CN114512667B - Electrode binder, preparation method thereof, negative electrode, lithium battery and vehicle - Google Patents
Electrode binder, preparation method thereof, negative electrode, lithium battery and vehicle Download PDFInfo
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- CN114512667B CN114512667B CN202011281396.3A CN202011281396A CN114512667B CN 114512667 B CN114512667 B CN 114512667B CN 202011281396 A CN202011281396 A CN 202011281396A CN 114512667 B CN114512667 B CN 114512667B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 43
- 239000011883 electrode binding agent Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000002608 ionic liquid Substances 0.000 claims abstract description 57
- 229920000642 polymer Polymers 0.000 claims abstract description 56
- -1 hexafluorophosphate Chemical compound 0.000 claims abstract description 27
- 239000002210 silicon-based material Substances 0.000 claims abstract description 19
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- VHSLGFZDYCMVHY-UHFFFAOYSA-N boric acid;oxalyl difluoride Chemical compound OB(O)O.FC(=O)C(F)=O VHSLGFZDYCMVHY-UHFFFAOYSA-N 0.000 claims abstract description 4
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims abstract description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 150000001450 anions Chemical class 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- 150000004985 diamines Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 10
- 125000004427 diamine group Chemical group 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- GMKMEZVLHJARHF-UHFFFAOYSA-N 2,6-diaminopimelic acid Chemical compound OC(=O)C(N)CCCC(N)C(O)=O GMKMEZVLHJARHF-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- LOPLXECQBMXEBQ-UHFFFAOYSA-N 2,4-diaminopentanedioic acid Chemical compound OC(=O)C(N)CC(N)C(O)=O LOPLXECQBMXEBQ-UHFFFAOYSA-N 0.000 claims description 3
- KLNKMGPJWOMQTJ-UHFFFAOYSA-N 2,5-diaminohexanedioic acid Chemical compound OC(=O)C(N)CCC(N)C(O)=O KLNKMGPJWOMQTJ-UHFFFAOYSA-N 0.000 claims description 3
- AHLPHDHHMVZTML-BYPYZUCNSA-N L-Ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 claims description 3
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- AHLPHDHHMVZTML-UHFFFAOYSA-N Orn-delta-NH2 Natural products NCCCC(N)C(O)=O AHLPHDHHMVZTML-UHFFFAOYSA-N 0.000 claims description 3
- UTJLXEIPEHZYQJ-UHFFFAOYSA-N Ornithine Natural products OC(=O)C(C)CCCN UTJLXEIPEHZYQJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 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 3
- 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 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229960003104 ornithine Drugs 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 33
- 229910052710 silicon Inorganic materials 0.000 abstract description 32
- 239000010703 silicon Substances 0.000 abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 230000008859 change Effects 0.000 abstract description 10
- 230000001351 cycling effect Effects 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 230000009286 beneficial effect Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 229920002125 Sokalan® Polymers 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000011856 silicon-based particle Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000005543 nano-size silicon particle Substances 0.000 description 5
- 239000004584 polyacrylic acid Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
Abstract
The application discloses an electrode binder and a preparation method thereof, a negative electrode, a lithium battery and a vehicle, wherein the electrode binder comprises the following components: the ionic liquid polymer comprises the ionic liquid polymer, and the structural formula of the ionic liquid polymer is as follows:wherein R is 1 And R is 2 Each independently is any one of bis (trifluoromethylsulfonyl) imide, bis (fluorosulfonyl) imide, perchlorate, hexafluorophosphate, hexafluoroarsenate, tetrafluoroborate, dioxaborate, difluorooxalate borate, or trifluoromethylsulfonate; m and a are each independently any integer between 1 and 20; b is any integer between 1 and 100; n and c are any integer between 1 and 100; x+y is equal to 1.0 and p+q is equal to 1.0. The adhesive has good cohesiveness, flexibility and ion conductivity, is favorable for preventing the silicon material from falling off, is suitable for the volume change of silicon and the diffusion and transmission of lithium ions in an electrode material, and improves the specific capacity and the cycling stability of a lithium battery.
Description
Technical Field
The application relates to the technical field of lithium batteries, in particular to an electrode binder, a preparation method thereof, a negative electrode, a lithium battery and a vehicle.
Background
The electrode slurry of the important components of the lithium battery comprises the following components: positive/negative electrode active material, conductive agent, binder, solvent, and other additives. The electrode slurry is coated on the surface of a current collector, and the electrode is manufactured after drying. Among the numerous non-carbon based negative electrode candidate materials, silicon has an ultra-high theoretical capacity (4200 mAh/g), and is considered as a good negative electrode material for developing high energy density batteries. However, silicon undergoes a huge volume change of about 300% during the delithiation process, resulting in pulverization of silicon particles, and further in loss of electrical contact between the silicon particles and the conductive agent, which damages the whole electrode structure, thereby causing capacity attenuation and poor cycle performance.
In research and practical production in the field of lithium batteries, for silicon negative electrode systems, the existing binders have the following problems: on one hand, the bonding between Van der Waals force and silicon is not enough to ensure that the silicon material does not fall off in the use process of the lithium battery, and on the other hand, the adhesive has high rigidity and cannot effectively eliminate the stress generated by the volume expansion of the silicon material; due to the above problems, the cycle stability of the lithium battery is poor.
Disclosure of Invention
In view of the foregoing drawbacks or shortcomings in the prior art, it is desirable to provide an electrode binder, a method for preparing the same, a negative electrode, a lithium battery, and a vehicle, so as to form a strong acting force between the binder and silicon, adapt to the volume change of silicon during charging and discharging, and improve the cycle stability of the silicon negative electrode.
In a first aspect, the present application provides an electrode binder comprising an ionic liquid polymer having the structural formula:
wherein R is 1 And R is 2 Each independently is any one of bis (trifluoromethylsulfonyl) imide, bis (fluorosulfonyl) imide, perchlorate, hexafluorophosphate, hexafluoroarsenate, tetrafluoroborate, dioxaborate, difluorooxalate borate, or trifluoromethylsulfonate;
m and a are each independently any integer between 1 and 20; b is any integer between 1 and 100; n and c are any integer between 1 and 100;
x and y are each independently any fraction between 0 and 1, and x+y is equal to 1.0;
p and q are each independently any fraction between 0 and 1, and p+q is equal to 1.0.
As an alternative scheme, x is more than or equal to 0.3 and less than or equal to 0.8, and y is more than or equal to 0.2 and less than or equal to 0.7; p is more than or equal to 0.3 and less than or equal to 0.8, q is more than or equal to 0.2 and less than or equal to 0.7.
As an alternative scheme, x is more than or equal to 0.5 and less than or equal to 0.7,0.3, and y is more than or equal to 0.5; p is more than or equal to 0.5 and less than or equal to 0.7,0.3, q is more than or equal to 0.5.
Alternatively, the molecular weight of the ionic liquid polymer is 10000-500000; the molecular weight of the preferred ionic liquid polymer is 50000-500000.
In a second aspect, the present application provides a method for preparing the electrode binder of the first aspect, comprising the steps of:
dissolving a compound containing diamine and carboxyl and PEG capped by diamine into a solvent to obtain a mixed solution I;
dropwise adding the mixture of formaldehyde and acetaldehyde into the mixture I, uniformly mixing, adding acid liquor to obtain a mixture II, and heating the mixture II to react to obtain a mixture III;
cooling, distilling under reduced pressure and washing the mixed solution III to obtain an ionic liquid polymer containing acid radical balance anions;
dissolving an ionic liquid polymer containing acid radical balance anions in water to obtain a mixed solution IV, and dropwise adding the mixed solution IV into an aqueous solution of an anion exchanger to react to generate a precipitate;
and washing and drying the precipitate to obtain the electrode binder.
Alternatively, the acid solution is any one of acetic acid, hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
Alternatively, the structural formula of the compound containing the diamine group and the carboxyl group is as follows:
wherein m and a are each independently any integer between 1 and 20; b is any integer between 1 and 100.
Alternatively, the compound containing a diamine group and a carboxyl group is any one of ornithine, lysine, 2, 4-diaminoglutaric acid, 2, 5-diaminoadipic acid, and 2, 6-diaminopimelic acid.
Alternatively, the anion exchanger is any one of lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium dioxaoxalato borate, lithium difluorooxalato borate or lithium trifluoromethylsulfonate.
In a third aspect, the present application provides a negative electrode for a lithium battery, comprising: a current collector and a silicon-based material layer formed on a surface of the current collector, the silicon-based material layer including the electrode binder of the first aspect.
In a fourth aspect, the present application provides a lithium battery comprising the negative electrode of the lithium battery of the third aspect.
In a fifth aspect, the present application provides a vehicle comprising the lithium battery of the fourth aspect.
The electrode binder provided by the application is an ionic liquid polymer, and the ionic liquid polymer comprises a chain segment with carboxyl and a PEG chain segment, when the electrode binder is used in a silicon negative electrode system, the carboxyl forms a strong hydrogen bond with a silicon material in the silicon negative electrode, so that the bonding performance between the binder and the silicon material is improved, and the silicon material is prevented from being separated from a current collector; the PEG chain segment has flexibility, so that the rigidity of the ionic liquid polymer can be reduced, the binder can adapt to the volume change of a silicon material in the charge and discharge process of a lithium battery, and the charge and discharge cycle stability of a silicon negative electrode is improved. In addition, the binder has good ionic conductivity, so that the diffusion and transmission of lithium ions in an electrode material are facilitated, the internal resistance of a lithium battery is reduced, and the specific capacity and the cycling stability of the lithium battery are improved.
Detailed Description
The present application will be described in further detail with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the application and are not limiting of the application. It should be noted that, for convenience of description, only the portions related to the application are shown in the embodiments.
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
The binder with hydroxyl, carboxyl, amino and other functional groups is researched to comprise polyacrylic acid (PAA), CMC/SBR (styrene-butadiene rubber), sodium alginate, chitosan and the like, wherein the molecular chain of the polyacrylic acid binder contains a large amount of carboxyl, and can form strong interaction with active substances and current collectors, so that the binder can be applied to a high-capacity silicon-based anode system. However, the traditional polyacrylic acid type adhesive has high rigidity, is not beneficial to eliminating the stress generated by the volume expansion of silicon, and causes poor battery cycle performance.
The embodiment of the application provides an electrode binder, which comprises an ionic liquid polymer, wherein the ionic liquid polymer has the following structural formula:
wherein R is 1 And R is 2 Each independently is any one of bis (trifluoromethylsulfonyl) imide, bis (fluorosulfonyl) imide, perchlorate, hexafluorophosphate, hexafluoroarsenate, tetrafluoroborate, dioxaborate, difluorooxalate borate, or trifluoromethylsulfonate;
m is any integer between 1 and 6; n is any integer between 1 and 20;
m and a are each independently any integer between 1 and 20; b is any integer between 1 and 100; n and c are any integer between 1 and 100;
x and y are each independently any fraction between 0 and 1, for representing the molar ratio between two structural units, and x+y is equal to 1.0;
p and q are each independently any fraction between 0 and 1, representing the molar ratio between the two structural units, and p+q is equal to 1.0.
Wherein m and a; b; n and c; the values of x and y, and p and q determine the chain length of the ionic liquid polymer, and influence the molecular weight of the ionic liquid polymer;
b, determining the number of carboxyl groups in the ionic liquid polymer, so as to influence the cohesiveness of the ionic liquid polymer;
the values of n and c determine the length of the PEG chain segment, thereby influencing the flexibility and ionic conductivity of the ionic liquid polymer;
the values of x, y, p and q are controlled, so that the cohesiveness, flexibility and ionic conductivity of the ionic liquid polymer are controlled.
The ionic liquid polymer provided by the embodiment of the application comprises a chain segment with carboxyl and a flexible PEG chain segment, wherein the carboxyl can form a strong hydrogen bond with silicon of the silicon negative electrode, so that the bonding performance of the adhesive is improved, and the silicon of the silicon negative electrode is prevented from being separated from the current collector; the PEG chain segment provides flexibility for the binder, so that the binder has higher flexibility, and is suitable for the volume change of silicon particles of the silicon anode in the charging and discharging process. The electrode binder improves the charge-discharge cycle stability of the silicon negative electrode.
The cations in the ionic liquid polymer provided by the embodiment of the application are imidazole cations on a polymer main chain, the imidazole cations have higher coulomb force, can interact with lithium ions to transmit the lithium ions, and meanwhile, the PEG chain segments can also be used for transmitting the lithium ions. Therefore, the electrode binder provided by the embodiment of the application has good ionic conductivity, is beneficial to the diffusion and transmission of lithium ions in an electrode material, and reduces the internal resistance of the battery, thereby improving the specific capacity and the cycling stability of the battery.
Compared with the traditional adhesive, the ionic liquid polymer has good adhesive property, flexibility and ion conductivity, is beneficial to preventing silicon from separating from a current collector and adapting to the volume change of silicon in the charge and discharge process, is beneficial to the diffusion and transmission of lithium ions in an electrode material, reduces the internal resistance of a battery, and further improves the specific capacity and the cycling stability of the battery.
Further, x is more than or equal to 0.3 and less than or equal to 0.8, and y is more than or equal to 0.2 and less than or equal to 0.7; p is more than or equal to 0.3 and less than or equal to 0.8, q is more than or equal to 0.2 and less than or equal to 0.7; for example, x and p are each 0.3,0.4,0.5,0.6,0.7,0.8, etc.; y and q are 0.2,0.3,0.4,0.5,0.6,0.7, respectively, and the like.
Preferably, x is more than or equal to 0.5 and less than or equal to 0.7,0.3 and y is more than or equal to 0.5; p is more than or equal to 0.5 and less than or equal to 0.7,0.3, q is more than or equal to 0.5. The value ranges of x, y, p and q disclosed by the application are beneficial to adjusting the contents of imidazole cationic chain segments, carboxyl-containing chain segments and PEG chain segments in the ionic liquid polymer, so that the cohesiveness, flexibility and ionic conductivity of the ionic liquid polymer are controlled, and the ionic liquid polymer has optimal performance.
Further, the molecular weight of the ionic liquid polymer is 10000-500000. For example: the molecular weight of the ionic liquid polymer may be 10000, 15000, 20000, 30000, 50000, 100000, 180000, 250000, 30000, 360000, 400000, 430000, 480000, 500000, etc. The molecular weight of the preferred ionic liquid polymer is 50000-500000. The embodiment of the application does not limit specific molecular weight. The molecular weight of the ionic liquid polymer disclosed by the embodiment of the application is favorable for the adhesive to have good cohesiveness, flexibility and ionic conductivity.
In conclusion, the electrode binder has good cohesiveness, flexibility and ion conductivity, is beneficial to preventing silicon from separating from a current collector and adapting to the volume change of silicon in the charge and discharge process, is beneficial to the diffusion and transmission of lithium ions in an electrode material, reduces the internal resistance of a battery, and further improves the specific capacity and the cycling stability of the battery;
and the content of each functional group is controlled, so that the cohesiveness, flexibility and ionic conductivity of the polymer lithium ions are controlled, the performance of the ionic liquid polymer is improved, and the charge-discharge cycling stability of the electrode is improved.
In a second aspect, embodiments of the present application provide a method for preparing the electrode binder of the first aspect, comprising the steps of:
dissolving a compound containing diamine and carboxyl and PEG capped by diamine into a solvent to obtain a mixed solution I;
dropwise adding the mixture of formaldehyde and acetaldehyde into the mixture I, uniformly mixing, adding acid liquor to obtain a mixture II, and heating the mixture II to react to obtain a mixture III;
cooling, distilling under reduced pressure and washing the mixed solution III to obtain an ionic liquid polymer containing acid radical balance anions;
dissolving an ionic liquid polymer containing acid radical balance anions in water to obtain a mixed solution IV, and dropwise adding the mixed solution IV into an aqueous solution of an anion exchanger to react to generate a precipitate;
and washing and drying the precipitate to obtain the electrode binder.
It should be noted that the number of the substrates,
the purpose of the acid solution addition is to provide acidic conditions while the acid ions act as counter anions to the cations of the synthetic ionic liquid polymer and are conducive to ion exchange with other ions;
the mixture of formaldehyde and acetaldehyde is used for reacting with a compound with diamine groups (namely a compound containing diamine groups and carboxyl groups and PEG capped by diamine groups) under an acidic condition to generate a polymer main chain containing imidazole groups and PEG, and introducing at least one carboxyl group on the polymer main chain; the number of carboxyl groups in the ionic liquid polymer is consistent with the number of carboxyl groups in the compound containing the diamido groups and the carboxyl groups, and the number of the carboxyl groups is at least one.
Wherein the compound containing the diamine group and the carboxyl group is mixed with the diamine-terminated compound in a certain ratio, and the ratio is not particularly limited herein.
The ionic liquid polymer containing the acid radical balance anions is dissolved in water for ion exchange, so that the ionic liquid polymer is prevented from being dissolved in an organic solvent due to the adoption of the organic solvent, separation and impurity removal are difficult, and the water is selected in the embodiment of the application, so that the ionic liquid polymer is separated and the impurity anions are removed.
By way of example only, the process may be performed,
will beDissolving in water to obtain a mixed solution I;
dropwise adding the mixed solution of formaldehyde and acetaldehyde into the mixed solution I under the condition of ice-water bath, stirring and uniformly mixing, adding acetic acid to obtain mixed solution II, heating the mixed solution II to 100 ℃, and reacting for 2 hours to obtain mixed solution III;
cooling, distilling under reduced pressure and washing the mixed solution III to obtain an ionic liquid polymer containing acetate balancing anions;
dissolving an ionic liquid polymer containing acetate balancing anions in water to obtain a mixed solution IV, dropwise adding the mixed solution IV into an aqueous solution of lithium bistrifluoromethylsulfonyl imide, and reacting to generate a precipitate;
the precipitate is washed and dried to obtain the electrode binder, and the structural formula can be expressed asWherein R is 1 Is bis (trifluoromethylsulfonyl) imide.
Further, the acid liquid is any one of acetic acid, hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
Further, the structural formula of the compound containing the diamine group and the carboxyl group is shown as follows:
wherein m and a are each independently any integer between 1 and 20; b is any integer between 1 and 100.
As a practical way, the compound containing the diamine and the carboxyl is any one of ornithine, lysine, 2, 4-diaminoglutaric acid, 2, 5-diaminoadipic acid and 2, 6-diaminopimelic acid, and the examples of the present application exemplify the compound partially meeting the requirements, but other compounds containing both the diamine and the carboxyl are also applicable to the examples of the present application, and the specific compounds are not limited to the examples of the present application.
Further, the solvent is any one of water, N-methylpyrrolidone, N-methylformamide, N-methylacetamide, N-dimethylformamide, sulfolane or dimethylsulfoxide.
Further, the conditions for obtaining the mixture II were: the temperature is 80-120 ℃ and the time is 0.5-4 h. For example, the temperature is 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, or the like; the time is 0.5h, 1h, 2h, 3h or 4h, etc. The embodiment of the application does not limit the specific reaction temperature and time. The condition that the mixture of formaldehyde and acetaldehyde disclosed by the embodiment of the application reacts with the diamido compound under the acidic condition is beneficial to promoting the reaction and improving the yield of the reactant.
Further, the anion exchanger is any one of lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluorooxalate borate or lithium trifluoromethylsulfonate.
In a third aspect, an embodiment of the present application provides a negative electrode of a lithium battery, including: a current collector and a silicon-based material layer formed on a surface of the current collector, the silicon-based material layer including the electrode binder of the first aspect. Those skilled in the art will appreciate that the negative electrode of the lithium battery has all of the features and advantages of the electrode binder described above and will not be described in detail herein.
In a specific example, a negative electrode of a lithium battery was prepared by the following procedure:
mixing a silicon-based active substance, a binder and a conductive agent, adding a dispersing agent, and fully and uniformly stirring to obtain electrode slurry, namely a silicon-based material layer;
and coating a silicon-based material layer on a current collector (such as copper foil), heating, drying and cutting according to specification requirements to obtain the negative electrode of the lithium battery.
The silicon-based active substance is a silicon-based material or a silicon-carbon composite material based on a silica gel material, and the silicon-based material is one of nano silicon, micro silicon, porous silicon, amorphous silicon or silicon oxide;
the conductive agent is at least one of graphite, acetylene black, super P, super S, graphene, carbon fiber, carbon nanotube and ketjen black;
the dispersing agent is at least one of N-methyl pyrrolidone (NMP), N-methyl formamide, N-methyl acetamide, N-dimethyl formamide, sulfolane and dimethyl sulfoxide;
illustratively, the mass percent of the binder is 5% -40% based on the total weight of the silicon-based material layer; the mass percentage of the silicon-based active substances is 20% -90%; the mass percentage of the conductive additive is 5-40%.
In a fourth aspect, embodiments of the present application provide a lithium battery comprising the negative electrode of the lithium battery of the third aspect. Those skilled in the art will appreciate that the lithium battery has all of the features and advantages of the electrode binders described above and will not be described in detail herein. In general, the lithium battery of the embodiment of the application has good specific capacity and cycle stability.
In a fifth aspect, the present application provides a vehicle comprising the lithium battery of the fourth aspect. For example, a plurality of battery packs consisting of the aforementioned lithium batteries may be included. Thus, the vehicle has all the features and advantages of the lithium battery described above, and will not be described in detail herein.
The present application is illustrated by the following specific examples, which are given for illustrative purposes only and are not intended to limit the scope of the present application in any way.
Example 1
(1) Preparation of electrode binders (Ionic liquid polymers)Wherein TFSI represents bis (trifluoromethylsulfonyl) imide, and the molar ratio of the two structural units is 5:5;
the specific process is as follows:
the structural formula of the compound containing the diamido and carboxyl isWherein m=2, the bisamine-terminated compound is +.>Wherein n=2, and the mixture is dissolved in water according to the proportion of 5:5 to obtain a mixed solution I;
dropwise adding the mixed solution of formaldehyde and acetaldehyde into the mixed solution I under the condition of ice-water bath, stirring and uniformly mixing, adding acetic acid to obtain mixed solution II, heating the mixed solution II to 100 ℃, and reacting for 2 hours to obtain mixed solution III;
cooling, distilling under reduced pressure and washing the mixed solution III to obtain an ionic liquid polymer containing acetate balancing anions;
dissolving an ionic liquid polymer containing acetate balancing anions in water to obtain a mixed solution IV, dropwise adding the mixed solution IV into an aqueous solution of lithium bistrifluoromethylsulfonyl imide, and reacting to generate a precipitate;
the precipitate is washed and dried to obtain the electrode binder, and the structural formula can be expressed as
(2) Half cell preparation
Dispersing nano silicon powder, conductive agent carbon black (Super-P) and a binder in NMP according to a mass ratio of 8:1:1, uniformly grinding in a mortar, and coating the slurry on a copper foil by using a coating machine, wherein the thickness of the coating slurry is 100 mu m; then airing at room temperature, cutting into wafers with the diameter of 13mm by using a slicing machine, then putting the wafers into a vacuum drying oven with the temperature of 80 ℃ for drying for 12 hours, and taking out when the temperature is reduced to room temperature after drying, thus obtaining the nano silicon negative electrode;
transfer the nano-silicon negative electrode into a glove box filled with argon (content O 2 ≤0.5ppm、H 2 O is less than or equal to 0.5 ppm), the nano silicon negative plate is weighed piece by piece in a glove box, the weighed mass is recorded, and a metal lithium plate is taken as a counter electrode, and 1mol/L LiPF is adopted 6 EC/DMC/DEC (v/v/v=1/1/1) solution as electrolyte, and a CR2025 type button half cell was assembled in a glove box.
Example 2
This embodiment differs from embodiment 1 in that:
preparation of ionic liquid polymersThe molar ratio of the two structural units is 6:4;
the structural formula of the compound containing the diamine and the carboxyl isWherein m=2, the bisamine-terminated compound is +.>Where n=2, are dissolved together in water in a ratio of 6:4.
Example 3
This embodiment differs from embodiment 1 in that:
preparation of ionic liquid polymersThe molar ratio of the two structural units is 7:3;
the structural formula of the compound containing the diamine and the carboxyl isWherein m=2, the bisamine-terminated compound is +.>Where n=2, are dissolved together in water in a ratio of 7:3.
Example 4
This embodiment differs from embodiment 1 in that:
preparation of ionic liquid polymersThe molar ratio of the two structural units is 4:6;
the structural formula of the compound containing the diamine and the carboxyl isWherein a=1, b=1, the diamine-terminated compound is +.>Where n=2, are dissolved together in water in a ratio of 4:6.
Example 5
This embodiment differs from embodiment 1 in that:
preparation of ionic liquid polymersThe molar ratio of the two structural units is 5:5；
the structural formula of the compound containing the diamine and the carboxyl isWherein a=1, b=1, the diamine-terminated compound is +.>Where n=2, are dissolved together in water in a ratio of 5:5.
Example 6
This embodiment differs from embodiment 1 in that:
preparation of ionic liquid polymersThe molar ratio of the two structural units is 6:4;
the structural formula of the compound containing the diamine and the carboxyl isWherein a=1, b=1, the diamine-terminated compound is +.>Where n=2, are dissolved together in water in a ratio of 6:4.
Comparative example 1
This comparative example differs from example 1 in that: the electrode binder is PAA (polyacrylic acid).
Comparative example 2
This comparative example differs from example 1 in that:
preparation of ionic liquid polymers
Comparative example 3
This comparative example differs from example 1 in that:
preparation of ionic liquid polymers
The half cells prepared in examples 1 to 6 and comparative examples 1 to 3 above were subjected to the following performance test to characterize the electrochemical performance of the electrode binders.
The test procedure was as follows: 10 batteries prepared in examples 1 to 6 and comparative examples 1 to 3 were each tested on a LAND CT 2001C secondary battery performance test device at 25.+ -. 1 ℃ in constant current charge-discharge cycles. The test conditions were: the discharge cutoff voltage is 0.01V and the charge cutoff voltage is 1.5V, and the charge and discharge cycle is carried out for 3 times under the current density of 100mA/g, and then the charge and discharge cycle is carried out under the current density of 500 mA/g.
The test results are shown in table 1:
TABLE 1 Performance test results of half cells prepared in examples 1 to 6 and comparative examples 1 to 3
The results shown in table 1 show that the half cells prepared in examples 1 to 6 are superior to the half cell prepared in comparative example 1 in both cell capacity and cycle performance, indicating that the electrode binder prepared according to the present application is advantageous in improving the performance of lithium batteries as compared to conventional binders.
The half cells prepared in examples 1 to 6 were superior to the half cells prepared in comparative examples 2 and 3 in both battery capacity and cycle performance; the half cell performance test of both comparative example 2 and comparative example 3 is superior to comparative example 1. The test results show that the ionic liquid polymer with the carboxyl chain segment or the ionic liquid polymer with the PEG chain segment cannot effectively improve the performance of the lithium battery; and compared with the existing PAA, the ionic liquid polymer improves the performance of the lithium battery. The electrode binder of the embodiment of the application is further described that under the synergistic effect of the chain segment with carboxyl and the PEG chain segment, the binding performance and flexibility of the binder are improved, the silicon of the silicon negative electrode is prevented from being separated from the current collector, the volume change of silicon particles of the silicon negative electrode in the charging and discharging process is favorably adapted, meanwhile, the electrode binder of the embodiment of the application has good ionic conductivity, the diffusion and transmission of lithium ions in an electrode material are favorably realized, the internal resistance of a battery is reduced, and the specific capacity and the cycling stability of the battery are improved.
By combining the results of table 1 and structural analysis of the electrode binder of the embodiment of the application, the electrode binder of the embodiment of the application improves the binding property, flexibility and ionic conductivity of the binder, is beneficial to fixing silicon in a silicon anode, is suitable for the volume change of silicon particles in the charge-discharge process, is beneficial to the diffusion and transmission of lithium ions in an electrode material, reduces the internal resistance of a battery, and further improves the specific capacity and the cycling stability of the battery.
The results in Table 1 show that the ratio of the compound containing both diamine and carboxyl groups to the diamine-terminated PEG compound has a large impact on the performance of the binder. For example: the results of comparative examples 1-3 demonstrate that when the ratio of the compound containing both diamine and carboxyl groups to the diamine-terminated PEG compound is 1:1, the battery is relatively more excellent in capacity and cycle stability; the possible reasons for the analysis are that the carboxyl-containing segment and the PEG segment give the binder an optimal cohesiveness, flexibility and ionic conductivity, which is advantageous for fixing the silicon material, adapting to the volume change of the silicon particles and improving the lithium ion conduction.
The above description is only illustrative of the preferred embodiments of the present application and of the principles of the technology employed. It will be appreciated by persons skilled in the art that the scope of the application referred to in the present application is not limited to the specific combinations of the technical features described above, but also covers other technical features formed by any combination of the technical features described above or their equivalents without departing from the inventive concept. Such as the above-mentioned features and the technical features disclosed in the present application (but not limited to) having similar functions are replaced with each other.
Claims (12)
1. An electrode binder, comprising an ionic liquid polymer having the structural formula:
wherein R is 1 And R is 2 Each independently is any one of bis (trifluoromethylsulfonyl) imide, bis (fluorosulfonyl) imide, perchlorate, hexafluorophosphate, hexafluoroarsenate, tetrafluoroborate, dioxaborate, difluorooxalate borate, or trifluoromethylsulfonate;
m is any integer between 1 and 6; n is any integer between 1 and 20, and a is any integer between 1 and 20; b is any integer between 1 and 100; c is any integer between 1 and 100;
0.3≤x≤0.8，0.2≤y≤0.7；0.3≤p≤0.8，0.2≤q≤0.7。
2. the electrode binder of claim 1 wherein 0.5.ltoreq.x.ltoreq. 0.7,0.3.ltoreq.y.ltoreq.0.5; p is more than or equal to 0.5 and less than or equal to 0.7,0.3, q is more than or equal to 0.5.
3. The electrode binder of claim 1 wherein the ionic liquid polymer has a molecular weight of 10000 to 500000.
4. The electrode binder of claim 3 wherein the ionic liquid polymer has a molecular weight of 50000 to 500000.
5. A method of preparing the electrode binder of any one of claims 1-4, comprising the steps of:
dissolving a compound containing diamine and carboxyl and PEG capped by diamine into a solvent to obtain a mixed solution I;
dropwise adding the mixture of formaldehyde and acetaldehyde into the mixture I, uniformly mixing, adding acid liquor to obtain a mixture II, and heating the mixture II to react to obtain a mixture III;
cooling, distilling under reduced pressure and washing the mixed solution III to obtain an ionic liquid polymer containing acid radical balance anions;
dissolving the ionic liquid polymer containing acid radical balance anions in water to obtain a mixed solution IV, and dropwise adding the mixed solution IV into an aqueous solution of an anion exchanger to react to generate a precipitate;
and washing and drying the precipitate to obtain the electrode binder.
6. The method according to claim 5, wherein the acid solution is any one of acetic acid, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
7. The method of claim 5, wherein the compound comprising a diamine group and a carboxyl group has the structural formula:
wherein m is any integer between 1 and 6; a is any integer between 1 and 20; b is any integer between 1 and 100.
8. The method according to claim 7, wherein the compound containing a diamine group and a carboxyl group is any one of ornithine, lysine, 2, 4-diaminoglutaric acid, 2, 5-diaminoadipic acid, 2, 6-diaminopimelic acid.
9. The method of claim 5, wherein the anion exchanger is any one of lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium dioxaoxalato borate, lithium difluorooxalato borate, or lithium trifluoromethylsulfonate.
10. A negative electrode for a lithium battery, comprising: a current collector and a silicon-based material layer formed on a surface of the current collector, wherein the silicon-based material layer comprises the electrode binder according to any one of claims 1 to 4.
11. A lithium battery comprising the negative electrode of the lithium battery of claim 10.
12. A vehicle comprising the lithium battery of claim 11.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009123523A (en) * | 2007-11-15 | 2009-06-04 | Jsr Corp | Binder composition for battery electrode, method of manufacturing the same, paste for battery electrode, battery electrode, and method of manufacturing battery electrode |
| CN103035915A (en) * | 2011-10-05 | 2013-04-10 | 三星Sdi株式会社 | Negative active material and lithium battery containing the negative active material |
| WO2016066271A1 (en) * | 2014-10-31 | 2016-05-06 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e. V. | Use of a poly(ionic liquid) as a binder material for electrodes in electrochemical devices |
| WO2017190355A1 (en) * | 2016-05-06 | 2017-11-09 | 深圳先进技术研究院 | Electrolyte solution, secondary battery containing electrolyte solution and preparation method therefor |
| CN109037689A (en) * | 2018-07-20 | 2018-12-18 | 亚士创能科技(上海)股份有限公司 | The polymeric binder of lithium ion silicon based anode material, lithium ion silicon based anode material and preparation method, battery cathode and lithium battery |
| CN109037622A (en) * | 2017-07-17 | 2018-12-18 | 浙江林奈新能源有限公司 | Ionomer electrode slurry |
| CN110071289A (en) * | 2019-04-15 | 2019-07-30 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery silicon substrate cathode compound binding agent and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102084807B1 (en) * | 2012-03-07 | 2020-03-04 | 메사추세츠 인스티튜트 오브 테크놀로지 | Rechargeable lithium battery for wide temperature operation |
-
2020
- 2020-11-16 CN CN202011281396.3A patent/CN114512667B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009123523A (en) * | 2007-11-15 | 2009-06-04 | Jsr Corp | Binder composition for battery electrode, method of manufacturing the same, paste for battery electrode, battery electrode, and method of manufacturing battery electrode |
| CN103035915A (en) * | 2011-10-05 | 2013-04-10 | 三星Sdi株式会社 | Negative active material and lithium battery containing the negative active material |
| WO2016066271A1 (en) * | 2014-10-31 | 2016-05-06 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e. V. | Use of a poly(ionic liquid) as a binder material for electrodes in electrochemical devices |
| WO2017190355A1 (en) * | 2016-05-06 | 2017-11-09 | 深圳先进技术研究院 | Electrolyte solution, secondary battery containing electrolyte solution and preparation method therefor |
| CN109037622A (en) * | 2017-07-17 | 2018-12-18 | 浙江林奈新能源有限公司 | Ionomer electrode slurry |
| CN109037689A (en) * | 2018-07-20 | 2018-12-18 | 亚士创能科技(上海)股份有限公司 | The polymeric binder of lithium ion silicon based anode material, lithium ion silicon based anode material and preparation method, battery cathode and lithium battery |
| CN110071289A (en) * | 2019-04-15 | 2019-07-30 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery silicon substrate cathode compound binding agent and its preparation method and application |
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