisture < 1ppm, oxygen < 1ppm), and then 14.0 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) Vinylene Carbonate (VC) in an amount of 1.5% based on the total mass of the electrolyte and fluoroethylene carbonate (FEC) in an amount of 10% based on the total mass of the electrolyte, and then stirred until they are completely dissolved, to obtain a commercial lithium ion battery electrolyte. And then the lithium ion battery with single electrolyte is assembled by the method.
Comparative example 2 Single electrolyte lithium ion Battery
In an argon-filled glove box (moisture < 1ppm, oxygen < 1ppm), fluoroethyl carbonate (FEMC), fluoroethylene carbonate (FEC), and Hydrofluoroether (HFE) were uniformly mixed at a mass ratio of 2:2:6, and then to the mixed solvent was slowly added lithium hexafluorophosphate (LiPF) in an amount of 14.0 wt% based on the total weight of the electrolyte6) Stirring until the nickel ions are completely dissolved to obtain the high-nickel-content ternary NCM811 positive electrolyte. And then the lithium ion battery with single electrolyte is assembled by the method.
Comparative example 3 Single electrolyte lithium ion Battery
Uniformly mixing ethylene glycol dimethyl ether (DME), fluoroethylene carbonate (FEC) and Hydrofluoroether (HFE) in a glove box (with the water content less than 1ppm and the oxygen content less than 1ppm) filled with argon according to the mass ratio of 2:2:6, slowly adding LiFSI (lithium iron phosphate) accounting for 14.0 wt% of the total weight of the electrolyte into the mixed solvent, and stirring until the LiFSI is completely dissolved to obtain the anode electrolyte adaptive to the silicon-carbon anode material. And then the lithium ion battery with single electrolyte is assembled by the method.
Comparative example 4 Single electrolyte lithium ion Battery
In an argon-filled glove box (moisture < 1ppm, oxygen < 1ppm), 28.0 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was charged6) Adding the solution into a beta-fluorinated sulfone (TFPMS) solvent, and stirring until the solution is completely dissolved to obtain the adaptive high-nickel ternary NCM811 positive electrolyte. And then the lithium ion battery with single electrolyte is assembled by the method.
Comparative example 5 Single electrolyte lithium ion Battery
Tetrahydrofuran (THF) and dimethyltetrahydrofuran (MTHF) were mixed uniformly in a mass ratio of 1:1 in an argon-filled glove box (moisture < 1ppm, oxygen < 1ppm), and then 28.0 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solvent6) Stirring until the solution is completely dissolved to obtain the negative electrode electrolyte adaptive to the silicon-carbon negative electrode material. And then the lithium ion battery with single electrolyte is assembled by the method.
Comparative example 6 Single electrolyte lithium ion Battery
28.0% by weight, based on the total weight of the electrolyte, of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) was dissolved in 1-methyl-1-propylpyrrolidine bis (trifluoromethylsulfonyl) imide salt (Pyr) in an argon-filled glove box (moisture < 1ppm, oxygen < 1ppm)13TFSI) and stirring until the solution is completely dissolved to obtain the lithium ion battery electrolyte matched with the high-nickel ternary NCM811 cathode material. And then the lithium ion battery with single electrolyte is assembled by the method.
Comparative example 7 Single electrolyte lithium ion Battery
Uniformly mixing ethylene glycol dimethyl ether (DME) and Hydrofluoroether (HFE) in a glove box (moisture is less than 1ppm and oxygen content is less than 1ppm) filled with argon gas in a mass ratio of 1:3, slowly adding 14.0 wt% of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) based on the total weight of the electrolyte into the mixed solvent, and stirring until the lithium bis (trifluoromethylsulfonyl) imide is completely dissolved to obtain the lithium ion battery electrolyte matched with the silicon-carbon negative electrode material. And then the lithium ion battery with single electrolyte is assembled by the method.
Effects of the embodiment
The results of cycle tests at 25 ℃ at room temperature in examples 1 to 3 and comparative examples 1 to 7 are shown in FIG. 2 (charge/discharge current density of 100 mA/g).
It can be seen from the above examples 1 to 3 and comparative examples 1 to 7 that a dual electrolyte system is constructed in the lithium ion battery, and the high-voltage resistant electrolyte and the low-voltage resistant electrolyte are respectively placed on the positive electrode side and the negative electrode side, which significantly improves the performance cycle of the battery. The high-energy-density long-cycle lithium ion battery can be realized based on the double-electrolyte battery technology. Compared with a single electrolyte, the thermodynamic window designed by the double-electrolyte lithium ion battery with the electrode compatible with the electrolyte can simultaneously meet the requirements of a high-voltage positive electrode and a low-voltage negative electrode. The lithium ion battery has the advantages that due to the fact that the appropriate electrolyte reaction environments are placed on the positive electrode side and the negative electrode side, the functional defects of the traditional single electrolyte are overcome by combining the advantages of the positive electrolyte and the negative electrolyte, and meanwhile the cycle life of the lithium ion battery based on the high-voltage nickel-rich ternary positive electrode material and the silicon-based negative electrode system is prolonged.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A high energy density dual electrolyte lithium ion battery, characterized in that: comprises a positive pole, a positive pole reaction chamber, a diaphragm, a negative pole and a negative pole reaction chamber;
a positive electrolyte channel is arranged above the positive reaction chamber, and a negative electrolyte channel is arranged above the negative reaction chamber;
the anode is contacted with the anode electrolyte, and the cathode is contacted with the cathode electrolyte;
the positive electrolyte and the negative electrolyte are separated by a diaphragm;
the positive electrolyte is one of perfluoro-based electrolyte, sulfone-based electrolyte and ionic liquid electrolyte;
the negative electrode electrolyte is one of an ether-based electrolyte, a fluorine ether-based electrolyte and a local high-concentration ether-based electrolyte.
2. The high energy density dual electrolyte lithium ion battery of claim 1, wherein:
the lithium salt in the perfluoro-based electrolyte is one or more of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethylsulfonyl) imide; the organic solvent is one or more of fluoroethyl carbonate, fluoroethylene carbonate and hydrofluoroether;
the lithium salt in the sulfone electrolyte is one or more of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethylsulfonyl) imide; the organic solvent is beta-fluorinated sulfone;
the lithium salt in the ionic liquid electrolyte is one or more of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethylsulfonyl) imide; the organic solvent is 1-methyl-1-propyl pyrrolidine bis (trifluoromethanesulfonyl) imide salt;
the lithium salt in the ether electrolyte is one or more of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethylsulfonyl) imide; the organic solvent is one or more of ethylene glycol dimethyl ether, fluoroethylene carbonate and hydrofluoroether;
the lithium salt in the fluoroether-based electrolyte is one or more of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethylsulfonyl) imide; the organic solvent is one or two of tetrahydrofuran and dimethyl tetrahydrofuran;
the lithium salt in the local high-concentration ether electrolyte is one or more of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethylsulfonyl) imide; the organic solvent is one or two of ethylene glycol dimethyl ether and hydrofluoroether.
3. The high energy density dual electrolyte lithium ion battery of claim 2, wherein:
the lithium salt in the perfluoro-based electrolyte is lithium bis (fluorosulfonyl) imide; the organic solvent is obtained by mixing fluoroethyl carbonate, fluoroethylene carbonate and hydrofluoroether according to the mass ratio of 2:2: 6;
the lithium salt in the sulfone-based electrolyte is lithium hexafluorophosphate; the organic solvent is beta-fluorinated sulfone;
the lithium salt in the ionic liquid electrolyte is bis (trifluoromethylsulfonyl) imide lithium; the organic solvent is 1-methyl-1-propyl pyrrolidine bis (trifluoromethanesulfonyl) imide salt;
the lithium salt in the ether electrolyte is lithium bis (fluorosulfonyl) imide; the organic solvent is obtained by mixing ethylene glycol dimethyl ether, fluoroethylene carbonate and hydrofluoroether according to the mass ratio of 2:2: 6;
the lithium salt in the fluoroether-based electrolyte is lithium hexafluorophosphate; the organic solvent is obtained by mixing tetrahydrofuran and dimethyl tetrahydrofuran according to the volume ratio of 1: 1;
the lithium salt in the local high-concentration ether-based electrolyte is lithium bis (trifluoromethylsulfonyl) imide; the organic solvent is obtained by mixing ethylene glycol dimethyl ether and hydrofluoroether according to the volume ratio of 1: 3.
4. The high energy density dual electrolyte lithium ion battery of claim 3, wherein:
the concentration of the positive electrolyte is 14-28% by mass percent;
the concentration of the negative electrode electrolyte is 14-28% by mass.
5. The high energy density dual electrolyte lithium ion battery of claim 1, wherein:
the concentration of the perfluoro-based electrolyte is 14 percent by mass;
the concentration of the sulfone-based electrolyte is 28 percent by mass;
the concentration of the ionic liquid electrolyte is 14% by mass;
the concentration of the ether electrolyte is 14% by mass;
the concentration of the fluorine ether-based electrolyte is 28% by mass;
the concentration of the local high-concentration ether-based electrolyte is 14% by mass.
6. The high energy density dual electrolyte lithium ion battery of claim 1, wherein:
the anode is a high-capacity high-voltage intercalation cathode and is prepared by the following method: LiNi as cathode active material0.8Co0.1Mn0.1O2Acetylene black and polyvinylidene fluoride according to a mass ratio of 95: 2: 3, uniformly mixing, adding N-methyl pyrrolidone serving as a solvent to prepare slurry, uniformly coating the slurry on an aluminum foil, and performing vacuum drying, rolling and slicing to obtain a high-capacity high-voltage intercalation cathode serving as the anode of the dual-electrolyte lithium ion battery.
7. The high energy density dual electrolyte lithium ion battery of claim 1, wherein:
the negative electrode is a high-capacity low-voltage silicon-based anode and is prepared by the following method: mixing a negative electrode active material Si/C-650, acetylene black, a binder styrene butadiene rubber and carboxymethyl cellulose according to a mass ratio of 95: 1: 2:2, adding deionized water serving as a solvent to prepare slurry, uniformly coating the slurry on an aluminum foil, and performing vacuum drying, rolling and slicing to obtain a high-capacity low-voltage anode serving as a cathode of the dual-electrolyte lithium ion battery.
8. The high energy density dual electrolyte lithium ion battery of claim 1, wherein:
two ends of the diaphragm, which are in contact with the positive electrolyte and the negative electrolyte, are provided with diaphragm protective layers;
the diaphragm is a perfluorinated sulfonic acid proton exchange membrane and is prepared by the following method:
putting the perfluorinated sulfonic acid proton exchange membrane into deionized water, boiling for 3-5 hours for pretreatment, then transferring the perfluorinated sulfonic acid proton exchange membrane into a hydrogen peroxide water solution with the concentration of 5% by volume, treating for 3-5 hours at 60 ℃, then putting the perfluorinated sulfonic acid proton exchange membrane into a dilute sulfuric acid solution, boiling for 2 hours, and cleaning with boiling deionized water; boiling the cleaned perfluorinated sulfonic acid proton exchange membrane in LiOH solution for 2 hours, cleaning, drying and punching to form a diaphragm to obtain a lithiated perfluorinated sulfonic acid proton exchange membrane;
the concentration of the dilute sulfuric acid solution is 5 mol/L;
the concentration of the LiOH solution is 1 mol/L;
the LiOH solution is prepared by the following method: adding LiOH into a mixture of ethanol and deionized water in a volume ratio of 1: 2 mixing the obtained solution to prepare a LiOH solution;
the drying conditions are as follows: vacuum drying at 80 deg.C for more than 5 days.
9. The method for preparing a high energy density dual electrolyte lithium ion battery as claimed in any of claims 1 to 8, comprising the steps of: preparing the positive electrolyte and the negative electrolyte, and then assembling according to the assembling sequence of the lithium ion battery to obtain the dual-electrolyte lithium ion battery.
10. The use of the high energy density dual electrolyte lithium ion battery of any of claims 1-8 in the field of lithium ion batteries.
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