CN105789573A - Positive electrode active material of lithium ion battery, preparation method for positive electrode active material, lithium ion battery positive electrode, and lithium ion battery - Google Patents
Positive electrode active material of lithium ion battery, preparation method for positive electrode active material, lithium ion battery positive electrode, and lithium ion battery Download PDFInfo
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- CN105789573A CN105789573A CN201610123982.2A CN201610123982A CN105789573A CN 105789573 A CN105789573 A CN 105789573A CN 201610123982 A CN201610123982 A CN 201610123982A CN 105789573 A CN105789573 A CN 105789573A
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- Prior art keywords
- lithium
- lithium ion
- ion battery
- source
- carbon
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 78
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 147
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 62
- 239000006258 conductive agent Substances 0.000 claims abstract description 55
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 51
- 239000002002 slurry Substances 0.000 claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000006229 carbon black Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 28
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims description 27
- 239000005011 phenolic resin Substances 0.000 claims description 26
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 24
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 24
- 239000008103 glucose Substances 0.000 claims description 24
- 229920001568 phenolic resin Polymers 0.000 claims description 24
- 239000006183 anode active material Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 12
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- -1 Lauxite Polymers 0.000 claims description 11
- 230000004888 barrier function Effects 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 150000002505 iron Chemical class 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- 239000001667 (E)-4-furan-2-ylbut-3-en-2-one Substances 0.000 claims description 2
- GBKGJMYPQZODMI-SNAWJCMRSA-N (e)-4-(furan-2-yl)but-3-en-2-one Chemical compound CC(=O)\C=C\C1=CC=CO1 GBKGJMYPQZODMI-SNAWJCMRSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
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- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003180 amino resin Polymers 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 229940046149 ferrous bromide Drugs 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 229960001781 ferrous sulfate Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- ANAGEECPKFGKEL-UHFFFAOYSA-N furan-2-carbaldehyde;phenol Chemical compound OC1=CC=CC=C1.O=CC1=CC=CO1 ANAGEECPKFGKEL-UHFFFAOYSA-N 0.000 claims description 2
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 2
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- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 28
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract 1
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 19
- 229940116007 ferrous phosphate Drugs 0.000 description 19
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 19
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 19
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 238000007599 discharging Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000008053 sultones Chemical class 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of a battery material, and discloses a positive electrode active material of a lithium ion battery, a preparation method for the positive electrode active material, a lithium ion battery positive electrode, and the lithium ion battery. The preparation method for the positive electrode active material of the lithium ion batter comprises the steps of (1) mixing a phosphorus source, an iron source, a lithium source, a carbon source and a solvent to obtain slurry; (2) drying the slurry to obtain a precursor, and then smashing the precursor to obtain precursor powder; and (3) roasting the precursor powder under protective atmosphere, wherein the carbon source comprises at least one kind of carbohydrate, thermosetting resin, carbon black conductive agent and graphene. The lithium iron phosphate material prepared by the method has an obvious and relatively high conductive performance; and the lithium ion battery prepared from the material has obvious and relatively low internal resistance and an obvious and relatively high cycling performance.
Description
Technical field
The present invention relates to field of lithium ion battery, in particular it relates to a kind of anode active material of lithium ion battery and preparation method thereof, lithium ion cell positive and lithium ion battery.
Background technology
Ferrousphosphate lithium material is one of mainstay material on present anode active material of lithium ion battery market both at home and abroad, because of the security performance of its brilliance, cycle performance, is the preferred material of current Prospect of EVS Powered with Batteries.But, because the feature of himself structure, its electric conductivity (such as electronic conductivity and ionic conductivity) is poor.This shortcoming makes the application of ferrousphosphate lithium material often be restricted.Present stage, being generally adopted carbothermic method and carry out carbon cladding, some, simultaneously also in relation with coated graphite, all achieves certain effect.But still can not reach some battery producer processing technology strict demand to anode active material of lithium ion battery performance.
Summary of the invention
The invention aims to overcome the defect that in prior art, the electric conductivity of ferrousphosphate lithium material is poor, it is provided that a kind of anode active material of lithium ion battery and preparation method thereof, lithium ion cell positive and lithium ion battery.
The present inventor has been surprisingly found that under study for action, when preparing anode active material of lithium ion battery LiFePO 4, add carbon source in the slurry, and carbon source is except including carbohydrate and thermosetting resin, also include in carbon black conductive agent and Graphene at least one time, the electric conductivity of the ferrousphosphate lithium material prepared can be significantly improved, and can substantially reduce the internal resistance of the lithium ion battery thus prepared and significantly improve the cycle performance of the lithium ion battery thus prepared.
Therefore, to achieve these goals, first aspect, the preparation method that the invention provides a kind of anode active material of lithium ion battery, the method includes:
(1) phosphorus source, source of iron, lithium source, carbon source and solvent are mixed, obtain slurry；
(2) by slurry drying, obtain presoma, then presoma is pulverized, obtain precursor powder；
(3) under protective atmosphere, precursor powder is carried out roasting；
Wherein, described carbon source includes at least one in carbohydrate, thermosetting resin and carbon black conductive agent and Graphene.
Second aspect, the invention provides the anode active material of lithium ion battery that method of the present invention prepares.
The third aspect, the invention provides a kind of lithium ion cell positive, described positive pole includes collector body and the positive electrode being positioned on collector body, described positive electrode contains positive electrode active materials, conductive agent and binding agent, and described positive electrode active materials is anode active material of lithium ion battery of the present invention.
Fourth aspect, the invention provides a kind of lithium ion battery, described lithium ion battery includes battery container and is positioned at the battery core assembly within battery container and electrolyte, and described battery core assembly includes positive pole, barrier film and negative pole, described lithium ion cell positive just extremely of the present invention.
By selecting specific carbon source to be obtained in that Surface coating has carbon in the method for the present invention, carbon dope covered effect is more excellent, there is the ferrous lithium phosphate cathode active material of specific morphology, and compared with the ferrousphosphate lithium material only selecting carbohydrate (such as glucose) to prepare as carbon source as carbon source or carbohydrate (such as glucose)+graphite as carbon source or carbon black conductive agent and/or Graphene as carbon source or thermosetting resin, the ferrousphosphate lithium material that the inventive method obtains has substantially better electric conductivity, its lithium ion battery prepared is adopted to have significantly lower internal resistance and better cycle performance.
A preferred embodiment of the invention, the 20Ah soft-package battery that the present invention prepares, internal resistance is at below 2m Ω, more preferably 1.0-1.2m Ω, Billy is with only selecting the carbohydrate (such as glucose) will low 40%-50% as the internal resistance of cell that the ferrousphosphate lithium material that carbon source or carbohydrate (such as glucose)+graphite prepare as carbon source is made as carbon source or carbon black conductive agent and/or Graphene as carbon source or thermosetting resin；23 DEG C, circulation 5000 times after capacity dimension holdup more than 76%, it is preferable that more than 81%.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Fig. 1 is the TEM figure of the anode active material of lithium ion battery LiFePO 4 that the embodiment of the present invention 1 prepares.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
First aspect, the preparation method that the invention provides a kind of anode active material of lithium ion battery, the method includes:
(1) phosphorus source, source of iron, lithium source, carbon source and solvent are mixed, obtain slurry；
(2) by slurry drying, obtain presoma, then presoma is pulverized, obtain precursor powder；
(3) under protective atmosphere, precursor powder is carried out roasting；
Wherein, described carbon source includes at least one in carbohydrate, thermosetting resin and carbon black conductive agent and Graphene.
In the method for the present invention, what those skilled in the art should understand that is, " carbon source includes at least one in carbohydrate, thermosetting resin and carbon black conductive agent and Graphene " refers to that carbon source is except including carbohydrate and thermosetting resin, also includes at least one in carbon black conductive agent and Graphene.
In the method for the present invention, the present inventor finds under study for action, when in P elements and carbon mole, the mol ratio of phosphorus source and carbon source is 1:(0.6-1.5) time, the electric conductivity of the ferrousphosphate lithium material prepared can be significantly improved, and can substantially reduce the internal resistance of the lithium ion battery thus prepared；When in P elements and carbon mole, the mol ratio of phosphorus source and carbon source is 1:(1.1-1.4) time, the electric conductivity of the ferrousphosphate lithium material prepared can be improved further, and the internal resistance of the lithium ion battery thus prepared can be reduced further.It is therefore preferable that in situation, in P elements and carbon mole, the mol ratio of phosphorus source and carbon source is 1:(0.6-1.5), more preferably 1:(1.1-1.4).
In the method for the present invention, the present inventor finds under study for action, when the ratio of the carbon molal quantity sum in the molal quantity of carbon and carbon black conductive agent and Graphene in the molal quantity of carbon, thermosetting resin in carbohydrate is 1:(0.2-1.1): time (0.3-1.6), the electric conductivity of the ferrousphosphate lithium material prepared can be significantly improved, and can substantially reduce the internal resistance of the lithium ion battery thus prepared；When the ratio of the carbon molal quantity sum in the molal quantity of carbon and carbon black conductive agent and Graphene in the molal quantity of carbon, thermosetting resin in carbohydrate is 1:(0.8-1): time (0.9-1.2), the electric conductivity of the ferrousphosphate lithium material prepared can be improved further, and the internal resistance of the lithium ion battery thus prepared can be reduced further.Therefore, under preferable case, in carbon source, in carbohydrate, in the molal quantity of carbon, thermosetting resin, the ratio of the carbon molal quantity sum in the molal quantity of carbon and carbon black conductive agent and Graphene is 1:(0.2-1.1): (0.3-1.6), more preferably 1:(0.8-1): (0.9-1.2).
It will be understood by those skilled in the art that when carbon source includes carbohydrate, thermosetting resin and carbon black conductive agent, the carbon molal quantity that carbon molal quantity sum is carbon black conductive agent in carbon black conductive agent and Graphene；The carbon molal quantity that carbon molal quantity sum is Graphene when carbon source includes carbohydrate, thermosetting resin and Graphene, in carbon black conductive agent and Graphene；The carbon molal quantity sum that carbon molal quantity sum is carbon black conductive agent and Graphene when carbon source includes carbohydrate, thermosetting resin, carbon black conductive agent and Graphene, in carbon black conductive agent and Graphene.
In the method for the present invention, under preferable case, carbon source includes carbohydrate, thermosetting resin and Graphene, further preferably, carbon source includes carbohydrate, thermosetting resin, carbon black conductive agent and Graphene, it is further preferred that the mol ratio of carbon black conductive agent and Graphene is 1:(0.1-0.4).
Process of the present invention it is preferred in situation, carbohydrate is selected from one or more in glucose, sucrose, lactose, citric acid, Polyethylene Glycol and stearic acid, more preferably glucose and/or sucrose.
In the method for the present invention, under preferable case, thermosetting resin is selected from one or more in phenolic resin, Lauxite, melamine formaldehyde resin, epoxy resin, unsaturated polyester resin, amino resins, silicon ether resin, polyamide, polybutadiene, furfural phenol resin, furfural acetone resin, furfuryl alcohol resin and organic siliconresin, more preferably one or more in phenolic resin, epoxy resin, polyamide and Lauxite, are further preferably phenolic resin.In the present invention, each thermosetting resin is all commercially available.
In the method for the present invention, under preferable case, one or more in acetylene black, SuperP, 350G, carbon fiber, CNT and Ketjen black of carbon black conductive agent, more preferably one or more in SuperP, 350G and CNT, are further preferably CNT.In the present invention, each carbon black conductive agent is all commercially available.And it will be understood by those skilled in the art that in carbon black conductive agent of the present invention and do not include Graphene and graphite.
Process of the present invention it is preferred in situation, the addition controlling phosphorus source, source of iron and lithium source makes the mol ratio of P elements, ferrum element and elemental lithium in the slurry obtained be 1:(0.97-1): (1-1.02).
In the method for the present invention, for phosphorus source, there is no particular limitation, it is possible to for various phosphorus source commonly used in the art, it is preferable that in situation, and phosphorus source is selected from one or more in phosphoric acid, hydrophosphate and orthophosphate；It is further preferred that hydrophosphate is selected from one or more in ammonium dihydrogen phosphate, lithium dihydrogen phosphate and diammonium phosphate, orthophosphate is selected from iron phosphate and/or ammonium phosphate.
In the method for the present invention, for source of iron, there is no particular limitation, it is possible to for various sources of iron commonly used in the art, it is preferable that in situation, and source of iron is selected from one or more in iron phosphate, ferrum oxide, ferrous oxide, solubility divalent iron salt and solubility trivalent iron salt；It is further preferred that solubility divalent iron salt is selected from one or more in ferrous bromide, ferrous chloride, ferrous sulfate and ferrous nitrate, solubility trivalent iron salt is selected from one or more in ferric bromide, iron chloride, iron sulfate, ferric perchlorate and ferric nitrate.
In the method for the present invention, for lithium source, there is no particular limitation, can be various lithium sources commonly used in the art, under preferable case, lithium source is selected from one or more in lithium, Lithium hydrate, lithium bicarbonate, lithium phosphate, lithium carbonate, lithium acetate, lithium chloride, lithium dihydrogen phosphate, lithium oxalate and lithium nitrate.
In the method for the present invention, for solvent, there is no particular limitation, it is possible to for various solvents commonly used in the art, it is preferable that in situation, and solvent is selected from one or more in deionized water, dehydrated alcohol, isopropanol and acetone.The addition of solvent can fluctuate in relative broad range, for instance the weight of the solvent of addition can be 1-1.8 times of phosphorus source, source of iron, lithium source and carbon source gross weight.
In the method for the present invention, for obtaining the method for slurry, there is no particular limitation, it is possible to for various methods commonly used in the art, for instance can be that the mixture that mixing phosphorus source, source of iron, lithium source, carbon source and solvent obtain is ground mixing.
In the method for the present invention, for dry method, there is no particular limitation, it is possible to for various drying meanss commonly used in the art, for instance can be microwave drying, oven drying etc..Under preferable case, in step (2), dry condition includes: temperature is 120-250 DEG C, and the time is 1-4h.
In the method for the present invention, it is also possible to include presoma is pulverized the screening of laggard row, it is preferable that cross 60-100 mesh sieve, obtain precursor powder.
In the method for the present invention, for protective atmosphere, there is no particular limitation, it is possible to for various inert atmospheres commonly used in the art, such as nitrogen atmosphere (purity 99.999%), argon gas atmosphere (purity 99.999%).
Process of the present invention it is preferred in situation, in step (3), the condition of roasting includes: temperature is 700-800 DEG C, the time is 6-12h.
In the method for the present invention, it is also possible to the product including roasting being obtained carries out pulverizing, sieving, it is preferable that cross 200-300 mesh sieve, obtain ferrousphosphate lithium material.
Second aspect, the invention provides the anode active material of lithium ion battery that said method prepares.
The third aspect, the invention provides a kind of lithium ion cell positive, described positive pole includes collector body and the positive electrode being positioned on collector body, and described positive electrode contains positive electrode active materials, conductive agent and binding agent, and described positive electrode active materials is above-mentioned anode active material of lithium ion battery.
In the lithium ion cell positive of the present invention, for collector body, conductive agent and binding agent, there is no particular limitation, it is possible to various positive electrode collectors respectively commonly used in the art, conductive agent and binding agent.Such as positive electrode collector can be aluminium foil；Conductive agent can be one or more in ketjen carbon black, acetylene black, Graphene, carbon fiber VGCF, conductive carbon black；Binding agent can be one or more in polyvinylidene fluoride (PVDF), politef (PTFE), butadiene-styrene rubber (SBR) and cellulose-based polymer, and cellulose-based polymer can be selected from one or more in methylcellulose, ethyl cellulose, hydroxypropyl methyl cellulose and Cellulose ethyl hydroxypropyl ether.The number-average molecular weight of polyolefin compound and cellulose-based polymer is generally 30-80 ten thousand.Under normal circumstances, with the total amount of positive electrode for benchmark, the content of positive electrode active materials can be 85-98.5 weight %；With the total amount of positive electrode for benchmark, the total content of binding agent can be 0.5-10 weight %；With the total amount of positive electrode for benchmark, the content of conductive agent can be 0.5-10 weight %.
Wherein, lithium ion cell positive can be prepared by various methods of the prior art, for instance, it is possible to by the slurry containing positive electrode active materials, conductive agent and binding agent and solvent being coated with and/or fills on the current collector, dry, roll or obtain after not rolling.For the acquisition pattern of the slurry containing positive electrode active materials, conductive agent and binding agent and solvent, there is no particular limitation, as long as can by the slurry mix homogeneously containing aforementioned component, such as, slurry containing positive electrode active materials, conductive agent and binding agent and solvent can by after first mixing homogeneously positive electrode active materials and conductive agent, then the binder solution formed with solvent with binding agent, solvent or binding agent is mixed homogeneously and obtained；Can also pass through first by positive electrode active materials, binding agent and solvent mix homogeneously, then mix homogeneously with conductive agent again, obtain slurry.Described solvent can be N-Methyl pyrrolidone (NMP).The consumption of solvent can make described pastel have viscosity and mobility, it is possible to is coated on described collector body.Method and the condition dry, rolled are well known to those skilled in the art, and do not repeat them here.
Fourth aspect, the invention provides a kind of lithium ion battery, described lithium ion battery includes battery container and is positioned at the battery core assembly within battery container and electrolyte, and described battery core assembly includes positive pole, barrier film and negative pole, described just extremely above-mentioned lithium ion cell positive.
In the lithium ion battery of the present invention, the barrier film and the electrolyte that form lithium ion battery can be barrier film commonly used in the art and nonaqueous electrolytic solution.
Wherein, barrier film is arranged between positive pole and negative pole, and it has electrical insulation capability and liquid retainability energy, and makes battery core assembly be contained in battery case together with nonaqueous electrolytic solution.Barrier film can be various barrier films commonly used in the art, such as high molecular polymer microporous membrane, including the MULTILAYER COMPOSITE microporous membrane of polypropylene microporous membrane and polypropylene and polyethylene.The position of barrier film, character and kind are well known to those skilled in the art, and do not repeat them here.
Wherein, nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvent, and it is not particularly limited, it is possible to use the nonaqueous electrolytic solution that this area is conventional.Such as electrolyte lithium salt is selected from lithium hexafluoro phosphate (LiPF6), lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, one or more in chlorine lithium aluminate and fluorocarbon based Sulfonic Lithium.Nonaqueous solvent selects chain acid esters and ring-type acid esters mixed solution, wherein chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and other is fluorine-containing, at least one in sulfur-bearing or the chain organosilane ester containing unsaturated bond, ring-type acid esters can be ethylene carbonate (EC), Allyl carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other is fluorine-containing, at least one in sulfur-bearing or the ring-type organosilane ester containing unsaturated bond.The injection rate of electrolyte is generally 5-8 gram/ampere-hour, and the concentration of electrolyte is generally 0.8-1.2 mol/L.
In the lithium ion battery of the present invention, for battery container, there is no particular limitation, it is possible to for various battery containers commonly used in the art, this is well known to those skilled in the art, and does not repeat them here.
In the lithium ion battery of the present invention, negative pole includes collector body and the negative material being positioned on collector body, and described negative material contains negative active core-shell material, conductive agent, thickening agent and binding agent.For collector body, negative active core-shell material, conductive agent, thickening agent and binding agent, there is no particular limitation, it is possible to various negative electrode collectors respectively commonly used in the art, negative active core-shell material, conductive agent, thickening agent and binding agent.Such as negative electrode collector can be stamped metal, metal forming, net metal, foamed metal, it is preferred to carbon coated aluminum foil or electrolytic aluminum foil, more preferably carbon coated aluminum foil；Negative active core-shell material can be Carbon anode, alloy type negative pole or lithium titanate etc.；Conductive agent can be one or more in ketjen carbon black, acetylene black, Graphene, carbon fiber VGCF and conductive carbon black；Thickening agent can be sodium carboxymethyl cellulose (CMC), and binding agent can be one or more in polyvinylidene fluoride (PVDF), politef (PTFE) and butadiene-styrene rubber (SBR).Under normal circumstances, with the total amount of negative material for benchmark, the content of negative active core-shell material can be 90-98 weight %；With the weight of negative active core-shell material for benchmark, the content of conductive agent can be 0.8-5 weight %；With the weight of negative active core-shell material for benchmark, the content of thickening agent can be 1-5 weight %；With the weight of negative active core-shell material for benchmark, the content of binding agent can be 1-5 weight %.
Wherein, lithium ion battery negative can be prepared by various methods of the prior art, for instance, it is possible to by the slurry containing negative active core-shell material, conductive agent, thickening agent and binding agent and solvent being coated with and/or fills on the current collector, dry, roll or obtain after not rolling.For the acquisition pattern of the slurry containing negative active core-shell material, conductive agent, thickening agent and binding agent and solvent, there is no particular limitation, as long as can by the slurry mix homogeneously containing aforementioned component, such as, slurry containing negative active core-shell material, conductive agent, thickening agent and binding agent and solvent can by after first mixing homogeneously negative active core-shell material, conductive agent and thickening agent, then the binder solution formed with solvent with binding agent, solvent or binding agent is mixed homogeneously and obtained；Can also pass through first by negative active core-shell material, thickening agent, binding agent and solvent mix homogeneously, then mix homogeneously with conductive agent again, obtain slurry.Described solvent is deionized water.The consumption of solvent can make described pastel have viscosity and mobility, it is possible to is coated on described collector body.Method and the condition dry, rolled are well known to those skilled in the art, and do not repeat them here.
In the lithium ion battery of the present invention, prepare the common method that method is this area of battery, in general, positive pole and negative pole and barrier film are constituted a battery core assembly, the battery core assembly obtained and nonaqueous electrolytic solution is sealed in battery case, lithium ion battery can be obtained.Concrete grammar is well known to those skilled in the art, and does not repeat them here.
Embodiment
Hereinafter being described the present invention by embodiment and comparative example, if no special instructions, material used is all commercially available, and method used is the conventional method of this area.
Phenolic resin is purchased from Hebei Huantai Yong Hui Chemical Co., Ltd., and model is PF-231.
Epoxy resin pacifies Chemical Co., Ltd. purchased from Guangzhou thousand, and model is A-20.
Polyamide rises peaking chemical product company limited purchased from Zhengzhou, and model is that ancient cooking vessel is big.
Lauxite is purchased from Jining 101 Chemical Co., Ltd., and model is M101A.
Embodiment 1
The present embodiment is for anode active material of lithium ion battery that the present invention is described and preparation method thereof, lithium ion cell positive and lithium ion battery.
(1) preparation of positive electrode active materials LiFePO 4
By 60kg iron phosphate, 14.85kg lithium carbonate, 4.8kg glucose, 2.4kg phenolic resin, 1.38kg CNT, 0.42kg Graphene and 120kg deionized water ground and mixed 4h in Ball-stirring mill, obtain slurry；Then by slurry dry 4h at 120 DEG C, obtain presoma, and gained presoma is pulverized, crosses 60 mesh sieves, obtain precursor powder.Under nitrogen protection atmosphere, by gained precursor powder constant temperature calcining 8h at 720 DEG C, roasting products therefrom is pulverized, crosses 300 mesh sieves, obtain 59.5kg LiFePO 4.The TEM figure of this LiFePO 4 is shown in Fig. 1.
(2) preparation of positive pole
2.5kg LiFePO 4,0.025kg adhesive PVDF and 0.1kg conductive agent white carbon black are mixed, method particularly includes: first with NMP for solvent, adhesive PVDF is dissolved the solution being configured to 6 weight %, and under agitation respectively LiFePO 4, conductive agent white carbon black are mixed with the solution of above-mentioned PVDF, stirring afterwards forms uniform slurry.
Being uniformly coated on aluminium foil by this slurry, then drying at 100 DEG C, roll-in, cut and prepare the positive pole being of a size of 120mm × 160mm, wherein on pole piece, the quality of positive electrode active materials LiFePO 4 is about 320g/m2。
(3) preparation of negative pole
2.5kg negative pole graphite, 0.05kg thickening agent CMC, 0.025kg white carbon black and 0.075kg binding agent SBR are mixed, method particularly includes: first with deionized water for solvent, binding agent SBR is dissolved the solution being configured to 6 weight %, and under agitation respectively negative pole graphite, CMC, white carbon black are mixed with the solution of above-mentioned SBR, stirring afterwards forms uniform slurry.
Being uniformly coated in carbon coated aluminum foil by this slurry, then drying at 90 DEG C, roll-in, cut to prepare and be of a size of the negative pole of 125mm × 165mm, wherein on pole piece, the quality of negative active core-shell material graphite is about 170g/m2。
(4) assembling of battery
Above-mentioned positive and negative electrode and polypropylene screen are built up the battery core assembly of a square soft bag lithium ionic cell, subsequently by LiPF6It is dissolved in the mixed solvent of EC/DMC=1:1 (volume ratio) by the concentration of 1 mol/L and forms nonaqueous electrolytic solution, this electrolyte is injected in battery case with the amount of 5g/Ah, seals, make 20Ah soft-package battery.
Embodiment 2
Method according to embodiment 1, the difference is that, step (1) is: by 60kg iron phosphate, 16.84kg Lithium hydroxide monohydrate, 4.6kg sucrose, 2.25kg phenolic resin, 1.5kg CNT, 0.24kg Graphene and 120kg deionized water ground and mixed 4h in Ball-stirring mill, obtain slurry；Then by slurry dry 2h at 180 DEG C, obtain presoma, and gained presoma is pulverized, crosses 60 mesh sieves, obtain precursor powder.Under argon atmosphere, by gained precursor powder constant temperature calcining 12h at 700 DEG C, roasting products therefrom is pulverized, crosses 300 mesh sieves, obtain 59.2kg LiFePO 4.
Embodiment 3
Method according to embodiment 1, the difference is that, step (1) is: by 60kg iron phosphate, 26.66kg lithium acetate, 4.8kg glucose, 2.8kg phenolic resin, 1.65kg CNT, 0.65kg Graphene and 120kg deionized water ground and mixed 4h in Ball-stirring mill, obtain slurry；Then by slurry dry 1.5h at 240 DEG C, obtain presoma, and gained presoma is pulverized, crosses 60 mesh sieves, obtain precursor powder.Under argon atmosphere, by gained precursor powder constant temperature calcining 6h at 780 DEG C, roasting products therefrom is pulverized, crosses 300 mesh sieves, obtain 59.3kg LiFePO 4.
Embodiment 4
Method according to embodiment 1, the difference is that, step (1) is: by 45.66kg ammonium dihydrogen phosphate, 28.50kg ferrous oxide, 17.01kg Lithium hydroxide monohydrate, 6kg sucrose, 5.8kg Lauxite, 1.25kg acetylene black, 0.25kg Graphene and 120kg deionized water ground and mixed 4h in Ball-stirring mill, obtain slurry；Then by slurry dry 4h at 120 DEG C, obtain presoma, and gained presoma is pulverized, crosses 60 mesh sieves, obtain precursor powder.Under nitrogen protection atmosphere, by gained precursor powder constant temperature calcining 6h at 780 DEG C, roasting products therefrom is pulverized, crosses 300 mesh sieves, obtain 58.9kg LiFePO 4.
Embodiment 5
Method according to embodiment 1, the difference is that, step (1) is: by 52.4kg phosphoric acid solution (75% mass concentration), 107.2kg Iron trichloride hexahydrate, 14.69kg lithium carbonate, 3kg stearic acid, 2.4kg epoxy resin, 1kgSuperP, 0.2kg Graphene and 120kg dehydrated alcohol ground and mixed 4h in Ball-stirring mill, obtain slurry；Then by slurry dry 2h at 210 DEG C, obtain presoma, and gained presoma is pulverized, crosses 60 mesh sieves, obtain precursor powder.Under argon atmosphere, by gained precursor powder constant temperature calcining 12h at 700 DEG C, roasting products therefrom is pulverized, crosses 300 mesh sieves, obtain 59.2kg LiFePO 4.
Embodiment 6
Method according to embodiment 1, the difference is that, in step (1), by 60kg iron phosphate, 14.85kg lithium carbonate, 2.6kg glucose, 1.3kg phenolic resin, 0.75kg CNT, 0.23kg Graphene and 120kg deionized water ground and mixed, obtain slurry.
Embodiment 7
Method according to embodiment 1, the difference is that, in step (1), by 60kg iron phosphate, 14.85kg lithium carbonate, 6.4kg glucose, 3.2kg phenolic resin, 1.8kg CNT, 0.56kg Graphene and 120kg deionized water ground and mixed, obtain slurry.
Embodiment 8
Method according to embodiment 1, the difference is that, in step (1), by 60kg iron phosphate, 14.85kg lithium carbonate, 6kg glucose, 2.1kg phenolic resin, 1.1kg CNT, 0.34kg Graphene and 120kg deionized water ground and mixed, obtain slurry.
Embodiment 9
Method according to embodiment 1, the difference is that, in step (1), by 60kg iron phosphate, 14.85kg lithium carbonate, 4.5kg glucose, 1.3kg phenolic resin, 2.1kg CNT, 0.6kg Graphene and 120kg deionized water ground and mixed, obtain slurry.
Embodiment 10
According to the method for embodiment 1, the difference is that, in step (1), phenolic resin replaces with containing the polyamide waiting mole C.
Embodiment 11
According to the method for embodiment 1, the difference is that, in step (1), replace 1.38kg CNT and 0.42kg Graphene with 1.8kg Graphene.
Comparative example 1
According to the method for embodiment 1, the difference is that, in step (1), carbon source is only glucose, without phenolic resin, CNT and Graphene, i.e. replaced by phenolic resin, CNT and the Graphene glucose of mole C such as containing.
Comparative example 2
According to the method for embodiment 1, the difference is that, in step (1), carbon source is only phenolic resin, without glucose, CNT and Graphene, i.e. replaced by glucose, CNT and the Graphene phenolic resin of mole C such as containing.
Comparative example 3
According to the method for embodiment 1, the difference is that, in step (1), carbon source is Graphene, without glucose, CNT and phenolic resin, i.e. replaced by glucose, CNT and the phenolic resin Graphene of mole C such as containing.
Comparative example 4
According to the method for embodiment 1, the difference is that, in step (1), carbon source is glucose and graphite, i.e. replaced by Graphene, CNT and the phenolic resin graphite of mole C such as containing.
Test example
Following test example measures the embodiment 1-11 lithium ion battery prepared respectively and comparative example 1-4 prepares the cycle performance of lithium ion battery and internal resistance.The measurement result of cycle performance and internal resistance is as shown in table 1.
Wherein, the assay method of cycle performance includes: under 23 DEG C of conditions, by lithium ion battery respectively with 1C current charges to 3.65V, with constant-potential charge after voltage rises to 3.65V, restriction voltage is 3.8V, and cut-off current is 0.1C, shelves 10 minutes；Battery to 2.0V, shelves 10 minutes with 1C current discharge.Repeating above step 5000 times, after obtaining 5000 circulations of battery, 1C current discharge is to the capacity of 2.0V, records the discharge capacity first that battery is at 23 DEG C, and is calculated capacity dimension holdup before and after circulation by following formula:
Capacity dimension holdup=(the 5000th cyclic discharge capacity/first cyclic discharge capacity) × 100%
Wherein, the internal resistance of cell is measured by BVIR battery voltage internal resistance tester.
Table 1
Those skilled in the art should it is well known that, in table 1,23 DEG C of capacity dimension holdups circulated after 5000 times are more high, it was shown that lithium ion battery has better charging-discharging performances and better cycle performance.Under same process, the internal resistance of lithium ion battery is more low, it was shown that the electric conductivity of positive electrode active materials is more excellent.
The data of embodiment 1-11 and comparative example 1-4 in table 1 are compared known, compared with the ferrousphosphate lithium material only selecting carbohydrate (such as glucose) to prepare as carbon source as carbon source or carbohydrate (such as glucose)+graphite as carbon source or carbon black conductive agent and/or Graphene as carbon source or thermosetting resin, the ferrousphosphate lithium material that the method for the present invention prepares has substantially better electric conductivity, adopts its lithium ion battery prepared to have significantly lower internal resistance and obvious better cycle performance.
Embodiment 1 in table 1 is compared known with the data of embodiment 4-5, when selecting iron phosphate to prepare slurry as source of iron, glucose and/or sucrose, CNT, Graphene, phenolic resin as carbon source, the electric conductivity of the ferrousphosphate lithium material prepared can be improved further, and reduce the internal resistance adopting its lithium ion battery prepared further and improve the cycle performance adopting its lithium ion battery prepared further.
Embodiment 1 in table 1 is compared known with the data of embodiment 6-7, when preparing slurry, in P elements and carbon mole, when the mol ratio of phosphorus source and carbon source is 1:1.1-1.4, the electric conductivity of the ferrousphosphate lithium material prepared can be improved further, and reduce the internal resistance adopting its lithium ion battery prepared further and improve the cycle performance adopting its lithium ion battery prepared further.
Embodiment 1 in table 1 is compared known with the data of embodiment 8-9, when preparing slurry, in carbon source, when in carbohydrate, in the molal quantity of carbon, thermosetting resin, the ratio of the carbon molal quantity sum in the molal quantity of carbon and carbon black conductive agent and Graphene is 1:0.8-1:0.9-1.2, the electric conductivity of the ferrousphosphate lithium material prepared can be improved further, and reduce the internal resistance adopting its lithium ion battery prepared further and improve the cycle performance adopting its lithium ion battery prepared further.
Embodiment 1 in table 1 is compared known with the data of embodiment 10, when thermosetting resin selects phenolic resin, the electric conductivity of the ferrousphosphate lithium material prepared can be improved further, and reduce the internal resistance adopting its lithium ion battery prepared further and improve the cycle performance adopting its lithium ion battery prepared further.
Embodiment 1 in table 1 is compared known with the data of embodiment 11, when carbon source includes carbohydrate, thermosetting resin, carbon black conductive agent and Graphene, the electric conductivity of the ferrousphosphate lithium material prepared can be improved further, and reduce the internal resistance adopting its lithium ion battery prepared further and improve the cycle performance adopting its lithium ion battery prepared further.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode, in order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. the preparation method of an anode active material of lithium ion battery, it is characterised in that the method includes:
(1) phosphorus source, source of iron, lithium source, carbon source and solvent are mixed, obtain slurry；
(2) by slurry drying, obtain presoma, then presoma is pulverized, obtain precursor powder；
(3) under protective atmosphere, precursor powder is carried out roasting；
Wherein, described carbon source includes at least one in carbohydrate, thermosetting resin and carbon black conductive agent and Graphene.
2. method according to claim 1, wherein, in P elements and carbon mole, the mol ratio of phosphorus source and carbon source is 1:0.6-1.5, it is preferred to 1:1.1-1.4；
Preferably, in described carbon source, in carbohydrate, in the molal quantity of carbon, thermosetting resin, the ratio of the carbon molal quantity sum in the molal quantity of carbon and carbon black conductive agent and Graphene is 1:0.2-1.1:0.3-1.6, more preferably 1:0.8-1:0.9-1.2.
3. method according to claim 1 and 2, wherein, described carbon source includes carbohydrate, thermosetting resin and Graphene, preferably, described carbon source includes carbohydrate, thermosetting resin, carbon black conductive agent and Graphene, it is further preferred that the mol ratio of carbon black conductive agent and Graphene is 1:0.1-0.4；
Preferably, described carbohydrate is selected from one or more in glucose, sucrose, lactose, citric acid, Polyethylene Glycol and stearic acid, more preferably glucose and/or sucrose；
Preferably, described thermosetting resin is selected from one or more in phenolic resin, Lauxite, melamine formaldehyde resin, epoxy resin, unsaturated polyester resin, amino resins, silicon ether resin, polyamide, polybutadiene, furfural phenol resin, furfural acetone resin, furfuryl alcohol resin and organic siliconresin, more preferably one or more in phenolic resin, epoxy resin, polyamide and Lauxite, are further preferably phenolic resin；
Preferably, one or more in acetylene black, SuperP, 350G, carbon fiber, CNT and Ketjen black of described carbon black conductive agent, more preferably one or more in SuperP, 350G and CNT, are further preferably CNT.
4. the method according to any one in claim 1-3, wherein, the addition controlling phosphorus source, source of iron and lithium source makes the mol ratio of P elements, ferrum element and elemental lithium in the slurry obtained be 1:0.97-1:1-1.02.
5. the method according to any one in claim 1-4, wherein, phosphorus source is selected from one or more in phosphoric acid, hydrophosphate and orthophosphate；Hydrophosphate is preferably selected from one or more in ammonium dihydrogen phosphate, lithium dihydrogen phosphate and diammonium phosphate, and orthophosphate is preferably selected from iron phosphate and/or ammonium phosphate；
Preferably, described source of iron is selected from one or more in iron phosphate, ferrum oxide, ferrous oxide, solubility divalent iron salt and solubility trivalent iron salt；It is further preferred that solubility divalent iron salt is selected from one or more in ferrous bromide, ferrous chloride, ferrous sulfate and ferrous nitrate, solubility trivalent iron salt is selected from one or more in ferric bromide, iron chloride, iron sulfate, ferric perchlorate and ferric nitrate；
Preferably, described lithium source is selected from one or more in lithium, Lithium hydrate, lithium bicarbonate, lithium phosphate, lithium carbonate, lithium acetate, lithium chloride, lithium dihydrogen phosphate, lithium oxalate and lithium nitrate；
Preferably, described solvent is selected from one or more in deionized water, dehydrated alcohol, isopropanol and acetone.
6. the method according to any one in claim 1-5, wherein, in step (2), described dry condition includes: temperature is 120-250 DEG C, and the time is 1-4h.
7. the method according to any one in claim 1-6, wherein, in step (3), the condition of described roasting includes: temperature is 700-800 DEG C, and the time is 6-12h.
8. the anode active material of lithium ion battery that in claim 1-7, method described in any one prepares.
9. a lithium ion cell positive, it is characterized in that, described positive pole includes collector body and the positive electrode being positioned on collector body, and described positive electrode contains positive electrode active materials, conductive agent and binding agent, and described positive electrode active materials is the anode active material of lithium ion battery described in claim 8.
10. a lithium ion battery, it is characterized in that, described lithium ion battery includes battery container and is positioned at the battery core assembly within battery container and electrolyte, and described battery core assembly includes positive pole, barrier film and negative pole, described just extremely lithium ion cell positive described in claim 9.
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Denomination of invention: The invention relates to a positive electrode active material of a lithium ion battery and a preparation method thereof, a positive electrode of a lithium ion battery and a lithium ion battery Effective date of registration: 20220627 Granted publication date: 20170609 Pledgee: Kaiyang sub branch of Bank of Guiyang Co.,Ltd. Pledgor: GUIZHOU ANDA TECHNOLOGY ENERGY CO.,LTD. Registration number: Y2022980008988 |
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Address after: 550,306 Bai Anying Village, Xicheng Sub district Office, Kaiyang County, Guiyang City, Guizhou Province Patentee after: GUIZHOU ANDA TECHNOLOGY ENERGY CO.,LTD. Country or region after: China Address before: 550300 Ping Shang, Chengxi village, Chengguan Town, Kaiyang County, Guiyang City, Guizhou Province Patentee before: GUIZHOU ANDA TECHNOLOGY ENERGY CO.,LTD. Country or region before: China |