CN107275574A - Preparation method, lithium battery anode piece and the lithium battery of positive pole aqueous slurry - Google Patents
Preparation method, lithium battery anode piece and the lithium battery of positive pole aqueous slurry Download PDFInfo
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- CN107275574A CN107275574A CN201710414118.2A CN201710414118A CN107275574A CN 107275574 A CN107275574 A CN 107275574A CN 201710414118 A CN201710414118 A CN 201710414118A CN 107275574 A CN107275574 A CN 107275574A
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- acid
- active material
- positive
- slurry
- aqueous solution
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- 239000002002 slurry Substances 0.000 title claims abstract description 55
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 claims abstract description 55
- 239000007864 aqueous solution Substances 0.000 claims abstract description 52
- 230000002378 acidificating effect Effects 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011230 binding agent Substances 0.000 claims abstract description 30
- 239000002562 thickening agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 239000006258 conductive agent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 238000009288 screen filtration Methods 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229910018058 Ni-Co-Al Inorganic materials 0.000 claims description 3
- 229910018102 Ni-Mn-Al Inorganic materials 0.000 claims description 3
- 229910018144 Ni—Co—Al Inorganic materials 0.000 claims description 3
- 229910018548 Ni—Mn—Al Inorganic materials 0.000 claims description 3
- 229910018539 Ni—Mn—Co Inorganic materials 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229960005137 succinic acid Drugs 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 230000033228 biological regulation Effects 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 9
- 239000000243 solution Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000005030 aluminium foil Substances 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 230000006378 damage Effects 0.000 abstract description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 20
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 238000004513 sizing Methods 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- -1 Ni-Co-Al systems Chemical class 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 1
- 206010049244 Ankyloglossia congenital Diseases 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000000368 destabilizing effect Effects 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002224 dissection Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 210000004508 polar body Anatomy 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000003643 water by type Substances 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/624—Electric conductive fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Preparation method, lithium battery anode piece and the lithium battery of positive pole aqueous slurry, the positive pole aqueous slurry are mixed by positive active material, conductive agent, thickener, binding agent and acidic aqueous solution, and step is as follows：Acidic aqueous solution and positive active material are mixed, positive active material is modified, the pH value for making system after mixing is 7~8；Add other components and carry out conjunction slurry.The present invention is modified using slightly acidic water solution to the positive active material of high ph-values, destruction of the acidic aqueous solution to water-based thickener and aqueous binders can be avoided, nickelic positive electrode high temperature storage is improved with this and expands larger defect, the storage stability and coating performance of slurry are improved, the cycle life of lithium ion battery is extended.And the corrosion of high ph-values positive electrode active material confrontation aluminium foil can be reduced, so as to lift product yield and improve production efficiency.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of preparation method of lithium battery anode slurry, lithium
Battery positive pole piece and lithium battery.
Background technology
Lithium ion battery is widely used in portable type electronic product as the energy storage device of current mainstream electronic product, electricity
On the product such as power driven tools and electric automobile.With the continuous expansion of domestic and international electric automobile market, the demand of lithium ion battery
Also constantly increase.Lithium ion battery is famous with green high-capacity environment-protecting, has that energy density is high due to it, has extended cycle life, works
The advantages of voltage is high, becomes one of electrical source of power for attracting most attention.
Traditional anode slice of lithium ion battery typically uses fluoropolymer, and such as Kynoar (PVDF) is as positive pole
The binding agent of material, PVDF binding agents need substantial amounts of organic solvent in use, such as N- methyl pyrrolidones (NMP),
Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) etc. are dissolved, then carry out slurry-stirring process.Because organic solvent is easy
Cause environmental pollution, therefore need in coating drying process to be added to and original reclaim organic solvent；On the other hand, NMP etc. has
Machine solvent belongs to high boiling solvent, and drying completely is wanted during coating, it is necessary to longer baking oven length and higher baking oven temperature
Degree, greatly, it is coated with the production efficiency that production capacity seriously limits enterprise to energy consumption during coating, has become the bottleneck work of restriction production capacity
Sequence.
In recent years, above-mentioned lack in order to produced when solving to make positive plate using fluoropolymer solvents type binding agent
Fall into, new green, environmentally friendly, the free of contamination aqueous positive-pole system of exploitation is being made great efforts in major lithium battery factories commercial city, yet with
Nickelic positive electrode shows stronger alkalescence in itself, and easy adsorbed water molecule simultaneously reacts with water, can heavy corrosion using water-based system
Aluminium foil, causes pole piece inside aperture greatly, pliability is poor, capacity reduction, cycle performance is deteriorated, it is impossible to meet electrodes of lithium-ion batteries
Production requirement, seriously limit the practical application of positive pole water system system.
In order to improve the electrical property of positive pole water-based system, Publication No. CN105940530A Chinese invention patent application is public
A kind of preparation method of the anode sizing agent for the lithium rechargeable battery opened, use acid neutralize mode come adjust the pH value of slurry with
The positive active material suppressed in anode sizing agent reacts with water, and this method is first by water-based thickener (CMC), aqueous binders, pH
Regulator (acidic aqueous solution) is kneaded in advance, and the positive active material of strong basicity is added after mixing.This method is mixed in early stage
CMC molecular structure can be greatly destroyed during refining acidic aqueous solution, causes its molecular weight step-down of degrading, reduces the anti-settling of CMC
Effect drops, while under acid condition, aqueous binders similarly have destabilizing factor, particle diameter is big, and the easy Precipitation of micelle is whole
Body positive pole water paste storage stability is poor, and coating yield is low.
The content of the invention
It is an object of the invention to provide a kind of preparation method of lithium ion cell positive aqueous slurry, in particular for containing
There is the positive pole aqueous slurry of the positive active material of high ph-values.
The present invention also aims to provide a kind of lithium battery anode piece and lithium battery.
To achieve these goals, the present invention takes following technical solution：
The preparation method of positive pole aqueous slurry, the positive pole aqueous slurry by positive active material, conductive agent, thickener,
Binding agent and acidic aqueous solution are mixed, and step is as follows：
Acidic aqueous solution and positive active material are mixed, positive active material is modified, makes body after mixing
The pH value of system is 7~8；
Add other components and carry out conjunction slurry.
More specifically, the acidic aqueous solution is slightly acidic water solution.
More specifically, the concentration of the acidic aqueous solution is 1%~5%.
More specifically, the acid in the acidic aqueous solution be phosphoric acid, oxalic acid, acetic acid, carbonic acid, malonic acid, butanedioic acid, oneself two
One kind in acid, phthalic acid, salicylic acid, citric acid, toluenesulfonic acid, tartaric acid.
More specifically, the acid in the acidic aqueous solution is phosphoric acid or oxalic acid or acetic acid or carbonic acid.
More specifically, when being modified to positive active material, positive active material and acidic aqueous solution are added in container,
It is stirred under low temperature, acidic aqueous solution is continuously added in whipping process, until the pH value of system is 7~8.
More specifically, the temperature that positive active material and acidic aqueous solution are mixed is 5~10 DEG C.
More specifically, closed after positive active material and acidic aqueous solution being mixed when starching, first add conductive agent slurry and
Thickener, regulation slurry is in dough, and it is 4000~6000mPa.s to add deionized water by pulp dilution to viscosity, then is added
Enter binding agent to continue to stir, finally vacuumize and positive pole water paste is obtained after removing bubble, screen filtration.
More specifically, the pH value of the positive active material is 11.5~12.5.
More specifically, positive active material is stated for nickeliferous lithium complex chemical compound.
More specifically, the positive active material is that Ni-Mn-Co systems or Ni-Mn-Al systems or Ni-Co-Al systems are combined chemical combination
Thing.
Lithium battery anode piece, including collector and the positive electrode active material layer that is formed on collection liquid surface, it is described just
Pole active material layer is coated on collection liquid surface by aforementioned positive electrode aqueous slurry and formed.
More specifically, the coating speed of positive pole aqueous slurry is 25~35m/s.
More specifically, be dried after coating with 5 sections of baking ovens, the temperature of every section of baking oven is respectively 60 DEG C, 70 DEG C, 90 DEG C,
120℃、120℃。
Lithium battery, is formed by anode pole piece, cathode pole piece and membrane winding, and the anode pole piece is foregoing lithium battery anode
Pole piece.
From above technical scheme, the present invention when preparing anode sizing agent using slightly acidic water solution to high ph-values just
Pole active material is modified, and can be avoided destruction of the acidic aqueous solution to water-based thickener and aqueous binders, be improved with this
Nickelic positive electrode high temperature storage expands larger defect, improves the storage stability and coating performance of slurry, extends lithium
The cycle life of ion battery.Due to reducing the corrosion of high ph-values positive electrode active material confrontation aluminium foil, using the inventive method system
Pole piece coating surface no significant defect made from standby slurry, so as to lift product yield, improves production efficiency.
Brief description of the drawings
Fig. 1 is embodiment 1-4 and comparative example 2-3 anode pole piece peel-force data.
Fig. 2 is that battery 60 DEG C of storages, 14 days expansion rate comparison diagrams are made in embodiment 1-4 and comparative example 2-3.
Fig. 3 is that 70 DEG C of storage 48h expansion rate comparison diagrams of battery are made in embodiment 1-4 and comparative example 2-3.
Fig. 4 is embodiment 3 and 25 DEG C of circulation volume conservation rate curve maps of battery made from comparative example 3.
The embodiment of the present invention is described in more detail below in conjunction with accompanying drawing.
Embodiment
In order to which above and other objects of the present invention, feature and advantage can be become apparent from, the embodiment of the present invention cited below particularly,
It is described below in detail.
It is water-soluble that the positive pole aqueous slurry of the present invention includes positive active material, conductive agent, thickener, binding agent and acidity
Liquid.Wherein, in positive active material, conductive agent, thickener, binding agent composition positive pole material, positive pole material, positive active material
The 91.0~96.0% of positive pole material gross weight are accounted for, conductive agent accounts for the 1.0~3.0% of positive pole material gross weight, and thickener is accounted for just
The 1.0~2.0% of pole material gross weight, binding agent accounts for the 2.0~4.0% of positive pole material gross weight.Positive pole material each component
Proportioning is identical with routine techniques.
The present invention positive active material be high ph-values positive active material, such as Ni-Mn-Co systems, Ni-Mn-Al systems and
The nickeliferous lithium complex chemical compound such as Ni-Co-Al systems, concretely LiNi0.8Co0.1Mn0.1O2、LiNiO2、LiNi0.8Co0.15Al0.05O2
Etc. the general positive active material 11.5~12.5 or so of pH value, show neutral positive electrode active material for pH value such as LiFePO4s
The matter present invention is without actual effect.
The conductive agent that the present invention is used is conventional conductive material, can be graphite, conductive black, acetylene black,
One or more mixing in Ketjen black, carbon fiber, CNT and graphene, preferably use conductive black (Super P).
Thickener is water-based thickener, can be sodium carboxymethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, fixed
At least one of excellent glue, chitosan and cross-linking type polysaccharide structures polymer, polyvinyl alcohol, polyacrylic acid or multiple combinations.
Binding agent is aqueous binders, can be polyacrylamide, polyethylene glycol oxide, polyvinylpyrrolidone, acryloyl
Amine-acrylonitrile copolymer, acrylic acid and acrylic ester copolymers, acrylic acid-acrylamide-acrylonitrile copolymer, acrylic acid-the third
Olefin(e) acid ester-acrylonitrile copolymer, but be not limited only to this, aqueous binders can be it is any it is existing it is commercially available it is all have cementability and
Oxidation resistant high molecular polymer, preferably acrylic acid-acrylic ester-acrylonitrile copolymer.
Acidic aqueous solution is non-strong acid, and acidic aqueous solution is used to adjust positive active material pH value in the range of 7~8,
The acid of acidic aqueous solution can select phosphoric acid, oxalic acid, acetic acid, carbonic acid, malonic acid, butanedioic acid, adipic acid, phthalic acid, water
Poplar acid, citric acid, toluenesulfonic acid, tartaric acid etc., preferably use phosphoric acid or oxalic acid or acetic acid or carbonic acid.Acidic aqueous solution can use city
High-purity acidic materials+deionized water is sold, the acid solution that concentration is 1~5% is diluted to.The present invention acidic aqueous solution it is dense
Degree should not be too high, when concentration higher acidic solution, and reaction is violent, and local acid number is too high, can destroy positive active material
Configuration, reduction gram volume is played.
The preparation method of anode sizing agent of the present invention is as follows：
Positive active material is modified with acidic aqueous solution first, the pH value of mixed positive electrode active material plastidome
Adjust in the range of 7~8, then add other components and carry out conjunction slurry, it is specific as follows：
Positive active material is added in container, is stirred at low temperature, acid water is continuously added in whipping process
Solution, until the pH value of system is 7~8；Then conductive agent slurry and thickener are added, it is in dough to make slurry, is added
Ionized water is diluted to slurry, and binding agent is added when slurry viscosity is 4000~6000mPa.s, continues to stir, finally vacuumizes
Remove and obtain positive pole water paste after bubble, screen filtration.It is preferred that, it is stirred at 5~10 DEG C, to avoid temperature mistake
Height, reaction is violent, destroys positive active material.
Below by specific embodiment and comparative example, the present invention is further illustrated.Arrived used in the description below
Reagent, material and instrument are conventional reagent, conventional material and conventional instrument as without special explanation, commercially available
Obtain, involved reagent can also be synthesized by conventional synthesis process to be obtained.
Embodiment 1
The positive active material of the present embodiment is LiNi0.8Co0.15Al0.05O2, conductive agent is Super-P, and thickener is carboxylic
Sodium carboxymethylcellulose pyce (Japanese papery 500LC), binding agent is acrylic acid-acrylic ester-acrylonitrile copolymer, each in positive pole material
The proportioning of component is：Positive active material：Conductive agent：Thickener：The 93.5% of binding agent：2.5%：1.0%：3.0% (ratio
Example is the ratio of siccative quality).The binding agent acrylic monomers of the present embodiment is water-soluble preferable between 30~40%, selects
PH value is 4~5 polymeric binder, can further neutralize the alkaline components in positive active material, and acidic aqueous solution is used
Concentration is 3% phosphate aqueous solution.
The step of the present embodiment prepares slurry is as follows：
LiNi is added into double planetary mixer0.8Co0.15Al0.05O2, agitator tank temperature is reduced to 5~10 DEG C, it is slow to add
Enter phosphate aqueous solution, revolved round the sun 10RPM, stirring at low speed 30min, and phosphate aqueous solution is continuously added during stirring, until system pH
For 7~8；
Ground conductive agent slurry and thickener is added, it is in dough to adjust to slurry, stirs 2 hours, then adds
Deionized water adjusts slurry viscosity most 4000~6000mPa.s, adds binding agent, and revolve round the sun 15RPM, stirs 30min, then take out
Vacuum 30min removes bubble, finally with the screen filtration of 150 mesh, completes the preparation of aqueous positive-pole slurry.
The preparation method of the present embodiment conductive agent slurry is as follows：The aqueous of 5% solid content is added into double planetary mixer
Acrylate adhesives 2kg, is added after 1kg deionized waters, stirring 30min, adds 100g conductive blacks, and charging process continues
20min is stirred, it is then scattered 1 hour at a high speed, then with nanometer mill grinding 2 times, that is, obtain scattered electrocondution slurry.
It is made after anode sizing agent, anode sizing agent is applied on the aluminium foil surface of 13 μ m-thicks using transfer coater, is coated with
Speed is 35m/s (coating speed can be 25~35m/s, compared with oiliness 20m/s efficiency highs), is dried after coating with 5 sections of baking ovens,
Baking oven length is 15 meters (short compared with oiliness baking oven 5~10 meters), the temperature of every section of baking oven is respectively 60 DEG C, 70 DEG C, 90 DEG C, 120 DEG C,
120 DEG C (low compared with 130 DEG C of temperature of oiliness), carries out pressurized treatments with roll squeezer, compacted density is 3.5g/cm after drying3, it is made just
Pole pole piece, pole piece toughness is qualified.
Cathode pole piece is prepared using conventional formulation, negative pole material includes Delanium, super P, CMC and SBR binding agents,
Delanium, super P, CMC and SBR binding agents are mixed and made into cathode size, cathode size is coated on copper foil and dried
And roll-in, cathode pole piece is made.
The barrier film used is one side ceramics+two-sided aqueous PVDF-HFP copolymers gluing barrier film.
Electrolyte is prepared using conventional electrolysis formula of liquid：LiPF6+ (EC+FEC+PC+DEC+SN+PS+PC) solvents.
By anode pole piece, cathode pole piece and membrane winding into battery core, encapsulated using aluminum plastic film, 48 are toasted under vacuum state small
When go after moisture removal, inject electrolyte, battery be melted into and sorted, obtain thick wide long respectively 10mm, 60mm, 160mm
Square Soft Roll capacity be 10Ah lithium ion battery.
Embodiment 2
The present embodiment place different from embodiment 1 is：Acidic aqueous solution use concentration for 5% oxalic acid aqueous solution,
NCA positive electrodes are modified using oxalic acid aqueous solution as nertralizer.
Embodiment 3
The present embodiment place different from embodiment 1 is：Acidic aqueous solution use concentration for 5% acetic acid aqueous solution,
NCA positive electrodes are modified.
Embodiment 4
The present embodiment place different from embodiment 1 is：Acidic aqueous solution uses the unsaturated carbonate aqueous solution, and carbonic acid is water-soluble
The preparation method of liquid is as follows：In CO2Under atmosphere, pressurize 0.3~0.5MPa, handles 120~480 seconds, carbonate aqueous solution is made.By
In CO2Constantly volatilization, carbonate aqueous solution is unstable, and the present embodiment dissolves 1 volume CO using 1 volume of water2Ratio prepare saturated carbon
Aqueous acid.
Comparative example 1
The place different from embodiment 1 of comparative example 1 is that the preparation method of anode sizing agent is different, other all sames, contrast
Example 1 prepares anode sizing agent using the method for CN105940530A patent application publications：Into double planetary mixer add CMC and
Aqueous binders, add acetic acid aqueous solution, stir 30min, add positive active material, and to slurry dough, stirring 2 is small
When, then qualified viscosity is diluted to deionized water, final system pH is 7.4,30min removing bubbles is vacuumized, finally with 150
Mesh sieve net filtration, completes the preparation of aqueous positive-pole slurry.
Comparative example 2
The place different from comparative example 1 of comparative example 2 is：CMC consumptions increase to 2% by 1%.
Comparative example 3
Comparative example 3 is not being modified positive active material using acidic aqueous solution with the different places of embodiment 1,
Final slurry pH value is 12.3.
The stability of anode sizing agent made from embodiment 1-4 and comparative example 1-3 is contrasted, as a result as shown in table 1.
Table 1
From table 1 it follows that embodiment 1 is modified using phosphoric acid to positive active material, places 20 hours and occur
Slight precipitation, illustrates that phosphoric acid carrys out uncertain factor to aqueous positive polar body frenulum, phosphoric acid is middle strong acid, may be in blending process
Influence is produced on sludge proof CMC, and causes CMC anti-settling effects under the reduction of CMC molecular weight or acid condition poor.Embodiment
2 to 4 are neutralized using weak acid, whole system pH value is maintained in the range of 7~8,48h slurries are not precipitated, no gelatin phenomenon.Contrast
Example 1 adds positive electrode using CMC+ aqueous binders+acidic aqueous solution mixing, in first step batch mixing, acidic aqueous solution
CMC+ aqueous binders is in sour environment, be unfavorable for CMC anti-settling, destroy CMC molecular structure, slurry glues
Degree is low, and is precipitated after standing serious.CMC additions are increased to 2% by comparative example 2, and anti-settling performance makes moderate progress, and are stood after 8h
Also precipitation generates.Comparative example 3 using acidic aqueous solution neutralize so that aqueous positive-pole slurry system pH value is higher, NCA easily with
Water reacts, and gel particle is produced after standing 4 hours, scraper is serious on a current collector for coating.
Battery made from embodiment 1-4 and comparative example 2-3 is subjected to peel test force, cycle charge discharge electrical testing and non-equality of temperature
The dilation test of the lower storage of degree, method of testing is with reference to company standard, and test result is as shown in table 2 and Fig. 1 to Fig. 4.
Table 2
The more unused acid of pole piece made from the anode sizing agent prepared it can be seen from table 2 and Fig. 1 to Fig. 4 with the inventive method
To pole piece made from the anode sizing agent of positive pole material modification, before and after roll-in, peeling force all increases significantly property solution, this be by
More stablize in the positive active material after modified neutralize, reduce the corrosion of strong basicity positive electrode active material confrontation foil, simultaneously
Add with aqueous binders compatibility, more uniformly spread positive active material, after coating coating densification flatness it is good.It is right
Ratio 2 is higher due to water-based thickener CMC contents, finds that portion of CMC is destroyed with reference to comparative example 1, peeling force is higher before roll-in,
Pressure process makes CMC strand displacements change, and the ability that destroyed CMC molecules resist extraneous stress is poor, therefore roll-in
Peeling force declines larger afterwards.
Lithium is not analysed in 0 degree of dissection of lithium battery made from embodiment 1 to 4, and lithium battery made from comparative example 2 slightly analyses lithium, mainly
Reason is water-based thickener CMC content increase, and battery internal resistance itself is larger.Lithium battery made from comparative example 3 has obvious analysis
Lithium phenomenon, illustrates that unneutralized NCA material scatters are poor, poor with water-based system matching.It follows that passing through the modified positive pole of acid
Active material, has neutralized the LiOH of residual, it is therefore prevented that the alkaline matter in NCA reacts with water, and then causes battery overall
Electrical property is obviously improved.The present invention also demonstrates weak acid system simultaneously, and such as oxalic acid and acetic acid have more preferable neutralization, compared
In phosphoric acid, acid weaker, reaction is gentle, will not destroy the physical property of water-based thickener, binding agent；Compared to carbonic acid, carbonic acid can be
Largely volatilized in coating process, cause remaining acidic materials to reduce, make neutralization not thorough, leave a part of alkaline matter.
From the point of view of 25 degree of 1C/1C loop test results, embodiment 3 is modified using acetic acid, for comparative example 3, circulates the longevity
Life is obviously improved, and is further illustrated the necessity of the modified positive pole NCA materials of acid, is prevented moisture and positive pole during repeated charge
A series of side reactions of alkaline matter in material.
In summary, the present invention is modified by acidic aqueous solution to positive active material, can improve aqueous positive-pole high
The electrical property of nickel system, is particularly helpful to reduce influence of the moisture content to high-nickel material, to improving anode pole piece planarization, reduction pair
The corrosivity of foil, improves pole piece peeling force, further improves the dilatancy of high temperature storage, while extending lithium ion battery
Cycle life.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
Embodiment illustrated herein is not intended to be limited to, and is to fit to consistent with principles disclosed herein and features of novelty
Widest range.
Claims (15)
1. the preparation method of positive pole aqueous slurry, the positive pole aqueous slurry is by positive active material, conductive agent, thickener, viscous
Knot agent and acidic aqueous solution are mixed, it is characterised in that step is as follows：
Acidic aqueous solution and positive active material are mixed, positive active material is modified, makes system after mixing
PH value is 7~8；
Add other components and carry out conjunction slurry.
2. the preparation method of positive pole aqueous slurry as claimed in claim 1, it is characterised in that：The acidic aqueous solution is weak acid
The property aqueous solution.
3. the preparation method of positive pole aqueous slurry as claimed in claim 1, it is characterised in that：The concentration of the acidic aqueous solution
For 1%~5%.
4. the preparation method of positive pole aqueous slurry as claimed in claim 1 or 2, it is characterised in that：In the acidic aqueous solution
Acid be phosphoric acid, oxalic acid, acetic acid, carbonic acid, malonic acid, butanedioic acid, adipic acid, phthalic acid, salicylic acid, citric acid, toluene
One kind in sulfonic acid, tartaric acid.
5. the preparation method of positive pole aqueous slurry as claimed in claim 1 or 2, it is characterised in that：In the acidic aqueous solution
Acid be phosphoric acid or oxalic acid or acetic acid or carbonic acid.
6. the preparation method of positive pole aqueous slurry as claimed in claim 1, it is characterised in that：Positive active material is modified
When, positive active material and acidic aqueous solution are added in container, is stirred, is continuously added in whipping process at low temperature
Acidic aqueous solution, until the pH value of system is 7~8.
7. the preparation method of the positive pole aqueous slurry as described in claim 1 or 6, it is characterised in that：Positive active material and acid
Property the aqueous solution mix temperature be 5~10 DEG C.
8. the preparation method of the positive pole aqueous slurry as described in claim 1 or 6, it is characterised in that：By positive active material with
When acidic aqueous solution closes slurry after mixing, first add conductive agent slurry and thickener, regulation slurry is in dough, add from
Pulp dilution to viscosity is 4000~6000mPa.s by sub- water, is added binding agent and is continued to stir, finally vacuumizes removing gas
Positive pole water paste is obtained after bubble, screen filtration.
9. the preparation method of positive pole aqueous slurry as claimed in claim 1, it is characterised in that：The pH of the positive active material
It is worth for 11.5~12.5.
10. the preparation method of the positive pole aqueous slurry as described in claim 1 or 9, it is characterised in that：The positive active material
For nickeliferous lithium complex chemical compound.
11. the preparation method of the positive pole aqueous slurry as described in claim 1 or 9, it is characterised in that：The positive active material
For Ni-Mn-Co systems or Ni-Mn-Al systems or Ni-Co-Al systems complex chemical compound.
12. lithium battery anode piece, including collector and the positive electrode active material layer being formed on collection liquid surface, its feature exist
In：The positive electrode active material layer is coated on afflux body surface as the positive pole aqueous slurry as described in any one of claim 1 to 11
Face is formed.
13. lithium battery anode piece as claimed in claim 12, it is characterised in that：The coating speed of positive pole aqueous slurry is 25
~35m/s.
14. lithium battery anode piece as claimed in claim 12, it is characterised in that：It is dried after coating with 5 sections of baking ovens, often
The temperature of section baking oven is respectively 60 DEG C, 70 DEG C, 90 DEG C, 120 DEG C, 120 DEG C.
15. lithium battery, is formed by anode pole piece, cathode pole piece and membrane winding, it is characterised in that：The anode pole piece is as weighed
Profit requires the lithium battery anode piece described in 12 to 14 any one.
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| CN108448069B (en) * | 2017-11-23 | 2020-08-11 | 山东省科学院能源研究所 | Method for modifying high-nickel lithium ion battery positive electrode material |
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| CN109616657A (en) * | 2018-12-17 | 2019-04-12 | 中科廊坊过程工程研究院 | A kind of nickelic composite positive pole and its preparation method and application |
| CN109616657B (en) * | 2018-12-17 | 2022-04-15 | 廊坊绿色工业技术服务中心 | High-nickel composite positive electrode material and preparation method and application thereof |
| CN109585780A (en) * | 2018-12-24 | 2019-04-05 | 珠海光宇电池有限公司 | A kind of anode composite pole piece and preparation method thereof and the lithium ion battery containing the pole piece |
| CN110148707A (en) * | 2019-05-20 | 2019-08-20 | 长虹格兰博科技股份有限公司 | A kind of anode of secondary battery and preparation method |
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| CN114639801A (en) * | 2022-03-08 | 2022-06-17 | 厦门海辰新能源科技有限公司 | Positive pole piece and preparation method and application thereof |
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Application publication date: 20171020 |