CN105742592A - W/W2Preparation method of C/Action Carbon coated lithium ion battery anode material - Google Patents
W/W2Preparation method of C/Action Carbon coated lithium ion battery anode material Download PDFInfo
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- CN105742592A CN105742592A CN201610119510.XA CN201610119510A CN105742592A CN 105742592 A CN105742592 A CN 105742592A CN 201610119510 A CN201610119510 A CN 201610119510A CN 105742592 A CN105742592 A CN 105742592A
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- lithium
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- anode material
- ion battery
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 101
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 59
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 230000009471 action Effects 0.000 title claims abstract description 41
- 239000010405 anode material Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 52
- 239000002243 precursor Substances 0.000 claims abstract description 52
- 238000005253 cladding Methods 0.000 claims abstract description 40
- 238000005245 sintering Methods 0.000 claims abstract description 39
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 39
- 239000010937 tungsten Substances 0.000 claims abstract description 39
- 230000008569 process Effects 0.000 claims abstract description 28
- 238000006722 reduction reaction Methods 0.000 claims abstract description 21
- 239000004576 sand Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001694 spray drying Methods 0.000 claims abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 38
- 229910052744 lithium Inorganic materials 0.000 claims description 38
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 34
- 229910052756 noble gas Inorganic materials 0.000 claims description 22
- 238000010792 warming Methods 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 19
- 230000000996 additive effect Effects 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 8
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical group [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 7
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 claims description 6
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 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 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 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 4
- 239000008103 glucose Substances 0.000 claims description 4
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002006 petroleum coke Substances 0.000 claims description 4
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 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 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 3
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910010710 LiFePO Inorganic materials 0.000 description 11
- 239000011247 coating layer Substances 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 8
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 229910011857 LiFe0.3Mn0.7PO4 Inorganic materials 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910001367 Li3V2(PO4)3 Inorganic materials 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910009731 Li2FeSiO4 Inorganic materials 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910011905 LiFe1-xMnxPO4 Inorganic materials 0.000 description 3
- 229910010596 LiFe1−xMnxPO4 Inorganic materials 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 2
- 229910013361 LiNixCoyAl1-x-yO2 Inorganic materials 0.000 description 2
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 description 2
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 description 2
- 229910020352 SiPO4 Inorganic materials 0.000 description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 2
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- RDVQTQJAUFDLFA-UHFFFAOYSA-N cadmium Chemical compound [Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd] RDVQTQJAUFDLFA-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- H01M4/36—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
-
- 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
-
- 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
- H01M4/626—Metals
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a W/W2A preparation method of a C/Action Carbon coated lithium ion battery anode material belongs to the field of electrochemical energy storage, and comprises two steps of composite precursor preparation and reduction reaction, wherein the lithium ion battery anode material is particularly a material needing Carbon coating. The preparation method of the precursor comprises the steps of loading a tungsten source on the surface of the precursor to form a composite precursor, wherein the specific operation method comprises a sand grinding spray drying process and a wet dipping process; the reduction reaction step is that the tungsten source on the surface of the composite precursor and the carbon source are reduced into functional W/W together by a carbon-thermal hydrogen reduction method2C/Action Carbon cladding. This functional W/W2C/Action Carbon cladding layer forming process skillfully utilizes Carbon thermal reducing atmosphere in the high-temperature sintering process of the Carbon-clad lithium ion battery anode material, and then reduction is carried out by combining a short hydrogen thermal reducing process to obtain the Carbon/Action Carbon cladding layer; the defects of the coated carbon layer can be effectively repaired, and the discharge specific capacity and the rate capability of the lithium ion battery anode material can be improved. The invention has simple operation and convenient use, and can be suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of W/W2The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, belongs to electrochemical energy storage field.
Background technology
Along with process of industrialization is accelerated to be skyrocketed through with economy, energy problem and environmental pollution have become as one of mankind's problem demanding prompt solution.Lithium from
Sub-battery, as new generation of green rechargable power supplies, owing to having the advantages such as energy density is big, running voltage is high, good cycle, the most gradually replaces
The batteries such as nickel/hydrogen, nickel/cadmium, suffer from being widely applied in fields such as electric automobile, hybrid vehicle, electric tool, 3C Product and energy storage
Prospect.The anode material for lithium-ion batteries being reported in media at present is of a great variety, including cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4), lithium nickelate
(LiNiO2), LiFePO4 (LiFePO4), nickel ion doped (LiNi0.5Mn1.5O4), iron manganese phosphate for lithium (LiFe1-xMnxPO4), ferric metasilicate lithium (Li2FeSiO4),
Phosphoric acid vanadium lithium (Li3V2(PO4)3), lithium manganese phosphate (LiMnPO4), ternary system material (nickle cobalt lithium manganate (LiNixCoyMn1-x-yO2), nickel cobalt lithium aluminate
(LiNixCoyAl1-x-yO2)), lithium-rich manganese base material (xLi2MnO3·(1-x)LiMnO2) etc.；Wherein only has mangaic acid in power lithium-ion battery field at present
Lithium (LiMn2O4), LiFePO4 (LiFePO4) and ternary system material (nickle cobalt lithium manganate (LiNixCoyMn1-x-yO2), nickel cobalt lithium aluminate
(LiNixCoyAl1-x-yO2)) etc. a small amount of material obtained large-scale commercial application.
LiFePO4 (LiFePO4) since Good enough and Padhi finds, high by safety, have extended cycle life, overcharging resisting and cross exoergic
The advantages such as power height, good, cheap, the environmental friendliness of high temperature circulation become one of most material of current driving force field of lithium ion battery application.But
The LiFePO of eigenstate4But can not directly use, main cause is eigenstate LiFePO4Electrical conductivity (10-9～10-10S/m) with lithium ion diffusion coefficient
(1.8·10-14cm2/ s) the most relatively low, the transmission close to insulator, lithium ion and electronics all suffers from the biggest resistance.Identical problem equally exists
In iron manganese phosphate for lithium (LiFe1-xMnxPO4), ferric metasilicate lithium (Li2FeSiO4), phosphoric acid vanadium lithium (Li3V2(PO4)3), lithium manganese phosphate (LiMnPO4) these
Levy with the anode material for lithium-ion batteries that state electrical conductivity is the lowest, hinder the commercial applications process of these positive electrodes.
Numerous studies show, the lithium ion that can be substantially improved these anode material for lithium-ion batteries by metal ion mixing and material with carbon-coated surface is spread
Speed and electronic conductivity.As patent CN1581537A points out that the LiFePO 4 material electronic conductivity through carbon coating layer is modified can reach
10-3S/m, its 0.2C specific discharge capacity can realize more than 145mAh/g.Yet with current LiFePO4 (LiFePO4) material heavy industrialization
Produce and typically use high temperature solid-state method, the shortcoming such as existence is mutually uneven, relatively big, the broad particle distribution of crystalline size, if carbon incorporation way and
Morphology Control aspect is improper, and carbon coating layer can be caused uneven, the most closely, there is carbon coating layer especially and peel off in follow-up crushing and classification processing procedure
Risk, thus cause material conductivity and chemical property to be deteriorated, also can directly reduce the bulk density of LiFePO4.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of W/W2The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding,
Utilize the carbon thermal reduction atmosphere in anode material of carbon-coated lithium ion battery high-temperature sintering process, in conjunction with of short duration hydrogen thermal process by lithium ion cell positive
The tungsten source on material precursor surface is reduced to functional W/W together with carbon source2C/Action Carbon clad, it is possible to effectively repair materials high temperature is solid
The defect that the independent carbon coating layer that phase method synthesis technique prepares exists, functional W/W2The lithium ion battery of C/Action Carbon clad cladding is just
Pole material high rate performance is the most excellent.
The present invention is achieved by the following technical solutions:
A kind of W/W2The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, anti-with reduction including the preparation of compound precursor thing
Answering two steps, described compound precursor thing preparation process is for be supported on precursor of lithium ionic cell positive material surface by tungsten source；Described reduction reaction walks
Rapid for compound precursor thing being carried out in reducing gas and noble gas high temperature sintering, make just to be coated on by controlling the technological parameter in sintering process
Carbon hot hydrogen reduction reaction generating functionality W/W is passed through in the tungsten source on material precursor surface, pole2C/Action Carbon clad is coated on lithium-ion electric
Pond positive electrode finished surface.
A kind of W/W of the present invention2The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, prepared by described compound precursor thing
Step uses sand milling-drying process with atomizing, stoichiometrically the raw material of anode material for lithium-ion batteries is added carbon source, additive A, tungsten source, mixed
Close, with water as dispersant, carry out nanorize dispersion process to slurry D by sand mill50Less than 200nm, obtain by the way of spray drying subsequently
To compound precursor thing；Or
Described compound precursor thing preparation process uses wet impregnation technique, stoichiometrically the raw material of anode material for lithium-ion batteries is added carbon source,
Additive B, mixing, with water as dispersant, carry out nanorize dispersion process to slurry D with sand mill50Less than 200nm, by be spray-dried
Mode obtains precursor of lithium ionic cell positive material, makes tungsten source be sufficiently mixed with the carrier in presoma subsequently by the way of solution impregnation is evaporated
To compound precursor thing.
A kind of W/W of the present invention2The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, described reduction reaction step is adopted
Use temperature programming sintering process:
(1)H2Atmosphere is warming up to 250～350 DEG C, is incubated 20～40min, then raises temperature to 550～650 DEG C, be incubated 20～40min；
(2)H2Atmosphere is warming up to the sintering temperature of positive electrode, is incubated 50～70min；
(3) by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until material has sintered the required time；
(4) noble gas N2Or Ar sintering atmosphere is cooled to 450～550 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace.
Anode material for lithium-ion batteries of the present invention refers in particular to LiFePO4 (LiFePO4), iron manganese phosphate for lithium (LiFe1-xMnxPO4), phosphoric acid vanadium lithium
(Li3V2(PO4)3), lithium manganese phosphate (LiMnPO4), ferric metasilicate lithium (Li2FeSiO4) arbitrary in this kind of anode material for lithium-ion batteries needing carbon to be coated with
Kind.
Tungsten source of the present invention is selected from ammonium paratungstate and/or ammonium metatungstate, and its content is 0.5～3% (wt) of compound precursor thing.
Additive A of the present invention is selected from oxalic acid and/or citric acid, and described additive A is 1:2～2:1 with the mass ratio in tungsten source.
The additive B of the present invention one or more mixture in Super P, Vulcan Carbon, petroleum coke；Described interpolation
Agent B and tungsten source quality ratio are 2:1～8:1.
Carbon source of the present invention is selected from sucrose, glucose, maltose, starch, cyclodextrin, phenolic resin, epoxy resin, Polyethylene Glycol, Colophonium
One or more mixture in this kind of organic carbon source.
Reduction reaction stage heating rate of the present invention is 1～3 DEG C/min；Temperature-fall period speed is 1～3 DEG C/min.
The beneficial effects of the present invention is:
First the present invention is soaked by sand milling-drying process with atomizing or wet method at the precursor of lithium ionic cell positive material preparatory phase needing carbon to be coated with
Tungsten source is supported on presoma surface by stain technique, and the reducing atmosphere formed followed by carbon source pyrolysis in high-temperature sintering process, in conjunction with the of short duration hot mistake of hydrogen
Tungsten source can be reduced to functional W/W together with carbon source by Cheng Caiyong temperature programming sintering process2C/Action Carbon clad is coated on lithium ion
Cell positive material finished surface, it is possible to effectively repair and form defect present in independent carbon coating layer.Due to W/W2C is the good material of electric conductivity
Material, it is thus possible to be effectively improved the chemical property of anode material for lithium-ion batteries.The present invention is unique in that compound precursor thing preparatory phase tungsten
The mode of loading in source: for sand milling-drying process with atomizing, be additive by adding oxalic acid or citric acid, tungsten source ammonium paratungstate or metatungstic acid can be promoted
Ammonium evaporates film forming at precursor of lithium ionic cell positive material surface crystallization；A certain amount of specific surface can be added in predecessor for wet impregnation technique
Long-pending bigger activated carbon is as tungsten source ammonium paratungstate or the POL of ammonium metatungstate, and then beneficially later stage tungsten source load is firm；Load the most complete
Tungsten source become realize in product generate the most functional W/W of performance2The key of C/Action Carbon clad.Present invention process is simple, behaviour
Facilitate, large-scale production can be suitable for.
Accompanying drawing explanation
W/W in Fig. 1: embodiment 52LiFePO4 (the LiFePO of C/Action Carbon clad cladding4) material different multiplying charging and discharging curve；
LiFePO4 (the LiFePO of common carbon coating layer cladding in Fig. 2: comparative example 14) material different multiplying charging and discharging curve；
W/W in Fig. 3: embodiment 62Lithium ferric manganese phosphate (the LiFe of C/Action Carbon clad cladding0.3Mn0.7PO4) material different multiplying charge and discharge
Electricity curve；
Lithium ferric manganese phosphate (the LiFe of common carbon coating layer cladding in Fig. 4: comparative example 20.3Mn0.7PO4) material different multiplying charging and discharging curve.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1:
Compound precursor thing preparatory phase:
With lithium manganese phosphate (LiMnPO4) add the lithium source of stoichiometric proportion based on molecular formula, phosphorus source, manganese source are raw material, add the poly-second of carbon source two
Alcohol, the tungsten source ammonium paratungstate of gross mass 0.5% and the additive oxalic acid with the 2 times of quality in tungsten source, carry out nanorize for dispersant by sand mill with water
Dispersion process is until slurry granularity D50Less than 200nm；Carry out granulating and drying by spray dried form subsequently and obtain compound precursor thing.
The reduction reaction stage:
A, by compound precursor thing at H2Atmosphere is warming up to 250 DEG C, is incubated 40min, then raises temperature to 600 DEG C, be incubated 20min；
b、H2Atmosphere is warming up to LiMnPO4The sintering temperature of material, is incubated 60min；
C, by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until LiMnPO4Material has sintered；
D, with noble gas N2Or Ar sintering atmosphere is cooled to 450 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace and i.e. can get functional
W/W2Lithium manganese phosphate (the LiMnPO of C/Action Carbon clad cladding4) positive electrode；
Wherein temperature rise period speed is 1 DEG C/min；Temperature-fall period speed is 3 DEG C/min.
Embodiment 2:
Compound precursor thing preparatory phase:
With ferric metasilicate lithium (Li2FeSiO4) add the lithium source of stoichiometric proportion based on molecular formula, source of iron, silicon source are raw material, add carbon source epoxy resin
With additive Super P, carry out nanorize dispersion process with water for dispersant by sand mill until slurry granularity D50Less than 200nm, with spray dried
Dry mode carries out granulating and drying and obtains presoma；Subsequently with ammonium metatungstate for tungsten source, impregnation method makes ammonium metatungstate enter on presoma surface in a wet process
Row load obtains compound precursor thing, is 1% (wt) by controlling tungsten source ammonium metatungstate content in the state modulator compound precursor things such as dip time and temperature.
Wherein additive Super P mass is 8 times of tungsten source ammonium metatungstate.
The reduction reaction stage:
A, by compound precursor thing at H2Atmosphere is warming up to 350 DEG C, is incubated 30min, then raises temperature to 600 DEG C, be incubated 40min；
b、H2Atmosphere is warming up to Li2SiPO4The sintering temperature of material, is incubated 60min；
C, by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until Li2SiPO4Material has sintered；
D, with noble gas N2Or Ar sintering atmosphere is cooled to 550 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace and i.e. can get functional
W/W2Ferric metasilicate lithium (the Li of C/Action Carbon clad cladding2FeSiO4) positive electrode；
Wherein temperature rise period speed is 2 DEG C/min；Temperature-fall period speed is 2 DEG C/min.
Embodiment 3:
Compound precursor thing preparatory phase:
With phosphoric acid vanadium lithium (Li3V2(PO4)3) add the lithium source of stoichiometric proportion based on molecular formula, phosphorus source, vanadium source are raw material, add carbon source Colophonium,
The tungsten source ammonium metatungstate of gross mass 1.5% and the additive citric acid with tungsten source 50% mass, carry out nanorize for dispersant by sand mill with water and divide
Dissipate and process until slurry granularity D50Less than 200nm；Carry out granulating and drying by spray dried form subsequently and obtain compound precursor thing.
The reduction reaction stage:
A, by compound precursor thing at H2Atmosphere is warming up to 300 DEG C, is incubated 20min, then raises temperature to 550 DEG C, be incubated 30min；
b、H2Atmosphere is warming up to Li3V2(PO4)3The sintering temperature of material, is incubated 70min；
C, by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until Li3V2(PO4)3Material has sintered；
D, with noble gas N2Or Ar sintering atmosphere is cooled to 500 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace and i.e. can get functional
W/W2Phosphoric acid vanadium lithium (the Li of C/Action Carbon clad cladding3V2(PO4)3) positive electrode；
Wherein temperature rise period speed is 1 DEG C/min；Temperature-fall period speed is 2 DEG C/min.
Embodiment 4:
Compound precursor thing preparatory phase:
With LiFePO4 (LiFePO4) add the lithium source of stoichiometric proportion based on molecular formula, source of iron, phosphorus source are raw material, add carbon source sucrose and interpolation
Agent petroleum coke, carries out nanorize dispersion process with water for dispersant by sand mill until slurry granularity D50Less than 200nm, with spray dried form
Carry out granulating and drying and obtain presoma；Subsequently with ammonium paratungstate for tungsten source, impregnation method makes ammonium metatungstate load on presoma surface in a wet process
Obtain compound precursor thing, be 2% (wt) by controlling tungsten source ammonium metatungstate content in the state modulator compound precursor things such as dip time and temperature.Wherein add
Add that agent Petroleum Coke is tungsten source ammonium metatungstate 2 times.
The reduction reaction stage:
A, by compound precursor thing at H2Atmosphere is warming up to 300 DEG C, is incubated 30min, then raises temperature to 650 DEG C, be incubated 30min；
b、H2Atmosphere is warming up to LiFePO4The sintering temperature of material, is incubated 50min；
C, by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until LiFePO4Material has sintered；
D, with noble gas N2Or Ar sintering atmosphere is cooled to 500 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace and i.e. can get functional
W/W2LiFePO4 (the LiFePO of C/Action Carbon clad cladding4) positive electrode；
Wherein temperature rise period speed is 3 DEG C/min；Temperature-fall period speed is 1 DEG C/min.
Embodiment 5:
Compound precursor thing preparatory phase:
With LiFePO4 (LiFePO4) add the lithium source of stoichiometric proportion based on molecular formula, phosphorus source, source of iron are raw material, add carbon source glucose,
The tungsten source ammonium paratungstate of gross mass 2% and the additive oxalic acid with quality such as tungsten sources, carried out at nanorize dispersion by sand mill with water for dispersant
Reason is until slurry granularity D50Less than 200nm；Carry out granulating and drying by spray dried form subsequently and obtain compound precursor thing.
The reduction reaction stage:
A, by compound precursor thing at H2Atmosphere is warming up to 300 DEG C, is incubated 30min, then raises temperature to 600 DEG C, be incubated 30min；
b、H2Atmosphere is warming up to LiFePO4The sintering temperature of material, is incubated 60min；
C, by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until LiFePO4Material has sintered；
D, with noble gas N2Or Ar sintering atmosphere is cooled to 500 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace and i.e. can get functional
W/W2LiFePO4 (the LiFePO of C/Action Carbon clad cladding4) positive electrode；
Wherein temperature rise period speed is 2 DEG C/min；Temperature-fall period speed is 2 DEG C/min.
Comparative example 1:
Predecessor preparatory phase:
With LiFePO4 (LiFePO4) add the lithium source of stoichiometric proportion based on molecular formula, phosphorus source, source of iron are raw material, add carbon source glucose,
The oxalic acid of gross mass 2%, carries out nanorize dispersion process with water for dispersant by sand mill until slurry granularity D50Less than 200nm；Lead to subsequently
Cross spray dried form to carry out granulating and drying and obtain predecessor.
The high temperature sintering stage:
A, by predecessor at noble gas N2Or Ar atmosphere is warming up to 300 DEG C, it is incubated 30min, then raises temperature to 600 DEG C, be incubated 30min；
B, noble gas N2Or Ar atmosphere is warming up to LiFePO4The sintering temperature of material, insulation is until LiFePO4Material has sintered, with stove
It is cooled to room temperature and i.e. can get the LiFePO4 (LiFePO of common carbon coating layer cladding4) positive electrode；
Wherein temperature rise period speed is 2 DEG C/min；Temperature-fall period speed is 2 DEG C/min.
Embodiment 6:
Compound precursor thing preparatory phase:
With lithium ferric manganese phosphate (LiFe0.3Mn0.7PO4) add the lithium source of stoichiometric proportion based on molecular formula, source of iron, phosphorus source, manganese source are raw material, add
Carbon source sucrose and additive Vulcan Carbon, carry out nanorize dispersion process with water for dispersant by sand mill until slurry granularity D50It is less than
200nm, carries out granulating and drying with spray dried form and obtains presoma；Subsequently with ammonium metatungstate for tungsten source, impregnation method makes metatungstic acid in a wet process
Ammonium carries out load on presoma surface and obtains compound precursor thing, by controlling tungsten source metatungstic acid in the state modulator compound precursor things such as dip time and temperature
Ammonium content is 3% (wt).Wherein additive Vulcan Carbon mass is 4 times of tungsten source ammonium metatungstate.
The reduction reaction stage:
A, by compound precursor thing at H2Atmosphere is warming up to 300 DEG C, is incubated 30min, then raises temperature to 600 DEG C, be incubated 30min；
b、H2Atmosphere is warming up to LiFe0.3Mn0.7PO4The sintering temperature of material, is incubated 60min；
C, by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until LiFe0.3Mn0.7PO4Material has sintered；
D, with noble gas N2Or Ar sintering atmosphere is cooled to 500 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace and i.e. can get functional
W/W2Lithium ferric manganese phosphate (the LiFe0.3Mn0.7PO of C/Action Carbon clad cladding4) positive electrode；
Wherein temperature rise period speed is 2 DEG C/min；Temperature-fall period speed is 2 DEG C/min.
Comparative example 2:
Predecessor preparatory phase:
With lithium ferric manganese phosphate (LiFe0.3Mn0.7PO4) add the lithium source of stoichiometric proportion based on molecular formula, source of iron, phosphorus source, manganese source are raw material, add
The Vulcan Carbon of carbon source sucrose and gross mass 12%, carries out nanorize dispersion process with water for dispersant by sand mill until slurry granularity D50
Less than 200nm, carry out granulating and drying with spray dried form and obtain presoma.
The high temperature sintering stage:
A, by predecessor at noble gas N2Or Ar atmosphere is warming up to 300 DEG C, it is incubated 30min, then raises temperature to 600 DEG C, be incubated 30min；
B, noble gas N2Or Ar atmosphere is warming up to LiFe0.3Mn0.7PO4The sintering temperature of material, insulation is until LiFe0.3Mn0.7PO4Material
Sintering completes, and cools to room temperature with the furnace and i.e. can get the lithium ferric manganese phosphate (LiFe of common carbon coating layer cladding0.3Mn0.7PO4) positive electrode；
Wherein temperature rise period speed is 2 DEG C/min；Temperature-fall period speed is 2 DEG C/min.
The functional W/W prepared for the detection present invention2The chemical property of the anode material for lithium-ion batteries of C/Action Carbon clad cladding,
Use 2016 button cells that it is carried out electrochemistry evaluation and test.The W/W obtained with embodiment 5 and comparative example 12C/Action Carbon clad with
LiFePO4 (the LiFePO of common carbon coating layer cladding4) material, and the W/W that embodiment 6 obtains with comparative example 22C/Action Carbon bag
Lithium ferric manganese phosphate (the LiFe that coating is coated with common carbon coating layer0.3Mn0.7PO4) material is as positive pole, with positive active material: conductive agent Super P:
The mass ratio of bonding agent Kynoar (PVDF)=80:10:10 carries out closing slurry, is subsequently coated at the baking of 120 DEG C of utter misery aluminum foil current collector surface
2h obtains anode pole piece, is assembled into button cell in full Ar glove box, and wherein metal lithium sheet is to electrode, and clegard2400 is barrier film,
The LiPF of 1mol/L6/ EC+DEC+DMC solution is electrolyte, uses Land battery test system to carry out constant current charge-discharge test, result such as figure
1～4, table 1～2.
LiFePO in table 1 embodiment 5 and comparative example 14Specific discharge capacity
| Discharge-rate | 0.2C | 0.5C | 1C | 2C |
| Embodiment 5 (mAh.g-1) | 154.5 | 144.7 | 140.2 | 129.3 |
| Comparative example 1 (mAh.g-1) | 152.7 | 141.7 | 136.5 | 125.0 |
LiFe in table 2 embodiment 6 and comparative example 20.3Mn0.7PO4Specific discharge capacity
| Discharge-rate | 0.2C | 0.5C | 1C | 2C | 3C |
| Embodiment 6 (mAh.g-1) | 131.6 | 127.8 | 125.6 | 121.8 | 118.5 |
| Comparative example 2 (mAh.g-1) | 129.4 | 121.9 | 117.3 | 115.7 | 114.8 |
Fig. 1 Yu Fig. 2 provides two kinds of LiFePO4 (LiFePO4) charging and discharging curve under material different multiplying, the electric discharge ratio under different multiplying listed by table 1
Capacity, comprehensive analysis finds W/W2The LiFePO of C/Action Carbon cladding4(154.5mAh.g-1) more common carbon cladding LiFePO4(152.7
mAh.g-1) material 0.2C specific discharge capacity 2mAh.g to be exceeded-1, the LiFePO of carbon the most common for the specific discharge capacity under bigger multiplying power cladding4
Want height, embody through W/W2Good LiFePO after C/Action Carbon cladding4There is discharge performance and the high rate performance of excellence.
Fig. 3 Yu Fig. 4 give also two kinds of lithium ferric manganese phosphate (LiFe simultaneously0.3Mn0.7PO4) charging and discharging curve of material different multiplying, under different multiplying
Specific discharge capacity is listed in table 2.Result display W/W2The LiFe of C/Action Carbon cladding0.3Mn0.7PO4Material discharging performance is with high rate performance all
More common carbon cladding LiFe0.3Mn0.7PO4Material to be got well, and further demonstrate that functional W/W2C/Action Carbon cladding can effectively modified lithium
The chemical property of ion battery positive electrode.
Above content is to combine concrete preferred implementation further description made for the present invention, it is impossible to assert being embodied as only of the present invention
It is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, it is also possible to
Make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (9)
1. a W/W2The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, it is characterized in that: including the preparation of compound precursor thing and two steps of reduction reaction, described compound precursor thing preparation process is for be supported on precursor of lithium ionic cell positive material surface by tungsten source；Described reduction reaction step, for compound precursor thing carries out in reducing gas and noble gas high temperature sintering, makes to be coated on the tungsten source on positive electrode material precursor surface by carbon hot hydrogen reduction reaction generating functionality W/W by controlling the technological parameter in sintering process2C/Action Carbon clad is coated on anode material for lithium-ion batteries finished surface.
A kind of W/W the most according to claim 12The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, it is characterized in that: described compound precursor thing preparation process uses sand milling-drying process with atomizing, stoichiometrically the raw material of anode material for lithium-ion batteries is added carbon source, additive A, tungsten source, mixing, with water as dispersant, carry out nanorize dispersion process to slurry D by sand mill50Less than 200nm, by the way of spray drying, obtain compound precursor thing subsequently；Or
Described compound precursor thing preparation process uses wet impregnation technique, and the raw material of anode material for lithium-ion batteries stoichiometrically adds carbon source, additive B, mixing, with water as dispersant, carries out nanorize dispersion process to slurry D with sand mill50Less than 200nm, by the way of spray drying, obtain precursor of lithium ionic cell positive material, make tungsten source be sufficiently mixed with the carrier in presoma subsequently by the way of solution impregnation is evaporated and obtain compound precursor thing.
A kind of W/W the most according to claim 1 and 22C/Action
The method for preparing anode material of lithium-ion battery of Carbon cladding, it is characterised in that described reduction reaction step employing temperature programming sintering process:
(1) H2Atmosphere is warming up to 250 ~ 350 DEG C, is incubated 20 ~ 40min, then raises temperature to 550 ~ 650 DEG C, be incubated 20 ~ 40min；
(2) H2Atmosphere is warming up to the sintering temperature of positive electrode, is incubated 50 ~ 70min；
(3) by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until material has sintered the required time；
(4) noble gas N2Or Ar sintering atmosphere is cooled to 450 ~ 550 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace.
A kind of W/W the most according to claim 12The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, it is characterised in that: described anode material for lithium-ion batteries is LiFePO4, iron manganese phosphate for lithium, phosphoric acid vanadium lithium, lithium manganese phosphate, any one in ferric metasilicate lithium.
A kind of W/W the most according to claim 1 and 22C/Action
The method for preparing anode material of lithium-ion battery of Carbon cladding, it is characterised in that: described tungsten source is selected from ammonium paratungstate and/or ammonium metatungstate, and its content is 0.5 ~ 3%wt of compound precursor thing.
A kind of W/W the most according to claim 22The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, it is characterised in that: described additive A is selected from oxalic acid and/or citric acid, and described additive A is 1:2 ~ 2:1 with the mass ratio in tungsten source.
A kind of W/W the most according to claim 22The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, it is characterised in that: described additive B is selected from Super P, Vulcan
One or more mixture in Carbon, petroleum coke；Described additive B and tungsten source quality ratio are 2:1 ~ 8:1.
A kind of W/W the most according to claim 22The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, it is characterised in that: the described carbon source one or more mixture in sucrose, glucose, maltose, starch, cyclodextrin, phenolic resin, epoxy resin, Polyethylene Glycol, Colophonium.
A kind of W/W the most according to claim 32The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, it is characterised in that: described reduction reaction step temperature-rise period speed is 1 ~ 3 DEG C/min；Temperature-fall period speed is 1 ~ 3 DEG C/min.
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| CN110299515B (en) * | 2018-03-23 | 2023-08-08 | 比亚迪股份有限公司 | Positive electrode active material, preparation method thereof, positive electrode and battery |
| CN110517808A (en) * | 2019-08-05 | 2019-11-29 | 中国民用航空飞行学院 | A kind of composite conductive thin film and preparation method thereof based on silver nanowires |
| CN110517808B (en) * | 2019-08-05 | 2021-06-18 | 中国民用航空飞行学院 | Composite conductive film based on silver nanowires and preparation method thereof |
| CN115974035A (en) * | 2022-12-28 | 2023-04-18 | 唐山亨坤新能源材料有限公司 | Method for adjusting lithium iron phosphate carbon-bundle |
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