CN114188599B - Double-electrolyte lithium ion battery with high energy density and preparation method and application thereof - Google Patents
Double-electrolyte lithium ion battery with high energy density and preparation method and application thereof Download PDFInfo
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- CN114188599B CN114188599B CN202111541289.4A CN202111541289A CN114188599B CN 114188599 B CN114188599 B CN 114188599B CN 202111541289 A CN202111541289 A CN 202111541289A CN 114188599 B CN114188599 B CN 114188599B
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 237
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000003411 electrode reaction Methods 0.000 claims abstract description 33
- -1 perfluoro Chemical group 0.000 claims abstract description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002608 ionic liquid Substances 0.000 claims abstract description 11
- 150000003457 sulfones Chemical class 0.000 claims abstract description 10
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims description 43
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 24
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical group [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 23
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 22
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims description 16
- 159000000002 lithium salts Chemical class 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 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
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 10
- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000009835 boiling Methods 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 230000009977 dual effect Effects 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 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
- 238000001035 drying Methods 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 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
- 238000004140 cleaning Methods 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims description 2
- 239000011149 active material Substances 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 229920000557 Nafion® Polymers 0.000 description 18
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 14
- 229910013870 LiPF 6 Inorganic materials 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052759 nickel Inorganic materials 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
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 230000003044 adaptive effect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 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 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910015965 LiNi0.8Mn0.1Co0.1O2 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
- 239000010406 cathode material Substances 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
- 239000011889 copper foil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 239000011241 protective layer Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a double-electrolyte lithium ion battery with high energy density and a preparation method and application thereof. The double-electrolyte lithium ion battery comprises a positive electrode, a positive electrode reaction chamber, a diaphragm, a negative electrode and a negative electrode reaction chamber; a positive electrode electrolyte channel is arranged above the positive electrode reaction chamber, and a negative electrode electrolyte channel is arranged above the negative electrode reaction chamber; the positive electrode is contacted with positive electrode electrolyte, and the negative electrode is contacted with negative electrode electrolyte; the positive electrode electrolyte and the negative electrode electrolyte are separated by a diaphragm; the positive electrode electrolyte is one of perfluoro-based electrolyte, sulfone-based electrolyte and ionic liquid electrolyte; the negative electrode electrolyte is one of ether-based electrolyte, fluoroether-based electrolyte and local high-concentration ether-based electrolyte. The invention combines the advantages of the positive electrode electrolyte and the negative electrode electrolyte, makes up the functional defect of the traditional single electrolyte, and improves the cycle life of the lithium ion battery at the same time, so that the cycle performance of the lithium ion battery is obviously improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a double-electrolyte lithium ion battery with high energy density, and a preparation method and application thereof.
Background
In order to meet the sharply increasing demands of electric traffic and large energy grid systems, it is necessary to develop batteries having high energy density and long cycle life. The reliable performance of high energy density long cycle lithium ion batteries will ultimately be achieved by structurally optimized electrode materials and custom-made electrolyte systems. Silicon-based composites are considered to be one of the most viable anode candidates for lithium ion batteries due to their high capacity and durability. However, during the sustained cycle, the extreme volume fluctuations thereof can lead to Si-fatal mechanical cracking, causing repeated damage to the surface. The formation of a stable Solid Electrolyte Interphase (SEI) can withstand the volumetric strain of silicon, which is critical to extend the cycle life of lithium ion batteries without further electrolyte decomposition. Although fluoroethylene carbonate (FEC) is used as a standard additive for anodic protection, its role in the reversibility of silicon-containing anodes remains controversial. In this regard, the discovery of new electrolytes that can remedy the shortcomings of conventional electrolytes, such as reduced battery cycle life, would facilitate the development of robust silicon-based anode materials.
Achieving high energy density lithium ion batteries must simultaneously achieve reliable cathode technology. Although the reversible capacity of the high voltage/high capacity intercalation nickel-rich cathode NCM (LiNi 0.8Mn0.1Co0.1O2, NCM 811) exceeds 200mAh/g, its practical use is hampered by problems of irreversible phase change and particle cracking during charging. Furthermore, at high pressures above 4.3V, excessive decomposition of Li/Li + by conventional carbonate electrolytes results in thickening of the catholyte interfacial phase (CEI). In contrast, the use of an electrolyte 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 continuously occurring adverse phase transition by reconstructing the cathode surface. However, despite extensive research into such high-voltage electrolytes, none of the high-voltage electrolytes has achieved both the desired high potential and low potential stability. Therefore, full cell lithium ion batteries based on high voltage electrolytes typically use electrodes with moderate potentials, thereby limiting the operating voltage and energy density. Although hybrid ionic liquids have been proposed to have synergistic effects, 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 necessary to explore an electrolyte design method that is simple to use to achieve 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, no electrolyte thermodynamic window can simultaneously meet 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 is limited. The use of conventional commercial electrolytes can result in excessively low energy densities and poor cycle life for the NCM811-Si/C based full cell.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provides a double-electrolyte lithium ion battery with high energy density.
The invention further aims at providing a preparation method of the high-energy-density double-electrolyte lithium ion battery.
It is a further object of the present invention to provide the use of the high energy density dual electrolyte lithium ion battery.
The aim of the invention is achieved by the following technical scheme:
a double-electrolyte lithium ion battery with high energy density comprises a positive electrode, a positive electrode reaction chamber, a diaphragm, a negative electrode and a negative electrode reaction chamber;
a positive electrode electrolyte channel is arranged above the positive electrode reaction chamber, and a negative electrode electrolyte channel is arranged above the negative electrode reaction chamber;
the positive electrode is contacted with positive electrode electrolyte, and the negative electrode is contacted with negative electrode electrolyte;
The positive electrode electrolyte and the negative electrode electrolyte are separated by a diaphragm;
the positive electrode electrolyte is one of perfluoro-based electrolyte, sulfone-based electrolyte and ionic liquid electrolyte;
The negative electrode electrolyte is one of ether-based electrolyte, fluoroether-based electrolyte and local high-concentration ether-based electrolyte.
The positive electrode is a high-capacity high-voltage intercalation cathode (contacted with a catholyte); further preferred is a positive electrode made of a high-pressure high-capacity nickel-rich NCM positive electrode material; still further preferred is a positive electrode made of a nickel-rich ternary NCM811 material; still more preferably, it is prepared by the following method: cathode active materials LiNi 0.8Co0.1Mn0.1O2, acetylene black and polyvinylidene fluoride are mixed according to the 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 carrying out vacuum drying, rolling and slicing to obtain a high-capacity high-voltage intercalation cathode which is used as the positive electrode of the double-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 (contacted with an anode electrolyte); a negative electrode preferably made of a silicon carbon material; more preferably, the preparation is carried out by the following method: the negative electrode active material Si/C-650, acetylene black, binder Styrene Butadiene Rubber (SBR) and carboxymethyl cellulose (CMC) are mixed according to the mass ratio of 95:1:2:2, adding deionized water as a solvent to prepare slurry, uniformly coating the slurry on an aluminum foil, and carrying out vacuum drying, rolling and slicing to obtain a high-capacity low-voltage anode serving as a negative electrode of the double-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 electrode electrolyte consists of lithium salt and organic solvent; wherein the positive electrolyte is high-pressure-resistant electrolyte, and the negative electrolyte is low-pressure-resistant electrolyte.
The lithium salt is one or more of lithium hexafluorophosphate (LiPF 6), lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI);
The organic solvent is one or more of fluoroethylmethyl 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-propylpyrrolidinyl bis (trifluoromethanesulfonyl) imide salt (Pyr 13 TFSI).
The concentration of the positive electrode electrolyte is 14-28% by mass (namely, the lithium salt of the positive electrode electrolyte accounts for 14-28% by mass of the total mass of the positive electrode 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 one or more of lithium hexafluorophosphate (LiPF 6), lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (preferably lithium bis (fluorosulfonyl) imide); the organic solvent is one or more of fluoroethylmethyl carbonate (FEMC), fluoroethylene carbonate (FEC) and Hydrofluoroether (HFE) (preferably the organic solvent is obtained by mixing fluoroethylmethyl carbonate, fluoroethylene carbonate and hydrofluoroether according to a mass ratio of 2:2:6).
The concentration of the perfluoro-based electrolyte is preferably 14% by mass.
The lithium salt in the sulfonyl electrolyte is one or more of lithium hexafluorophosphate (LiPF 6), 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 sulfonyl electrolyte is preferably 28% by mass.
The lithium salt in the ionic liquid electrolyte is one or more of lithium hexafluorophosphate (LiPF 6), lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) (preferably lithium bis (trifluoromethylsulfonyl) imide); the organic solvent was 1-methyl-1-propylpyrrolidinbis (trifluoromethanesulfonyl) imide salt (Pyr 13 TFSI).
The concentration of the ionic liquid electrolyte is preferably 14% by mass.
The lithium salt in the ether electrolyte is one or more of lithium hexafluorophosphate (LiPF 6), 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 the organic solvent obtained by mixing ethylene glycol dimethyl ether, fluoroethylene carbonate and hydrofluoroether according to a mass ratio of 2:2:6).
The concentration of the ether electrolyte is preferably 14% by mass.
The lithium salt in the fluoroether electrolyte is one or more of lithium hexafluorophosphate (LiPF 6), 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 the organic solvent obtained by mixing tetrahydrofuran and dimethyl tetrahydrofuran according to the volume ratio of 1:1).
The concentration of the fluoroether electrolyte is preferably 28% by mass.
The lithium salt in the local high-concentration ether-based electrolyte is one or more of lithium hexafluorophosphate (LiPF 6), 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 the organic solvent obtained by mixing ethylene glycol dimethyl ether and hydrofluoroether according to a volume ratio of 1:3).
The concentration of the local high-concentration ether-based electrolyte is preferably 14% by mass.
And the two ends of the diaphragm, which are in contact with the positive electrode electrolyte and the negative electrode electrolyte, are provided with diaphragm protection layers.
The membrane is a perfluorosulfonic acid proton exchange membrane (Nafion-based membrane); 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:
Boiling the perfluorosulfonic acid proton exchange membrane in deionized water for 3-5 hours for pretreatment, then transferring the perfluorosulfonic acid proton exchange membrane into a hydrogen peroxide water solution with the concentration of 5% by volume, treating the perfluorosulfonic acid proton exchange membrane for 3-5 hours at 60 ℃, putting the perfluorosulfonic acid proton exchange membrane into a dilute sulfuric acid solution, boiling the perfluorosulfonic acid proton exchange membrane for 2 hours, and cleaning the perfluorosulfonic acid proton exchange membrane with the boiled deionized water; and then boiling the washed perfluorosulfonic acid proton exchange membrane in LiOH solution for 2 hours, washing, drying and punching to form a membrane, thus obtaining the lithiated perfluorosulfonic acid proton exchange membrane (lithiated Nafion-based membrane).
The concentration of the dilute sulfuric acid solution is preferably 5mol/L.
The concentration of the LiOH solution is preferably 1mol/L.
The LiOH solution is preferably prepared by the following method: liOH is added into ethanol and deionized water according to the volume ratio of 1:2, mixing the obtained solutions to prepare LiOH solution.
The drying conditions are preferably as follows: vacuum drying at 80deg.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: firstly preparing positive electrolyte and negative electrolyte, and then assembling according to the assembling sequence of the lithium ion battery to obtain the double-electrolyte lithium ion battery.
The double-electrolyte lithium ion battery with high energy density 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 thermodynamic window of the single electrolyte cannot simultaneously meet the requirements of a high-voltage positive electrode and a low-voltage negative electrode, and the invention overcomes the functional defects of the traditional single electrolyte by combining the advantages of the positive electrolyte and the negative electrolyte, and simultaneously improves the cycle life of the lithium ion battery based on a high-voltage ternary positive electrode material and a silicon-carbon negative electrode system, so that the cycle performance of the lithium ion battery is obviously improved.
(2) The double-electrolyte battery system of the high-energy-density lithium ion battery electrode compatible electrolyte comprises an anode electrolyte, an anode reaction chamber, an anode material and a diaphragm; the positive electrode electrolyte is high-voltage-resistant electrolyte, the negative electrode electrolyte is 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 the diaphragm is a lithiated perfluorosulfonic acid proton exchange membrane (Nafion-based diaphragm), the positive electrode reaction chamber and the negative electrode reaction chamber are separated by the lithiated perfluorosulfonic acid proton exchange membrane, and an independent electrolyte environment is built through measuring at the positive electrode and the negative electrode, so that the positive electrode corresponds to a good reaction environment, and the electrochemical window of the lithium ion battery is further widened.
Drawings
Fig. 1 is a diagram of a structure of a double-electrolyte lithium ion battery (in the diagram, 1 is a positive electrode, 2 is a negative electrode, 3 is a positive electrode reaction chamber, 4 is a positive electrode electrolyte, 5 is a negative electrode reaction chamber, 6 is a negative electrode electrolyte, 7 is a diaphragm, and 8 is a diaphragm protection layer).
FIG. 2 is a graph showing the results of the cyclic test at room temperature of 25℃for 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 embodiments of the present invention are not limited thereto. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The experimental methods of the specific experimental conditions are not noted in the following examples, and generally follow the conventional experimental conditions. The reagents and starting materials used in the present invention are commercially available unless otherwise specified.
The structure of the double-electrolyte lithium ion battery in the embodiment of the invention is shown in fig. 1, and the double-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 positive electrode reaction chamber 3 is provided with a positive electrode electrolyte channel, and the negative electrode reaction chamber 5 is provided with a negative electrode electrolyte channel; electrolyte channels are designed on the positive electrode reaction chamber 3 and the negative electrode reaction chamber 5, so that liquid can be injected from the outside, namely positive electrode electrolyte 4 enters the positive electrode reaction chamber 3 through the positive electrode electrolyte channel to participate in the reaction, and negative electrode electrolyte 6 enters the negative electrode reaction chamber 5 through the negative electrode electrolyte channel to participate in the reaction;
the positive electrode reaction chamber 3 is filled with positive electrode electrolyte 4, and the negative electrode reaction chamber 5 is filled with 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;
the two ends of the diaphragm 7, which are in contact with the positive electrode electrolyte 4 and the negative electrode 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:
Pretreatment is carried out on a commercial perfluorosulfonic acid proton exchange membrane, and the process is as follows: firstly, in order to convert the Nafion membrane into the form of-SO 3 H, boiling a perfluorinated sulfonic acid proton exchange membrane (Nafion membrane) in deionized water for 3-5 hours for pretreatment, and then transferring the membrane into another aqueous solution containing 5% (v/v) hydrogen peroxide (H 2O2) for 3-5 hours at 60 ℃; then boiling the Nafion film in dilute sulfuric acid (0.5M) solution for 2 hours, and cleaning with boiled deionized water; subsequent Li + exchange procedure the Nafion film was boiled in a 1M LiOH solution (1:2 by volume ethanol to deionized water) for 2 hours with vigorous stirring; rinsing the Nafion membrane and again washing in boiling deionized water to remove residual salts and ethanol; finally, after drying in vacuo at 80 ℃ for 5 days, the lithiated Nafion membrane was transferred into an argon filled glove box and punched into a membrane (19 mm diameter) to give a lithiated Nafion-based membrane. The separator used in the examples below was a lithiated Nafion-based separator.
In the experiment, after the parts are sealed and fixed by a clamping device, respectively injecting positive electrode electrolyte and negative electrode electrolyte into a lithium ion battery shell, wherein the positive electrode is contacted with the positive electrode electrolyte, and the negative electrode is contacted with the negative electrode electrolyte; the positive electrode reaction chamber and the negative electrode reaction chamber are separated by the diaphragm, so that the situation that the positive electrode electrolyte and the negative electrode electrolyte are mixed does not occur, and the concentration of the electrolyte in the positive electrode reaction chamber and the negative electrode reaction chamber at the two sides of the diaphragm can be freely adjusted respectively.
(II), the anode (the anode 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: the negative electrode active material Si/C-650 (China colored Guilin mineral institute), acetylene black, styrene Butadiene Rubber (SBR) as a binder and carboxymethyl cellulose (CMC) (purchased from China Koidz) were mixed in a mass ratio of 95:1:2:2, uniformly mixing the materials according to the mass ratio, taking deionized water as a solvent, preparing slurry, uniformly coating the anode slurry on a copper foil, and carrying out vacuum drying, rolling and slicing to prepare the anode with the diameter of 1.6 cm, namely the anode of the double-electrolyte lithium ion battery, wherein the surface density is 3mg/cm –2.
(III), the cathode (anode material is high-capacity high-voltage intercalation cathode) of the lithium ion battery is prepared by the following method: the cathode active material LiNi 0.8Co0.1Mn0.1O2 (purchased from China Corp.), acetylene black and polyvinylidene fluoride are mixed according to the mass ratio of 95:2:3, uniformly mixing, using N-methyl pyrrolidone (NMP) as a solvent, preparing slurry, uniformly coating the cathode slurry on an aluminum foil, and carrying out vacuum drying, rolling and slicing to prepare the anode with the diameter of 1.4 cm, namely the cathode of the double-electrolyte lithium ion battery, wherein the surface density is 7.7mg/cm –2.
Fourth, the test method of the double electrohydraulic 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: and (3) carrying out constant current charge and discharge test on the double-electrohydraulic lithium ion battery by adopting a battery Xinwei tester, wherein the charge and discharge current density is at least one of 20mA/g,100mA/g or 200mA/g, and the charge and discharge voltage interval is 3.0V-4.35V. After 200 cycles of charge and discharge, the retention rate of the 200 th cycle capacity was calculated. The calculation formula is as follows: 200 th cycle capacity retention (%) = (200 th cycle discharge capacity/1 st cycle discharge capacity) ×100%. Wherein,
The double-electrohydraulic lithium ion battery comprises the following steps: in an argon-filled glove box (moisture < 1ppm, oxygen < 1 ppm), a self-made H-type electrolyzer was used to assemble a double electrohydraulic lithium ion battery as shown in fig. 1. The lithiated Nafion-based diaphragm is first fixed in the middle of the H-type cell, and then protected by a diaphragm protective layer to prevent leakage. And injecting positive electrolyte into the positive reaction chamber, injecting negative electrolyte into the negative reaction chamber, finally, immersing the positive plate and the negative plate fixed by the polytetrafluoroethylene conductive clip into the electrolyte corresponding to each other, and sealing the cover to prevent water and air from entering.
The single electrolyte lithium ion battery is assembled by adopting the conventional 2032 button battery to the anode and the cathode of the lithium ion battery prepared by the method and the electrolyte in the comparative example.
Fifth, fluoroethyl methyl carbonate (FEMC), fluoroethylene carbonate (FEC), and β -fluorinated sulfone (TFPMS) were purchased from su-multi-chemical technology limited, china.
Example 1 double electrolyte lithium ion battery
In a glove box filled with argon (moisture < 1ppm, oxygen content < 1 ppm), fluoroethylcarbonate (FEMC), fluoroethylene carbonate (FEC), hydrofluoroether (HFE) were mixed uniformly in a mass ratio of 2:2:6, then 14.0wt% lithium hexafluorophosphate (LiPF 6) based on the total weight of the positive electrode electrolyte was slowly added to the mixed solution and stirred until it was completely dissolved, to obtain an adapted high nickel ternary NCM811 positive electrode electrolyte. Ethylene glycol dimethyl ether (DME), fluoroethylene carbonate (FEC) and Hydrofluoroether (HFE) are uniformly mixed in a mass ratio of 2:2:6, and then 14.0wt% of lithium bis (fluorosulfonyl) imide (LiFSI) based on the total weight of the negative electrode electrolyte is slowly added into the mixed solution and stirred until the lithium bis (fluorosulfonyl) imide (LiFSI) is completely dissolved, so that the negative electrode electrolyte of the adaptive silicon carbon positive electrode material is obtained. And assembling the lithium Nafion-based diaphragm by using the method to obtain the double-electrolyte lithium ion battery.
Example 2 double electrolyte lithium ion battery
In an argon-filled glove box (moisture < 1ppm, oxygen content < 1 ppm), 28.0wt% lithium hexafluorophosphate (LiPF 6) based on the total weight of the positive electrode electrolyte was added to the beta-fluorinated sulfone (TFPMS) solvent and stirred until it was completely dissolved, yielding an adapted high nickel ternary NCM811 positive electrode electrolyte. Tetrahydrofuran (THF) and dimethyl tetrahydrofuran (MTHF) are uniformly mixed in a mass ratio of 1:1, and then 28.0wt% of lithium hexafluorophosphate (LiPF 6) based on the total weight of the negative electrode electrolyte is slowly added into the mixed solvent and stirred until the lithium hexafluorophosphate and the lithium hexafluorophosphate are completely dissolved, so that the positive electrode electrolyte of the adaptive silicon carbon anode material is obtained. And assembling the lithium Nafion-based diaphragm by using the method to obtain the double-electrolyte lithium ion battery.
Example 3 double electrolyte lithium ion battery
In an argon-filled glove box (moisture < 1ppm, oxygen content < 1 ppm), 14.0wt% 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 (Pyr 13 TFSI), and stirred until it was completely dissolved, to obtain an adapted 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 14.0wt% of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) based on the total weight of the negative electrode electrolyte into the mixed solvent, and stirring until the lithium bis (trifluoromethylsulfonyl) imide and the LiTFSI are completely dissolved to obtain the negative electrode electrolyte of the adaptive silicon-carbon negative electrode material. And assembling the lithium Nafion-based diaphragm by using the method to obtain the double-electrolyte lithium ion battery.
Comparative example 1 Single electrolyte lithium ion Battery
In a glove box filled with argon gas (moisture < 1ppm, oxygen content < 1 ppm), ethylene Carbonate (EC), diethyl carbonate (DEC) and ethylmethyl carbonate (EMC) were uniformly mixed at a mass ratio of 3:2:5, and then lithium hexafluorophosphate (LiPF 6) of 14.0wt% based on the total weight of the electrolyte, vinylene Carbonate (VC) of 1.5% based on the total mass of the electrolyte and fluoroethylene carbonate (FEC) of 10% based on the total mass of the electrolyte were slowly added to the mixed solution, followed by stirring until they were 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 a glove box filled with argon (moisture < 1ppm, oxygen content < 1 ppm), fluoroethylcarbonate (FEMC), fluoroethylene carbonate (FEC), and Hydrofluoroether (HFE) were mixed uniformly in a mass ratio of 2:2:6, and then lithium hexafluorophosphate (LiPF 6) was slowly added to the mixed solvent in an amount of 14.0wt% based on the total weight of the electrolyte, and stirred until it was completely dissolved, to obtain an adapted high nickel ternary NCM811 positive electrode electrolyte. And then the lithium ion battery with single electrolyte is assembled by the method.
Comparative example 3 Single electrolyte lithium ion Battery
In a glove box filled with argon (moisture is less than 1ppm, oxygen is less than 1 ppm), ethylene glycol dimethyl ether (DME), fluoroethylene carbonate (FEC) and Hydrofluoroether (HFE) are uniformly mixed in a mass ratio of 2:2:6, and then LiFSI accounting for 14.0wt% of the total weight of the electrolyte is slowly added into the mixed solvent and stirred until the LiFSI is completely dissolved, so that the positive electrode electrolyte of the adaptive silicon carbon positive electrode material is obtained. 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 content < 1 ppm), 28.0wt% lithium hexafluorophosphate (LiPF 6) based on the total weight of the electrolyte was added to the beta-fluorinated sulfone (TFPMS) solvent and stirred until it was completely dissolved to give an adapted 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
In a glove box filled with argon (moisture < 1ppm, oxygen content < 1 ppm), tetrahydrofuran (THF) and dimethyltetrahydrofuran (MTHF) were mixed uniformly in a mass ratio of 1:1, and then 28.0wt% lithium hexafluorophosphate (LiPF 6) based on the total weight of the electrolyte was slowly added to the mixed solvent and stirred until it was completely dissolved, to obtain a negative electrode electrolyte adapted to a 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
In a glove box filled with argon (moisture < 1ppm, oxygen content < 1 ppm), 28.0wt% of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) based on the total weight of the electrolyte was dissolved in 1-methyl-1-propylpyrrolidine bis (trifluoromethylsulfonyl) imide salt (Pyr 13 TFSI), and stirred until it was completely dissolved, to obtain a lithium ion battery electrolyte adapted to a 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
In a glove box filled with argon (moisture < 1ppm, oxygen content < 1 ppm), ethylene glycol dimethyl ether (DME) and Hydrofluoroether (HFE) are uniformly mixed in a mass ratio of 1:3, and then lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) accounting for 14.0wt% of the total weight of the electrolyte is slowly added into the mixed solvent, and stirred until the lithium bis (trifluoromethylsulfonyl) imide is completely dissolved, so that the lithium ion battery electrolyte which is suitable for a silicon-carbon negative electrode material is obtained. And then the lithium ion battery with single electrolyte is assembled by the method.
Effect examples
The results of the cyclic test at room temperature of 25℃for examples 1 to 3 and comparative examples 1 to 7 are shown in FIG. 2 (charge-discharge current density 100 mA/g).
As can be seen from the above examples 1 to 3 and comparative examples 1 to 7, a dual electrolyte system was constructed in a lithium ion battery, and a high pressure-resistant electrolyte was placed on the positive electrode side and a low pressure-resistant electrolyte was placed on the negative electrode side, respectively, which significantly improved the performance cycle performance of the battery. The high-energy density long-cycle lithium ion battery can be realized based on the double-electrolyte battery technology. Compared with single electrolyte, the thermodynamic window of the double-electrolyte lithium ion battery design with the electrodes 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 is characterized in that a proper electrolyte reaction environment is arranged on the positive electrode side and the negative electrode side, the functional defect of the traditional single electrolyte is overcome by combining the advantages of the positive electrode electrolyte and the negative electrode electrolyte, and 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 improved.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. A double-electrolyte lithium ion battery with high energy density is characterized in that: the device comprises a positive electrode, a positive electrode reaction chamber, a diaphragm, a negative electrode and a negative electrode reaction chamber;
a positive electrode electrolyte channel is arranged above the positive electrode reaction chamber, and a negative electrode electrolyte channel is arranged above the negative electrode reaction chamber;
the positive electrode is contacted with positive electrode electrolyte, and the negative electrode is contacted with negative electrode electrolyte;
The positive electrode electrolyte and the negative electrode electrolyte are separated by a diaphragm;
the positive electrode electrolyte is one of perfluoro-based electrolyte, sulfone-based electrolyte and ionic liquid electrolyte;
the lithium salt in the perfluoro-based electrolyte is lithium hexafluorophosphate, and the organic solvent is obtained by mixing fluoroethyl methyl carbonate, fluoroethylene carbonate and hydrofluoroether according to a mass ratio of 2:2:6;
the lithium salt in the sulfonyl electrolyte is lithium hexafluorophosphate, and the organic solvent is beta-fluorinated sulfone;
The lithium salt in the ionic liquid electrolyte is lithium bis (trifluoromethylsulfonyl) imide, and the organic solvent is 1-methyl-1-propylpyrrolidine bis (trifluoromethylsulfonyl) imide salt;
The negative electrode electrolyte is one of ether-based electrolyte, fluoroether-based electrolyte and local high-concentration ether-based electrolyte;
the lithium salt in the ether electrolyte is lithium bis (fluorosulfonyl) imide, and the organic solvent is obtained by mixing ethylene glycol dimethyl ether, fluoroethylene carbonate and hydrofluoroether according to a mass ratio of 2:2:6;
The lithium salt in the fluoroether electrolyte is lithium hexafluorophosphate, and the organic solvent is obtained by mixing tetrahydrofuran and dimethyl tetrahydrofuran according to a volume ratio of 1:1;
The lithium salt in the local high-concentration ether-based electrolyte is lithium bis (trifluoromethylsulfonyl) imide, and the organic solvent is an organic solvent obtained by mixing ethylene glycol dimethyl ether and hydrofluoroether according to a volume ratio of 1:3;
the concentration of the positive electrode electrolyte is 14-28% by mass;
the concentration of the negative electrode electrolyte is 14-28% by mass;
The positive electrode is a high-capacity high-voltage intercalation cathode, and the active material of the positive electrode is LiNi 0.8Co0.1Mn0.1O2;
the negative electrode is a high-capacity low-voltage silicon-based anode, and the active material is Si/C-650;
the membrane is a lithiated perfluorinated sulfonic acid proton exchange membrane.
2. The high energy density dual electrolyte lithium ion battery of claim 1 wherein:
the concentration of the perfluoro-based electrolyte is 14% by mass;
the concentration of the sulfonyl electrolyte is 28 mass percent;
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 fluoroether electrolyte is 28% by mass;
the concentration of the local high-concentration ether-based electrolyte is 14% by mass.
3. The high energy density dual electrolyte lithium ion battery of claim 1 wherein:
The positive electrode is prepared by the following method: cathode active materials LiNi 0.8Co0.1Mn0.1O2, acetylene black and polyvinylidene fluoride are mixed according to the mass ratio of 95:2:3, uniformly mixing, adding N-methyl pyrrolidone as a solvent to prepare slurry, uniformly coating the slurry on an aluminum foil, and carrying out vacuum drying, rolling and slicing to obtain a high-capacity high-voltage intercalation cathode which is used as the positive electrode of the double-electrolyte lithium ion battery.
4. The high energy density dual electrolyte lithium ion battery of claim 1 wherein:
The negative electrode is prepared by the following steps: the negative electrode active material Si/C-650, acetylene black, binder styrene-butadiene rubber and carboxymethyl cellulose are mixed according to the mass ratio of 95:1:2:2, adding deionized water as a solvent to prepare slurry, uniformly coating the slurry on an aluminum foil, and carrying out vacuum drying, rolling and slicing to obtain a high-capacity low-voltage anode serving as a negative electrode of the double-electrolyte lithium ion battery.
5. The high energy density dual electrolyte lithium ion battery of claim 1 wherein:
the two ends of the diaphragm, which are in contact with the positive electrode electrolyte and the negative electrode electrolyte, are provided with diaphragm protection layers;
The membrane is a perfluorosulfonic acid proton exchange membrane and is prepared by the following method:
Boiling the perfluorosulfonic acid proton exchange membrane in deionized water for 3-5 hours for pretreatment, then transferring the perfluorosulfonic acid proton exchange membrane into a hydrogen peroxide water solution with the concentration of 5% by volume, treating the perfluorosulfonic acid proton exchange membrane for 3-5 hours at 60 ℃, putting the perfluorosulfonic acid proton exchange membrane into a dilute sulfuric acid solution, boiling the perfluorosulfonic acid proton exchange membrane for 2 hours, and cleaning the perfluorosulfonic acid proton exchange membrane with the boiled deionized water; boiling the washed perfluorinated sulfonic acid proton exchange membrane in LiOH solution for 2 hours, washing, drying and punching into a diaphragm to obtain the lithiated perfluorinated sulfonic acid proton exchange membrane;
The concentration of the dilute sulfuric acid solution is 5mol/L;
The concentration of the LiOH solution is 1mol/L;
The LiOH solution is prepared by the following method: liOH is added into ethanol and deionized water according to the volume ratio of 1:2, preparing LiOH solution in the mixed solution;
The drying conditions are as follows: vacuum drying at 80deg.C for more than 5 days.
6. The method for preparing the high-energy-density double-electrolyte lithium ion battery according to any one of claims 1 to 5, comprising the following steps: firstly preparing positive electrolyte and negative electrolyte, and then assembling according to the assembling sequence of the lithium ion battery to obtain the double-electrolyte lithium ion battery.
7. Use of the high energy density dual electrolyte lithium ion battery of any of claims 1 to 5 in the field of lithium ion batteries.
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