CN114843516A - Dispersing agent for lithium ion battery anode slurry - Google Patents
Dispersing agent for lithium ion battery anode slurry Download PDFInfo
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- CN114843516A CN114843516A CN202210526719.3A CN202210526719A CN114843516A CN 114843516 A CN114843516 A CN 114843516A CN 202210526719 A CN202210526719 A CN 202210526719A CN 114843516 A CN114843516 A CN 114843516A
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- Prior art keywords
- positive electrode
- electrode slurry
- dispersant
- lithium ion
- ion battery
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- 239000002270 dispersing agent Substances 0.000 title claims abstract description 99
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 20
- 239000006256 anode slurry Substances 0.000 title description 30
- 239000011267 electrode slurry Substances 0.000 claims abstract description 73
- 239000007787 solid Substances 0.000 claims abstract description 47
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- 229920000570 polyether Polymers 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 229920002635 polyurethane Polymers 0.000 claims abstract description 10
- 239000004814 polyurethane Substances 0.000 claims abstract description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 50
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 48
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 25
- 239000002033 PVDF binder Substances 0.000 claims description 23
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- -1 polyoxyethylene copolymer Polymers 0.000 claims description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 19
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 19
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 19
- 239000006258 conductive agent Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 229920001296 polysiloxane Polymers 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000006257 cathode slurry Substances 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 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 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 19
- 239000011268 mixed slurry Substances 0.000 abstract description 11
- 239000011888 foil Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 8
- 230000037303 wrinkles Effects 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 abstract 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 13
- 239000007772 electrode material Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000001514 detection method Methods 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PJVRNNRZWASOIT-UHFFFAOYSA-N 1-isocyanato-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(N=C=O)C=C1 PJVRNNRZWASOIT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- SOXJQKKNADFEOW-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].[Fe+2].[Li+] Chemical compound S(=O)(=O)([O-])[O-].[Fe+2].[Li+] SOXJQKKNADFEOW-UHFFFAOYSA-L 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000009736 wetting 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
-
- 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
-
- 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
-
- 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
- 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
- H01M4/624—Electric conductive fillers
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Abstract
The invention provides a dispersant for lithium battery positive electrode slurry. The dispersing agent comprises 5-15 wt% of component A, 15-60 wt% of polyether polyurethane containing a comb-like structure, 0.01-1 wt% of component B, 0.001-0.1 wt% of component C and the balance of organic solvent, wherein the total weight of the dispersing agent is 100 wt%. Compared with the prior art, when the solid content of the positive electrode slurry is the same, the positive electrode slurry has lower viscosity, and when the viscosity of the positive electrode slurry is the same, the positive electrode slurry has higher solid content, and can realize uniform dispersion of the positive electrode slurry by using relatively less solvent; in addition, the positive electrode slurry obtained by dispersing the dispersant of the invention can effectively overcome the problems of wrinkle, broken tape or scratch and foil leakage after coating, has better flexibility, and can effectively improve the viscosity when the dispersant of the invention is added into mixed slurry containing a commercial binder.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a dispersing agent for lithium ion battery anode slurry.
Background
The lithium ion battery is a high and new technology product, and compared with nickel-cadmium and nickel-hydrogen batteries, the lithium ion battery has the advantages of high voltage, large specific energy, long cycle life, good safety performance, small self-discharge, no memory effect, rapid charge and discharge, wide working temperature range and the like. Lithium iron phosphate lithium ion batteries have been extensively developed and applied in electric tools, energy storage and electric vehicles.
The traditional lithium iron phosphate electrode mainly comprises a current collector and an electrode material attached to the current collector, wherein the current collector is aluminum, the electrode material layer mainly comprises an active substance, a conductive additive and a binder, and the preparation method generally comprises the following steps: adding lithium iron phosphate, a binder and a conductive agent into an organic solvent, uniformly stirring to prepare electrode slurry, then coating the electrode slurry on an aluminum foil by an extrusion coating or transfer coating method, and drying and cold pressing to obtain the lithium iron phosphate electrode.
The electrode is prepared by the method for the lithium iron phosphate with larger granularity (more than micron level), so that the lithium iron phosphate can be uniformly dispersed, and the whole electrode has better conductivity. However, for a nanoscale lithium iron phosphate material, the number of nanoscale lithium iron phosphate particles is larger than that of lithium iron phosphate particles above the micron level, and the nanoscale lithium iron phosphate material is more difficult to disperse, and the same amount of conductive agent (the same as the amount of conductive agent used in an electrode prepared from lithium iron sulfate above the micron level) cannot form a good conductive effect among the nanoscale lithium iron phosphate particles, and increasing the amount of conductive agent can correspondingly reduce the amount of active material (i.e., lithium iron phosphate), thereby reducing the capacity density of the lithium iron phosphate battery.
For increasing the battery capacity, there are generally two methods: firstly, the specific capacity of the electrode active material is improved; and secondly, the proportion of electrode active substances in the electrode material is improved, namely, the content of other substances such as a binder, a conductive agent and the like is reduced, or the solid content of the electrode material is increased, and the using amount of a solvent is reduced. The specific capacity of the electrode active material is the characteristic of the electrode active material, and the specific capacity of the electrode active material can be improved only by improving the electrode active material, and the method usually has higher requirements on the technology. The method commonly used at present is to reduce the amount of solvent used by reducing the content of the conductive agent in the electrode material, increasing the content of the electrode active substance, or increasing the solid content of the electrode material. The solid content of the electrode material is increased, and the reduction of the solvent amount generally leads to the increase of the viscosity of the electrode material, so that the fluidity of the electrode slurry is reduced, and the electrical performance is reduced. How to balance the relationship between the two and effectively improve the battery capacity is a problem to be solved urgently in the field.
How to solve the above problems in the prior art is a problem to be solved urgently by those skilled in the art.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a dispersing agent for lithium ion battery anode slurry, so that the anode slurry prepared from the dispersing agent has higher solid content and lower viscosity, can be uniformly dispersed by using less solvent, has better flexibility, and can solve the problems of wrinkles, broken bands or scratches and foil leakage after coating.
The technical scheme is as follows: in order to solve the problems in the prior art, the invention provides a dispersant for lithium ion battery anode slurry, which comprises the following components by weight percent based on the total weight of 100 percent: 5 to 15wt% (e.g., 5wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%) of component A, 15 to 60wt% (e.g., 15wt%, 17 wt%, 18 wt%, 20 wt%, 22 wt%, 24 wt%, 25 wt%, 26 wt%, 28 wt%, 30 wt%, 32 wt%, 34 wt%, 35 wt%, 36 wt%, 38 wt%, 40 wt%, 42 wt%, 44 wt%, 45 wt%, 46 wt%, 48 wt%, 50 wt%, 52 wt%, 54 wt%, 56 wt%, 58 wt%, 60 wt%) of a polyether urethane containing a comb structure, 0.01 to 1wt% (e.g., 0.01 wt%, 0.05 wt%, 0.1wt%, 0.12 wt%, 0.14 wt%, 0.16 wt%, 0.18 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.55 wt%, 0.6 wt%, 0.55 wt%, 0., 0.65 wt%, 0.7 wt%, 0.75 wt%, 0.8 wt%, 0.85 wt%, 0.9 wt%, 0.95 wt%, 1 wt%) of the B component, 0.001 to 0.1wt% (e.g., 0.001 wt%, 0.004 wt%, 0.006 wt%, 0.008 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%) of the C component, and the balance of an organic solvent,
wherein, the first and the second end of the pipe are connected with each other,
the component A is selected from one or the combination of at least two of polyvinylpyrrolidone, polyacrylamide, hydroxyethyl cellulose and polyoxyethylene copolymer;
the component B is selected from one or the combination of at least two of hexamethylene diamine, tertiary amine and ethanolamine; and
the component C is selected from one or the combination of at least two of polysiloxane, polyether compound and modified organosilicon.
In some embodiments of the invention, the a component is preferably polyvinylpyrrolidone.
In some embodiments of the present invention, the comb-structure containing polyether polyurethane is a compound of formula I:
wherein the content of the first and second substances,
n represents an integer of 0 to 100 (e.g., 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, 100);
A 1 represents an H atom, an alkyl group having 1 to 5 (e.g., 1, 2, 3, 4, 5) carbon atoms, an alkoxy group having 1 to 4 (e.g., 1, 2, 3, 4) carbon atoms, or an alkenyl group having 2 to 5 (e.g., 2, 3, 4, 5) carbon atoms;
Indicates the attachment site in the bonded structure.
The polyurethane compound shown in the general formula I has a comb-shaped structure, the tail end of the polyurethane compound is a multi-branched chain structure formed by polytetrahydrofuran and polyethylene glycol block copolymer, the space resistance of further condensation among solid particles is formed, in addition, the polar structure of the polyurethane compound has stronger affinity with a solvent, and the wetting degree of the solid particles by the solvent is increased. When the dispersion agent is combined with the component A, the component B and the component C and then used as a dispersing agent to be applied to the anode slurry, a good dispersing effect can be achieved, the viscosity of the anode slurry is greatly reduced, the uniformity and the flexibility of the anode slurry during coating can be improved, and the problems of wrinkling, strip breakage and foil leakage cannot be caused during coating.
In some embodiments of the invention, the B component is preferably ethanolamine.
In some embodiments of the invention, component C is preferably a polysiloxane.
In some embodiments of the present invention, in the dispersant, the organic solvent is selected from one or a combination of at least two of N-methylpyrrolidone, dimethyl carbonate, diethyl carbonate, ethyl acetate, and methyl propionate, and preferably, the organic solvent is N-methylpyrrolidone.
In some embodiments of the present invention, the dispersant for the lithium ion battery positive electrode slurry comprises the following components, by total weight of 100 wt%: 5-15 wt% of polyvinylpyrrolidone, 15-60 wt% of polyether polyurethane containing a comb structure, 0.01-1 wt% of ethanolamine, 0.001-0.1 wt% of polysiloxane and the balance of organic solvent.
In some embodiments of the present invention, the dispersant for the lithium ion battery positive electrode slurry comprises the following components, by total weight of 100 wt%: 5-15 wt% of polyvinylpyrrolidone, 15-60 wt% of polyether polyurethane containing a comb structure and shown in a general formula I, 0.01-1 wt% of ethanolamine, 0.001-0.1 wt% of polysiloxane, and the balance of organic solvent:
wherein the content of the first and second substances,
n represents 0 to 100;
A 1 represents H atom, alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 4 carbon atoms, or alkenyl group having 2 to 5 carbon atoms;
Denotes the carbon atom in the bonded structure.
In another aspect, the invention provides a positive electrode slurry comprising the dispersant of the invention, which is prepared by mixing a solid dry material and an organic solvent.
In some embodiments of the invention, the dry solid material in the positive electrode slurry comprises 85 to 98 wt% (e.g., 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%) of lithium iron phosphate, 0.5 to 8 wt% (e.g., 0.5 wt%, 0.8 wt%, 1wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%) of a conductive agent, 0.1 to 1wt% (e.g., 0.1wt%, 0.12 wt%, 0.14 wt%, 0.16 wt%, 0.18 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.55 wt%, 0.5 wt%, 6 wt%, 0.5 wt%, and/wt% of a conductive agent, based on 100wt% of the total weight of the total, 0.75 wt%, 0.8 wt%, 0.85 wt%, 0.9 wt%, 0.95 wt%, 1 wt%) of a dispersant, and 1 to 8 wt% (e.g., 1wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%) of a binder.
In some embodiments of the invention, the weight of the organic solvent in the cathode slurry is 35 to 50 wt% (e.g., 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%) of the total weight of the cathode slurry.
In the present invention, the higher the solid content in the positive electrode slurry, the more advantageous the battery capacity is. When the dispersant is applied to the positive electrode slurry, the solid content is high, the viscosity is low, and the problems of wrinkles, broken belts or scratches and foil leakage can be solved after the dispersant is coated, so that the dispersant is suitable for industrial use.
In some embodiments of the present invention, the conductive agent is selected from one or a combination of at least two of graphite conductive agent, conductive carbon black, graphene and metal powder, preferably, the graphite conductive agent is selected from one or a combination of at least two of KS-6, KS-15, SFG-6, SFG-15, preferably, the conductive carbon black comprises one or a combination of at least two of acetylene black, Super P, Super S, 350G, carbon fiber, carbon nanotube, ketjen black, and activated carbon, preferably, the metal powder is selected from one or a combination of at least two of zinc powder, copper powder, aluminum powder, silver powder, gold powder, tungsten powder, and tin powder.
In some embodiments of the invention, the binder is selected from one or a combination of at least two of polyvinylidene fluoride, sodium carboxymethylcellulose, styrene butadiene rubber, sodium alginate, polyacrylic acid and polyethylene oxide.
In some embodiments of the invention, the binder is selected from polyvinylidene fluoride having a molecular weight of 60 to 100 million.
In some embodiments of the present invention, in the positive electrode slurry, the organic solvent is selected from one or a combination of at least two of N-methylpyrrolidone, dimethyl carbonate, diethyl carbonate, ethyl acetate, and methyl propionate, preferably N-methylpyrrolidone.
In the invention, the anode slurry can be uniformly dispersed by uniformly mixing the lithium iron phosphate, the conductive agent, the dispersing agent and the binder in the solvent in a stirring and/or ultrasonic dispersion mode. The stirring may be conventional mechanical stirring, magnetic stirring or stirring with a shear dispersion emulsifier. The mixing order of the lithium iron phosphate, the conductive agent, the dispersing agent, the binder and the solvent is not particularly limited, and the mixing order may be that the conductive agent, the binder and the solvent are uniformly mixed first, then the lithium iron phosphate is added, and finally the dispersing agent is added to uniformly mix, or that the lithium iron phosphate, the conductive agent and the binder are uniformly mixed first, then the solvent is added, and finally the dispersing agent is added to uniformly mix. The stirring can adopt primary stirring and secondary stirring, the speed of the primary stirring is 100-500 r/min, the stirring time is 5-30 min, the speed of the secondary stirring is more than or equal to 2000 r/min, and the stirring time is 10-300 min.
Has the advantages that: the positive pole slurry prepared by the dispersant has higher solid content and lower viscosity, compared with the prior art, when the solid content in the positive pole slurry is the same, the positive pole slurry has lower viscosity, when the viscosity in the positive pole slurry is the same, the positive pole slurry has higher solid content, can be prepared in shorter time, can realize the uniform dispersion of the positive pole slurry by using relatively less solvent, effectively saves the time of a production process, and improves the production efficiency; in addition, after the positive electrode slurry obtained by dispersing the dispersing agent disclosed by the invention is coated, the problems of wrinkles, broken strips or scratches and foil leakage are effectively solved, the positive electrode slurry has better flexibility and is suitable for industrial production, and the viscosity of the positive electrode slurry can be effectively improved by adding the dispersing agent disclosed by the invention into mixed slurry containing a commercially available binder.
Detailed Description
The invention will be illustrated below with reference to specific embodiments. It should be noted that the following examples are illustrative of the present invention, and are not intended to limit the present invention. Other combinations and various modifications within the spirit or scope of the present invention may be made without departing from the spirit or scope of the present invention.
The synthesis method of the polyether polyurethane with the structure of the general formula I comprises the following steps:
step 1. Synthesis of intermediate Z-1:
1mol of isophorone diisocyanate (IPDI) is fully dissolved in 300mL of tetrahydrofuran, 0.5g of dibutyltin dilaurate is added in a nitrogen environment, the temperature is controlled to be 30 ℃, 1mol of hydroxyethyl acrylate is dropwise added into a reaction system at a constant speed within 2-3 h, the temperature is controlled to be 30 ℃, and the NCO reaction is monitored to be complete by a titration method. Eluting solvent, dissolving the product in mixed solvent of n-hexane and anhydrous ethyl acetate (weight ratio of n-hexane to anhydrous ethyl acetate is 4:1), separating by column chromatography, and rotary evaporating to obtain Z-1 compound.
Step 2. Synthesis of intermediate monomer Z-2:
1mol of C-1 compound (purchased from Wanhua chemical group Co., Ltd.) was dissolved in 1000mL of anhydrous tetrahydrofuran, 3.1mol of p-isopropylphenylisocyanate was added, 0.1g of dibutyltin dilaurate was added under a nitrogen atmosphere, the temperature was controlled at 25 ℃ and the completion of NCO reaction was monitored by titration. Eluting solvent, dissolving the product in mixed solvent of n-hexane and anhydrous ethyl acetate (weight ratio of n-hexane to anhydrous ethyl acetate is 4:1), separating by column chromatography, and rotary evaporating to obtain Z-2 compound.
Step 3. synthesis of compounds of general formula I:
100g of the compound (100 g Z-1) and 1g of azobisisobutyronitrile were dissolved in 100g of toluene sufficiently to prepare a solution (D) to be titrated. Adding 100g of toluene into a reaction bottle, controlling the temperature to be 70 ℃ under stirring, dropwise adding the solution D to be titrated into the reaction system at a constant speed within 3-4 h, reacting for 1h at 70 ℃, and performing infrared detection by 1640cm- 1 After the absorption peak disappears, the reaction is complete to obtain the compound of Z-3:
controlling the system temperature to be 25-35 ℃, adding a Z-2 compound, reacting at room temperature for 48 h, monitoring the NCO reaction by a titration method to be complete, and eluting a solvent to obtain a compound I-1:
the following examples respectively prepare dispersants for positive electrode slurry pertaining to the present invention using specific component amounts, and non-enumerated dispersants pertaining to the scope of the present invention have the same use effects.
Example 1
The dispersant comprised 5wt% of polyvinylpyrrolidone, 15wt% of the polyether urethane of formula I-1, 0.08 wt% of ethanolamine, 0.01 wt% of polysiloxane, and 79.91 wt% of N-methylpyrrolidone, which were thoroughly mixed, based on the total weight of 100wt%, to give dispersant 1 of the present example.
Example 2
The dispersant comprised 10 wt% of polyvinylpyrrolidone, 20 wt% of the polyether urethane of formula I-1, 0.1wt% of ethanolamine, 0.02 wt% of polysiloxane, and 69.88 wt% of N-methylpyrrolidone, which were thoroughly mixed, based on 100wt% of the total weight, to give dispersant 2 of this example.
Example 3
The dispersant comprised 15wt% of polyvinylpyrrolidone, 35 wt% of the polyether urethane of formula I-1, 0.15 wt% of ethanolamine, 0.01 wt% of polysiloxane, and 49.84 wt% of N-methylpyrrolidone, which were thoroughly mixed, based on the total weight of 100wt%, to give dispersant 3 of the present example.
Example 4
The dispersant comprised 5wt% of polyvinylpyrrolidone, 40 wt% of the polyether urethane of formula I-1, 0.1wt% of ethanolamine, 0.02 wt% of polysiloxane, and 54.88 wt% of N-methylpyrrolidone, all based on 100wt% of the total weight, were thoroughly mixed to give dispersant 4 of this example.
Example 5
The dispersant comprised 10 wt% of polyvinylpyrrolidone, 50 wt% of the polyether urethane of formula I-1, 0.15 wt% of ethanolamine, 0.01 wt% of polysiloxane, and 39.84 wt% of N-methylpyrrolidone, which were thoroughly mixed, based on the total weight of 100wt%, to give dispersant 5 of the present example.
Example 6
The dispersant comprised 15wt% of polyvinylpyrrolidone, 60wt% of the polyether urethane of formula I-1, 0.1wt% of ethanolamine, 0.02 wt% of polysiloxane, and 24.88 wt% of N-methylpyrrolidone, all based on 100wt% of the total weight, which were thoroughly mixed, to give dispersant 6 of this example.
Example 7
The dispersant comprised 5wt% of polyvinylpyrrolidone, 25 wt% of the polyether urethane of formula I-1, 0.2 wt% of ethanolamine, 0.01 wt% of polysiloxane, and 69.79 wt% of N-methylpyrrolidone, all based on 100wt% of the total weight, and was thoroughly mixed to give dispersant 7 of this example.
Example 8
The dispersant comprised 10% by weight of polyvinylpyrrolidone, 30% by weight of the polyether urethane of formula I-1, 0.4% by weight of ethanolamine, 0.02% by weight of polysiloxane, and 59.58% by weight of N-methylpyrrolidone, all of which were thoroughly mixed, based on 100% by weight of the total dispersant, to give dispersant 8 of this example.
Example 9
The dispersant comprised 15wt% of polyvinylpyrrolidone, 45 wt% of the polyether urethane of formula I-1, 0.5 wt% of ethanolamine, 0.02 wt% of polysiloxane, and 39.48 wt% of N-methylpyrrolidone, all based on 100wt% of the total weight, were thoroughly mixed to give dispersant 9 of this example.
Example 10
The dispersant of this example 10 was obtained by thoroughly and uniformly mixing 10 wt% of polyacrylamide, 20 wt% of the polyether urethane of formula I-1, 0.1wt% of ethanolamine, and 0.02 wt% of polysiloxane in 69.88 wt% of N-methylpyrrolidone, based on 100wt% of the total weight.
Example 11
The dispersant of this example, dispersant 11, was obtained by thoroughly and uniformly mixing 10 wt% of polyvinylpyrrolidone, 20 wt% of the polyether urethane of formula I-1, 0.1wt% of hexamethylenediamine, and 0.02 wt% of polysiloxane in 69.88 wt% of N-methylpyrrolidone, based on 100wt% of the total weight.
Example 12
The dispersant of this example 12 was obtained by thoroughly and uniformly mixing 10 wt% of polyvinylpyrrolidone, 20 wt% of the polyether urethane of formula I-1, 0.1wt% of ethanolamine, and 0.02 wt% of polysiloxane in 69.88 wt% of dimethyl carbonate, based on 100wt% of the total weight.
Comparative example 1
The dispersant comprised 30 wt% of polyvinylpyrrolidone, 0.1wt% of ethanolamine, 0.02 wt% of polysiloxane, and 69.88 wt% of N-methylpyrrolidone, which were thoroughly mixed, based on 100wt% of the total weight, to obtain dispersant 13 of this comparative example.
To illustrate the dispersing effect of the dispersant of the present invention, the dispersant prepared in examples 1 to 12 was added to a mixed slurry of a commercially available binder-N-methylpyrrolidone (e.g., HSV 900-N-methylpyrrolidone mixed slurry, and suwei 5130-N-methylpyrrolidone mixed slurry), the viscosity value of the mixed slurry after the addition of the dispersant of the present invention was measured, and whether there was a color change or not was observed.
Wherein, the weight ratio of each component in each embodiment is kept consistent, and the weight ratio of the total weight of the binder and the dispersant to the N-methyl pyrrolidone is 1: 49.
TABLE 1 viscosity number and color change test results
Wherein the content of the first and second substances,
the detection method of the viscosity comprises the following steps: keeping the temperature of a sample to be detected in a constant-temperature water bath at 25 ℃ for 1h, and detecting by using an NDJ-5S digital rotational viscometer, wherein a rotor: number 4; rotating speed: 6rpm, detection temperature: at 25 ℃.
As can be seen from the test results in table 1, when the dispersant of the present invention is added to a commercially available binder-N-methylpyrrolidone mixed slurry, the viscosity of the mixed slurry can be effectively improved, and when the component a is preferably polyvinylpyrrolidone, the component B is preferably ethanolamine, and the solvent is preferably N-methylpyrrolidone, the viscosity is greatly improved, and the effect is remarkably improved. While the dispersant 13 prepared in comparative example 1 was able to improve only slightly the viscosity of the commercial binder-N-methylpyrrolidone mixed slurry, and the effect was not significantly improved, it was found that the dispersant of the present invention has an excellent dispersing effect and can significantly improve the viscosity of the mixed slurry.
The following examples respectively prepare positive electrode pastes pertaining to the present invention using specific component amounts, and positive electrode pastes not listed within the scope of the present invention have the same effects of use.
Example 13
The lithium iron phosphate battery positive electrode slurry is formed by mixing solid dry materials and N-methyl pyrrolidone (wherein the weight of the N-methyl pyrrolidone is 41.75 wt% of the total weight of the positive electrode slurry). Based on the total weight of 100 wt%: the solid dry materials in the anode slurry comprise 94.75 wt% of lithium iron phosphate, 2.5 wt% of Super P, 0.15 wt% of dispersing agent 2 and 2.6 wt% of polyvinylidene fluoride.
Polyvinylidene fluoride and Super P are stirred in N-methylpyrrolidone for 20 minutes at a speed of 400 rpm, lithium iron phosphate is added and stirred for 10 minutes at a speed of 200 rpm, dispersant 2 is added and stirred for 70 minutes at a speed of 2000 rpm, and anode slurry 1 is obtained.
Example 14
The lithium iron phosphate battery positive electrode slurry is formed by mixing solid dry materials and N-methyl pyrrolidone (wherein the weight of the N-methyl pyrrolidone is 41.9 wt% of the total weight of the positive electrode slurry). Based on the total weight of 100 wt%: the solid dry materials in the anode slurry comprise 94.1 wt% of lithium iron phosphate, 2.8 wt% of Super P, 0.2 wt% of dispersing agent 3 and 2.9 wt% of polyvinylidene fluoride.
Polyvinylidene fluoride and Super P are stirred in N-methylpyrrolidone for 20 minutes at a speed of 400 rpm, lithium iron phosphate is added and stirred for 10 minutes at a speed of 200 rpm, a dispersing agent 3 is added and then stirred for 60 minutes at a speed of 2000 rpm, and an anode slurry 2 is obtained.
Example 15
The lithium iron phosphate battery positive electrode slurry is formed by mixing solid dry materials and N-methyl pyrrolidone (wherein the weight of the N-methyl pyrrolidone is 41.7 wt% of the total weight of the positive electrode slurry). Based on the total weight of 100 wt%: the solid dry materials in the anode slurry comprise 93.9 wt% of lithium iron phosphate, 2.9 wt% of Super P, 0.3 wt% of dispersing agent 4 and 2.9 wt% of polyvinylidene fluoride.
Polyvinylidene fluoride and Super P are stirred in N-methylpyrrolidone for 20 minutes at a speed of 400 rpm, lithium iron phosphate is added and stirred for 10 minutes at a speed of 200 rpm, a dispersing agent 4 is added and then stirred for 70 minutes at a speed of 2000 rpm, and anode slurry 3 is obtained.
Example 16
The lithium iron phosphate battery positive electrode slurry is formed by mixing solid dry materials and N-methyl pyrrolidone (wherein the weight of the N-methyl pyrrolidone is 41.7 wt% of the total weight of the positive electrode slurry). Based on the total weight of 100 wt%: the solid dry materials in the anode slurry comprise 93.75 wt% of lithium iron phosphate, 3 wt% of Super P, 0.25 wt% of dispersing agent 5 and 3 wt% of polyvinylidene fluoride.
Polyvinylidene fluoride and Super P are stirred in N-methylpyrrolidone for 20 minutes at a speed of 400 rpm, lithium iron phosphate is added and stirred for 10 minutes at a speed of 200 rpm, a dispersing agent 5 is added and then stirred for 70 minutes at a speed of 2000 rpm, and anode slurry 4 is obtained.
Example 17
The lithium iron phosphate battery positive electrode slurry is formed by mixing solid dry materials and N-methyl pyrrolidone (wherein the weight of the N-methyl pyrrolidone is 41.75 wt% of the total weight of the positive electrode slurry). Based on the total weight of 100 wt%: the solid dry materials in the anode slurry comprise 94.75 wt% of lithium iron phosphate, 2.5 wt% of Super P, 0.15 wt% of dispersing agent 10 and 2.6 wt% of polyvinylidene fluoride.
Polyvinylidene fluoride and Super P are stirred in N-methylpyrrolidone for 20 minutes at a speed of 400 rpm, lithium iron phosphate is added and stirred for 10 minutes at a speed of 200 rpm, a dispersing agent 10 is added and then stirred for 120 minutes at a speed of 2000 rpm, and anode slurry 5 is obtained.
Example 18
The lithium iron phosphate battery positive electrode slurry is formed by mixing solid dry materials and N-methyl pyrrolidone (wherein the weight of the N-methyl pyrrolidone is 41.9 wt% of the total weight of the positive electrode slurry). Based on the total weight of 100 wt%: the solid dry materials in the anode slurry comprise 94.1 wt% of lithium iron phosphate, 2.8 wt% of Super P, 0.2 wt% of dispersing agent 11 and 2.9 wt% of polyvinylidene fluoride.
Polyvinylidene fluoride and Super P are stirred in N-methylpyrrolidone for 20 minutes at a speed of 400 rpm, lithium iron phosphate is added and stirred for 10 minutes at a speed of 200 rpm, a dispersing agent 11 is added and then stirred for 140 minutes at a speed of 2000 rpm, and the anode slurry 6 is obtained.
Example 19
The lithium iron phosphate battery positive electrode slurry is formed by mixing solid dry materials and N-methyl pyrrolidone (wherein the weight of the N-methyl pyrrolidone is 41.7 wt% of the total weight of the positive electrode slurry). Based on the total weight of 100 wt%: the solid dry materials in the anode slurry comprise 93.9 wt% of lithium iron phosphate, 2.9 wt% of Super P, 0.3 wt% of dispersing agent 12 and 2.9 wt% of polyvinylidene fluoride.
Polyvinylidene fluoride and Super P are stirred in N-methylpyrrolidone for 20 minutes at a speed of 400 rpm, lithium iron phosphate is added and stirred for 10 minutes at a speed of 200 rpm, a dispersing agent 12 is added and then stirred for 150 minutes at a speed of 2000 rpm, and anode slurry 7 is obtained.
Example 20
The lithium iron phosphate battery positive electrode slurry is formed by mixing solid dry materials and N-methyl pyrrolidone (wherein the weight of the N-methyl pyrrolidone is 37.35 wt% of the total weight of the positive electrode slurry). Based on the total weight of 100 wt%: the solid dry materials in the anode slurry comprise 94.1 wt% of lithium iron phosphate, 2.8 wt% of Super P, 0.2 wt% of dispersing agent 3 and 2.9 wt% of polyvinylidene fluoride.
Polyvinylidene fluoride and Super P are stirred in N-methylpyrrolidone for 20 minutes at a speed of 400 rpm, lithium iron phosphate is added and stirred for 10 minutes at a speed of 200 rpm, dispersant 3 is added and then stirred for 160 minutes at a speed of 2000 rpm, and anode slurry 8 is obtained.
Example 21
The lithium iron phosphate battery positive electrode slurry is formed by mixing solid dry materials and N-methyl pyrrolidone (wherein the weight of the N-methyl pyrrolidone is 35.8 wt% of the total weight of the positive electrode slurry). Based on the total weight of 100 wt%: the solid dry materials in the anode slurry comprise 93.75 wt% of lithium iron phosphate, 3 wt% of Super P, 0.25 wt% of dispersing agent 4 and 3 wt% of polyvinylidene fluoride.
Polyvinylidene fluoride and Super P are stirred in N-methylpyrrolidone for 20 minutes at a speed of 400 rpm, lithium iron phosphate is added and stirred for 10 minutes at a speed of 200 rpm, dispersant 4 is added and stirred for 170 minutes at a speed of 2000 rpm, and anode slurry 9 is obtained.
Comparative example 2
The lithium iron phosphate battery positive electrode slurry is formed by mixing solid dry materials and N-methyl pyrrolidone (wherein the weight of the N-methyl pyrrolidone is 41.7 wt% of the total weight of the positive electrode slurry). Based on the total weight of 100 wt%: the solid dry materials in the anode slurry comprise 93.75 wt% of lithium iron phosphate, 3 wt% of Super P, 0.25 wt% of dispersing agent 13 and 3 wt% of polyvinylidene fluoride.
Polyvinylidene fluoride and Super P are stirred in N-methylpyrrolidone for 20 minutes at a speed of 400 rpm, lithium iron phosphate is added and stirred for 10 minutes at a speed of 200 rpm, dispersing agent 13 is added and then stirred for 270 minutes at a speed of 2000 rpm, and anode slurry 10 is obtained.
As can be seen from comparison of the positive electrode pastes 1 to 9 prepared in examples 13 to 21 with the positive electrode paste 10 prepared in comparative example 2, the positive electrode paste prepared from the dispersant of the present invention can be uniformly dispersed with less solvent, and can be prepared in a shorter time.
The solid content and the viscosity of the positive electrode slurry 1-10 were respectively detected, and the detection results are shown in table 2.
TABLE 2 solid content and viscosity of positive electrode slurry 1-10
Solid content (%) | Viscosity (mPa.s) | |
Example 13 | 58.1 | 9078 |
Example 14 | 57.9 | 8869 |
Example 15 | 58.2 | 9106 |
Example 16 | 58.1 | 9085 |
Example 17 | 58.1 | 9445 |
Example 18 | 57.9 | 9558 |
Example 19 | 58.2 | 9668 |
Example 20 | 62.5 | 13895 |
Example 21 | 64.1 | 14057 |
Comparative example 2 | 58.1 | 14327 |
Wherein the content of the first and second substances,
the solid content detection method comprises the following steps: the percentage of the weight of the sample after being dried at 120 ℃ for 4 hours to the weight of the sample before being dried;
the detection method of the viscosity comprises the following steps: keeping the temperature of a sample to be detected in a constant-temperature water bath at 25 ℃ for 1h, and detecting by using an NDJ-5S digital rotational viscometer, wherein a rotor: number 4; rotating speed: 6rpm, detection temperature: at 25 ℃.
As can be seen from a comparison of example 16 and comparative example 2, the positive electrode slurry prepared using the dispersant of the present invention has the same solid content as the positive electrode slurry prepared in comparative example 2, but the positive electrode slurry prepared using the dispersant of example 2 of the present invention has significantly less viscosity; as can be seen from a comparison between example 21 and comparative example 2, when the positive electrode slurry prepared by the dispersant of the present invention has a viscosity comparable to that of the positive electrode slurry prepared by comparative example 2, the positive electrode slurry prepared by the dispersant of the present invention has a relatively high solid content, and uniform dispersion of the positive electrode slurry can be achieved using relatively less solvent.
From the comparison of example 17 with example 13, the comparison of example 18 with example 14, and the comparison of example 19 with example 15, it can be seen that when the a component is preferably polyvinylpyrrolidone, the B component is preferably ethanolamine, and the organic solvent is N-methylpyrrolidone, the positive electrode slurry prepared by the present invention has a better viscosity at the same solid content.
In summary, compared with the prior art, when the solid content in the positive electrode slurry is the same, the positive electrode slurry of the invention has lower viscosity, and when the viscosity in the positive electrode slurry is the same, the positive electrode slurry of the invention has higher solid content. Namely, the positive electrode slurry prepared by the dispersant provided by the invention has both lower viscosity and higher solid content.
Coating the positive electrode slurry 1-10 on a positive electrode sheet, drying to obtain a positive electrode sheet core, and observing whether the surface of the chip has wrinkles, broken strips or scratches and foil leakage, wherein the detection results are shown in table 3.
TABLE 3 results of the coating effect test
Fold (A) | Broken belt | Scratch leaking foil | |
Example 13 | √ | √ | √ |
Example 14 | √ | √ | √ |
Example 15 | √ | √ | √ |
Example 16 | √ | √ | √ |
Example 17 | √ | √ | √ |
Example 18 | √ | √ | √ |
Example 19 | √ | √ | √ |
Example 20 | √ | √ | √ |
Example 21 | √ | √ | √ |
Comparative example 2 | √ | √ | × |
Note: the "check" indicates a pass and the "no-pass" indicates an "x".
The results in table 3 show that the dispersant of the present invention has good coating effect, no wrinkle, tape breakage or scratch and foil leakage, and good flexibility when applied to the positive electrode slurry.
In conclusion, the positive electrode slurry prepared by the dispersant has higher solid content and lower viscosity, can realize uniform dispersion of the positive electrode slurry by using relatively less solvent, effectively saves the time of a production process and improves the production efficiency; in addition, after the positive electrode slurry obtained by dispersing the dispersing agent disclosed by the invention is coated, the problems of wrinkles, broken strips or scratches and foil leakage can be effectively solved, the dispersing agent has better flexibility and is suitable for industrial production, and the viscosity of the positive electrode slurry can be effectively improved by adding the dispersing agent disclosed by the invention into a commercially available binder-N-methyl pyrrolidone mixed slurry.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the present invention is not limited thereto, and equivalent changes and modifications made according to the spirit of the present invention should be covered thereby.
Claims (10)
1. The dispersing agent for the lithium ion battery positive electrode slurry is characterized by comprising the following components in percentage by weight of 100wt% in total: 5-15 wt% of component A, 15-60 wt% of polyether polyurethane containing comb structure, 0.01-1 wt% of component B, 0.001-0.1 wt% of component C, and the balance of organic solvent,
wherein the content of the first and second substances,
the component A is selected from one or the combination of at least two of polyvinylpyrrolidone, polyacrylamide, hydroxyethyl cellulose and polyoxyethylene copolymer;
the component B is selected from one or the combination of at least two of hexamethylene diamine, tertiary amine and ethanolamine; and
the component C is selected from one or a combination of at least two of polysiloxane, polyether compound and modified organosilicon.
2. The dispersing agent for the lithium ion battery positive electrode slurry according to claim 1, wherein the polyether polyurethane containing the comb-like structure is a compound represented by a general formula I:
wherein the content of the first and second substances,
n represents an integer of 0 to 100;
A 1 represents H atom, alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 4 carbon atoms, or alkenyl group having 2 to 5 carbon atoms;
Denotes the attachment site in the bonded structure.
5. The dispersant for lithium ion battery positive electrode slurry according to claim 1, wherein the organic solvent is one or a combination of at least two selected from the group consisting of N-methylpyrrolidone, dimethyl carbonate, diethyl carbonate, ethyl acetate, and methyl propionate.
6. A lithium ion battery positive electrode slurry comprising the dispersant of any one of claims 1 to 5, wherein the positive electrode slurry is formed by mixing a solid dry material and an organic solvent.
7. The positive electrode slurry of the lithium ion battery according to claim 6, wherein the solid dry materials in the positive electrode slurry comprise 85-98 wt% of lithium iron phosphate, 0.5-8 wt% of a conductive agent, 0.1-1 wt% of the dispersing agent, and 1-8 wt% of a binder, based on 100wt% of the total weight.
8. The lithium ion battery cathode slurry according to claim 6, wherein the weight of the organic solvent is 35-50 wt% of the total weight of the cathode slurry.
9. The lithium ion battery positive electrode slurry according to claim 7, wherein the conductive agent is selected from one or a combination of at least two of a graphite conductive agent, conductive carbon black, graphene and a metal powder.
10. The lithium ion battery positive electrode slurry according to claim 7, wherein the binder is one or a combination of at least two selected from polyvinylidene fluoride, sodium carboxymethylcellulose, styrene-butadiene rubber, sodium alginate, polyacrylic acid and polyethylene oxide.
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CN115863643A (en) * | 2022-12-10 | 2023-03-28 | 安徽皓飞新材料有限公司 | Dispersing and softening agent for lithium ion battery anode slurry and application thereof |
CN116589649A (en) * | 2023-07-14 | 2023-08-15 | 宁德时代新能源科技股份有限公司 | Polymer, preparation method, dispersing agent, positive electrode slurry, positive electrode plate, secondary battery and electricity utilization device |
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CN116589649B (en) * | 2023-07-14 | 2023-12-22 | 宁德时代新能源科技股份有限公司 | Polymer, preparation method, dispersing agent, positive electrode slurry, positive electrode plate, secondary battery and electricity utilization device |
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