CN116675205A - Preparation method of power type lithium iron phosphate agglomerate positive electrode material - Google Patents
Preparation method of power type lithium iron phosphate agglomerate positive electrode material Download PDFInfo
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- CN116675205A CN116675205A CN202310790881.0A CN202310790881A CN116675205A CN 116675205 A CN116675205 A CN 116675205A CN 202310790881 A CN202310790881 A CN 202310790881A CN 116675205 A CN116675205 A CN 116675205A
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- lithium
- iron phosphate
- carbon source
- phosphate
- lithium iron
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 42
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 49
- 229910052799 carbon Inorganic materials 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 18
- 239000007921 spray Substances 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 11
- 239000005955 Ferric phosphate Substances 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229940032958 ferric phosphate Drugs 0.000 claims description 9
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 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 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011164 primary particle Substances 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910000859 α-Fe Inorganic materials 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 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 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 230000002262 irrigation Effects 0.000 claims description 3
- 238000003973 irrigation Methods 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 235000010643 Leucaena leucocephala Nutrition 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 230000004931 aggregating effect Effects 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 239000000783 alginic acid Substances 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 229960001126 alginic acid Drugs 0.000 claims description 2
- 150000004781 alginic acids Chemical class 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 230000000873 masking effect Effects 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 239000011163 secondary particle Substances 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 241000220479 Acacia Species 0.000 claims 1
- 235000021551 crystal sugar Nutrition 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005056 compaction Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940014259 gelatin Drugs 0.000 description 1
- 238000001879 gelation Methods 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of a power type lithium iron phosphate aggregate positive electrode material, which belongs to the technical field of lithium ion batteries.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a preparation method of a high-tap-density high-performance power lithium iron phosphate aggregate large-particle positive electrode material.
Background
With the rapid development of economy, market demands for smaller and lighter electronic products and electric vehicles, etc., thus battery technology is required to be continuously improved, including having higher battery energy density, wider operating temperature range, longer service life, and simultaneously having fast charging capability and safety and also having low cost. The positive electrode materials on the market are mainly LiCoO2, liMn2O4 and LiCo x Mn y Ni 1-x-y O 2 And LiFePO 4 . Wherein LiFePO 4 The material has the advantages of stable structure, good safety, ultra-long cycle life, low cost and the like, and along with the advent of a blade battery, the LiFePO is solved 4 The material has low energy density, safety and other problems, so that the material is widely applied. In view of environmental protection and cost saving, the dry coating process is widely studied, the modification direction of the lithium iron phosphate material meeting the requirement of the dry process is clearly defined, the requirement of the lithium iron phosphate material with higher tap density is put forward, and the dry coating process has higher requirement on the processing performance of the lithium iron phosphate material.
Tap density refers to the mass per unit volume measured after the powder in the container has been tapped under specified conditions. Generally, the larger the tap density, the higher the capacity of the battery, so the tap density is also regarded as one of the reference indexes of the energy density of the material, and under certain process conditions, the larger the tap density, the higher the capacity of the battery. In particular, in the peak period of the current new energy automobile, in order to widely apply the lithium iron phosphate to the new energy electric automobile and the hybrid electric automobile, the lithium iron phosphate must be further appliedAnd the tap density of the lithium iron manganese phosphate is improved. The tap density of lithium iron phosphate in the current industry is generally 0.8-1.3 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Therefore, on the basis of ensuring the electrical performance of the lithium iron phosphate material, the tap density of the material is improved, and the volume specific capacity of the material is further improved, so that the lithium iron phosphate material becomes one of the problems to be solved in large-scale commercial application.
The patent application with publication number of CN 114804058A discloses a preparation method of a high tap density lithium iron phosphate positive electrode material, which comprises the steps of sequentially carrying out grinding treatment and spraying treatment on a mixed solution of an iron source, a lithium source, a carbon source and an ion doping agent to obtain precursor powder; and sintering the precursor powder at high temperature to obtain the lithium iron phosphate anode material. Although the method is simple in process, high in production efficiency, slightly improved in tap density and specific capacity and unique in appearance, can be mixed with ternary materials for use, can ensure the safety of the lithium iron phosphate battery, and can also have the characteristics of high energy density and low temperature resistance of the ternary battery, due to the porous structure of primary particles, agglomerate particles have poor mechanical strength, the initial DCR of the pole piece is higher, the overall circulation stability is influenced, in addition, the overall pole piece compaction is influenced, the energy density is reduced, the poor mechanical strength is mixed with the ternary materials for use, the risk of particle breakage is caused after the mixing, the overall uniformity and the safety are influenced, and the current market demand cannot be met. The method comprises the steps of carrying out solid-phase mixing on an iron source, a phosphorus source, a lithium source, an additive and a carbon source to obtain a mixture, carrying out ball milling and spray drying treatment to obtain yellow brown precursor powder, and placing the yellow brown precursor powder in a tube furnace rich in inert gas for high-temperature sintering to obtain the magnesium doped lithium iron phosphate/carbon composite microsphere with high tap density. Patent application with publication number CN 107623117B, using polyethylene glycol, sucrose and phenolic resin as carbon source, adding ironMixing the raw materials in a conventional mode, spray drying, and performing two-stage sintering to obtain the high-capacity high-tap-density lithium iron phosphate material. Although the capacity and rate performance of the agglomerates are obviously improved, the tap density of the sample is only 1.2g/cm after the improvement due to the porous structure of the synthesized agglomerates 3 The compacted density is lower and the requirement of high energy density cannot be met. Therefore, a product with high tap density and compaction density and good processability is urgently needed in the market on the basis of ensuring good power performance and mechanical strength, and innovation of market demands is realized.
Disclosure of Invention
Aiming at the problem of application of the current power type agglomerate lithium iron phosphate material, the invention provides a method for preparing high-performance high-tap-density lithium iron phosphate agglomerate large particles, which is simple in process synthesis, easy to implement and low in cost.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the power type lithium iron phosphate agglomerate positive electrode material comprises the following steps:
weighing a carbon source, a lithium source and ferric phosphate;
mixing a carbon source and a lithium source in a dry method and/or in a solvent, crushing and dissolving in a wall breaking machine until the dissolution is completed, and obtaining a milky mesophase polymer;
dissolving ferric phosphate in a solvent, and controlling the solid content to form a uniform phosphorus ferrite solution;
slowly adding a phosphorus ferrite solution into the mesophase polymer, and mixing under the action of a differential centrifugal stirrer to form a gel-like copolymer;
adding a solution prepared by an additive and a solvent into the gel-like copolymer in a flood irrigation mode while stirring, and carrying out classified grinding, spray drying and sieving on the slurry after uniform mixing to obtain a precursor;
sintering the obtained precursor under the protection of inert atmosphere, cooling and sieving to obtain the lithium iron phosphate agglomerate anode material; the lithium iron phosphate aggregate positive electrode material is aggregate secondary particles formed by aggregating small particles, the particle size of primary particles is 200-300 nm, and the particle size of secondary aggregates is 10-15 mu m.
Preferably, the molar ratio of lithium source to iron phosphate, li: p=1, (1.0-1.1), preferably 1, (1.0-1.02); the mass of the carbon source is 5-15% of that of the ferric phosphate.
Preferably, the lithium source is one or more of lithium phosphate, lithium carbonate, lithium hydroxide, dilithium phosphate, and lithium dihydrogen phosphate.
Preferably, the carbon source is one or more of sucrose, glucose, rock candy, cellulose, phenolic resin, polyethylene glycol, polyvinylpyrrolidone, starch, polyvinyl alcohol, ionic cellulose gum carbon source and inorganic carbon source.
More preferably, the inorganic carbon source is one or more of graphite, carbon nanotubes, graphene, and the like.
More preferably, the ionic cellulose gum carbon source is one or more of gelatin, acacia, alginic acid gum, and sodium carboxymethyl cellulose.
Preferably, the solid content of the ferric phosphate solution is 30% -50%.
Preferably, the additive is at least one of titanium dioxide, tetrabutyl titanate, magnesium oxide, magnesium hydroxide, zinc oxide, zirconium dioxide, vanadium pentoxide and ammonium metavanadate; the mass fraction of the additive in the solution is 0.005%, but not limited to, and the adding amount is set according to actual needs.
Preferably, the solvent added in all the steps is at least one of water and an organic solvent, and the organic solvent is one of methanol, ethanol and acetone, preferably water.
Preferably, the classified grinding comprises the steps of firstly crushing by a coarse grinding machine, and controlling the grain size of slurry to be 700-800 nm; then fine masking is carried out by using a fine grinding sand mill, and the granularity of the slurry is controlled to be 200-500 nm; the median diameter D50 of the sizing agent after graded grinding is less than or equal to 300nm.
Preferably, the spray dryer used for spray drying is a centrifugal dryer, a pressure dryer, a fluid dryer or other types of special dryers; the air inlet temperature of the spray is 200-280 ℃, the air outlet temperature of the spray is 60-110 ℃, and the median particle diameter D50 of the spray is 8-15 mu m.
Preferably, the sintering condition is that the temperature is raised at a temperature raising rate of 1-10 ℃/min, the temperature is raised to 200-350 ℃ from the room temperature, and the temperature is kept for 1-5 h; heating to 400-500 ℃, and preserving heat for 3-7 h; and then heating to 700-800 ℃ continuously, and preserving heat for 5-15 h.
Preferably, the sintering mode is one of roller kiln, pusher kiln, tube furnace, box furnace, bell furnace and muffle furnace.
The technical scheme of the invention has the following advantages:
1. the invention adopts a grading mixing technology, the added raw materials are mixed with the assistance of equipment such as a wall breaking machine, a differential centrifugal stirrer and the like, and the materials are configured in a echelon manner, so that the unique effect of the carbon source in the mixing process is fully exerted. The carbon source forms a unique interface forming layer through contact with the lithium source, the ferric phosphate and the solvent, even in the subsequent grinding process, the special connection capability of the carbon source body can be fully exerted, the continuous formation of the interface forming layer is kept, and the length of the carbon layer is shortened due to the fact that the molecular structure of the carbon layer is damaged by grinding, so that other raw materials are wrapped by the aid of the continuously enhanced binding force, and the overall density is improved.
2. According to the invention, a grading grinding technology is adopted, and in the slurry grinding process, two phases with approximately the same particle size are tightly connected by a specific carbon source to form a stable bound aggregate, so that the grinding efficiency is improved, the slurry is more uniform, the particle uniformity in the drying and granulating process is improved, the span distribution of the aggregate is greatly improved, and the overall quality is improved.
3. According to the invention, a specific carbon source, especially a carboxymethyl cellulose sodium, gelatin, sodium alginate and other plasma cellulose gum carbon sources are added, and after the carbon sources are mixed, the color of the slurry is changed into milky white, and the shape is changed into emulsion, so that the grinding efficiency is improved.
4. The solvent selected by the invention is preferably an aqueous solvent, and after a carbon source is dissolved in water, the cellulose derivative has a large number of hydrophilic groups in a molecular chain: the OH group and COONa group can be adhered to the surfaces of the iron phosphate and the lithium source after being contacted with the lithium iron phosphate material, and form tight connection through gelation, and graphitized carbon with higher strength can be formed at high temperature due to the special structure of the lithium iron phosphate material, so that dense package is formed on the lithium iron phosphate, and the overall strength is further improved; in addition, after the carbon layer is subjected to high temperature, the carbon layer can shrink from outside to inside, and the compact carbon layer can further compress the gap between the carbon layer and the inside, so that the overall tap density is improved.
5. The invention prepares the high-tap-density high-performance power lithium iron phosphate agglomerate positive electrode material, improves the processing performance of the material while maintaining the good multiplying power performance of the inner power material, and simultaneously further improves the compaction density of the pole piece and the energy density. The method has the advantages of higher overall yield, simple preparation process and suitability for mass production.
Drawings
Fig. 1 is an SEM image of lithium iron phosphate prepared in example 1 of the present invention.
Fig. 2 is an XRD pattern of lithium iron phosphate prepared in example 1 of the present invention.
FIG. 3 is a plot of the capacity test of lithium iron phosphate prepared in example 1 of the present invention.
Fig. 4 is an SEM image of lithium iron phosphate prepared in example 6 of the present invention.
Detailed Description
In order to make the technical features and advantages or technical effects of the technical scheme of the present invention more obvious and understandable, the following examples are listed and described in detail with reference to the accompanying drawings.
Example 1
1) Lithium carbonate and iron phosphate were weighed respectively in a molar ratio of Li: p=1:1.012, and sodium carboxymethylcellulose and glucose were weighed as carbon sources, the mass of which was 10% of that of the iron phosphate.
2) Mixing the weighed lithium carbonate and sodium carboxymethyl cellulose by a dry method, adding an aqueous solution of glucose, and carrying out differential mixing under the action of a wall breaking machine until a uniform white milky mesophase polymer appears.
3) The ferric phosphate is dissolved in water through a filter screen to form a solution with the solid content of about 50 percent.
4) The iron phosphate solution was slowly added to the mesophase polymer, and a pale yellow gel-like copolymer was formed under the action of a differential centrifugal stirrer and transferred to a compounding tank.
5) Adding 0.005% titanium dioxide aqueous solution into a mixing tank in a flood irrigation mode while stirring, continuing stirring for 30min, starting to crush by a coarse sand mill, transferring to a fine sand mill for fine grinding after the granularity reaches 700-800 nm, and finally obtaining the granularity D50 of 200-220 nm; the slurry is spray dried, a two-fluid dryer is selected as the spray dryer, the gas pressure is 0.45MPa, the inlet temperature is 240 ℃, the air outlet temperature is 80 ℃, the median particle diameter D50 of spray is 8-15 mu m, the dried powder is sieved by a 300-mesh vibrating screen, and the sieved powder is a precursor.
6) Placing the precursor powder into a roller kiln protected by nitrogen, heating from room temperature to 280 ℃ at a heating rate of 5 ℃/min, and preserving heat for 3 hours; heating to 460 ℃ at the same heating rate, and preserving heat for 5 hours; then continuously heating to 750 ℃ at the same heating rate, and preserving heat for 8 hours; and naturally cooling to room temperature, and performing secondary screening treatment to obtain the lithium iron phosphate aggregate anode material.
The lithium iron phosphate particles prepared in example 1 were characterized for their properties as follows:
fig. 1 is an SEM image of lithium iron phosphate prepared in example 1. The obtained sample can be clearly observed to have a part of large particles of 12-15 mu m, the primary particles are small particles of about 220nm in the shape of small rice grains or sheets, the small particles are uniformly distributed, the particle surfaces are smooth and compact, the sphericity is high, and the tap density of the powder reaches 1.96g/cm 3 The mechanical strength of the agglomerate can reach 100MPa, and meanwhile, good electrical property and multiplying power performance can be ensured.
Fig. 2 is an XRD pattern of lithium iron phosphate prepared in example 1, the abscissa represents the 2θ diffraction angle of X-ray, and the ordinate represents the diffraction intensity. The diffraction peaks in the figure correspond very well to the lithium iron phosphate standard peak (JCPDS 19-0721) in PDF cards, and there are no impurity peaks.
Fig. 3 is a graph showing a capacity test of lithium iron phosphate prepared in example 1 of the present invention, in which the abscissa represents charge and discharge capacity and the ordinate represents electrode voltage. From the capacity test results, it can be seen that: the sample 0.1C discharge can reach 160mAh/g.
Example 2
1) The lithium source, carbon source and iron phosphate were weighed as in example 1, except that the molar ratio Li: p=1:1.05, the mass of the carbon source being 15% of that of the iron phosphate.
2) The difference from step 2) of example 1 is that when lithium carbonate is mixed with sodium carboxymethyl cellulose, three batches of lithium carbonate and sodium carboxymethyl cellulose are added in a crossover, one third of each time, and the other are the same.
3) The difference from step 3) of example 1 is that the iron phosphate is dissolved in water in four additions with a solids content of 30%.
4) The same as in step 4) of example 1.
5) The difference from step 5) of example 1 is that the slurry is spray dried by a two-fluid dryer with a gas pressure of 0.45MPa, an inlet temperature of 200deg.C and an outlet temperature of 60deg.C, all other things being equal.
6) Placing the precursor into a laboratory tube furnace protected by nitrogen, heating to 350 ℃ at a heating rate of 10 ℃/min, and preserving heat for 1h; then heating to 500 ℃ at the same heating rate, and preserving heat for 3 hours; then continuously heating to 800 ℃ at the same heating rate, and preserving heat for 5 hours; and naturally cooling to room temperature to obtain the lithium iron phosphate aggregate anode material.
Example 3
1) The weighed lithium source, carbon source and iron phosphate were the same as in example 1, except that the molar ratio Li: p=1:1.1, the mass of the carbon source was 5% of that of the iron phosphate.
Steps 2) and 4) were identical to example 1, with the solids content in step 3) being controlled at 40%.
5) The difference from step 5) of example 1 is that the slurry is spray dried using a two-fluid dryer, the spray dryer is a two-fluid dryer, the gas pressure is 0.45MPa, the inlet temperature is 280 ℃, and the outlet temperature is 110 ℃.
6) Placing the precursor in a roller kiln protected by nitrogen, heating from room temperature to 200 ℃ at a heating rate of 1 ℃/min, and preserving heat for 5 hours; then heating to 400 ℃ at the same heating rate, and preserving heat for 7h; then continuously heating to 700 ℃ at the same heating rate, and preserving heat for 15 hours; and naturally cooling to room temperature, and performing secondary screening treatment to obtain the lithium iron phosphate aggregate anode material.
Example 4
This example differs from example 1 in that the carbon source was glucose alone and the slurry was spray dried using a centrifugal dryer. The others are the same.
Example 5
The difference between this example and example 1 is that the carbon source is glucose and polyvinylpyrrolidone, the slurry is spray dried by a pressure dryer, and the feeding pressure is controlled at 20-30 bar. The others are the same.
Example 6
This example differs from example 1 only in that the water solvent was replaced entirely with methanol. The others are the same.
Fig. 4 is an SEM image of lithium iron phosphate prepared in example 6. It can be clearly observed that the particle size of the sample is uniformly dispersed, the D50 is 8-10 mu m, the sphericity of the particles is poor, the surface porosity of the microspheres is high, the compactness is poor, and the particles are loose.
Table 1A list of performance results for the various examples
| Test item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Tap density (g/cm) 3 ) | 1.96 | 1.98 | 1.57 | 1.38 | 1.21 | 1.06 |
| First week discharge (mAh/g) | 158.7 | 149.0 | 149.7 | 157.1 | 160.2 | 157.6 |
| 1C discharge (mAh/g) | 140.7 | 126.5 | 126.2 | 139.8 | 141.2 | 151.4 |
| Density of compaction (g/cm) 3 ) | 2.37 | 2.42 | 2.48 | 2.31 | 2.18 | 2.16 |
| D50(μm) | 13.514 | 12.636 | 14.403 | 17.414 | 7.807 | 17.272 |
| D100(μm) | 41.034 | 47.419 | 41.832 | 64.524 | 38.176 | 61.208 |
From the above table, it is clear that (1) in example 6, the index of tap density, compaction density, etc. is reduced due to the change of solvent from water to organic solvent, which indicates that the method of the invention selects water as solvent significantly better than organic solvent; (2) Example 2 in steps 2) and 3) the addition of lithium source, carbon source and iron phosphate in multiple batches is more advantageous for solvent mixing and can increase tap density.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and those skilled in the art may modify or substitute the technical solution of the present invention, and the scope of the present invention is defined by the claims.
Claims (10)
1. The preparation method of the power type lithium iron phosphate aggregate positive electrode material is characterized by comprising the following steps of:
weighing a carbon source, a lithium source and ferric phosphate;
mixing a carbon source and a lithium source in a dry method and/or in a solvent, crushing and dissolving in a wall breaking machine until the dissolution is completed, and obtaining a milky mesophase polymer;
dissolving ferric phosphate in a solvent, and controlling the solid content to form a uniform phosphorus ferrite solution;
slowly adding a phosphorus ferrite solution into the mesophase polymer, and mixing under the action of a differential centrifugal stirrer to form a gel-like copolymer;
adding a solution prepared by an additive and a solvent into the gel-like copolymer in a flood irrigation mode while stirring, and carrying out classified grinding, spray drying and sieving on the slurry after uniform mixing to obtain a precursor;
sintering the obtained precursor under the protection of inert atmosphere, cooling and sieving to obtain the lithium iron phosphate agglomerate anode material; the lithium iron phosphate aggregate positive electrode material is aggregate secondary particles formed by aggregating small particles, the particle size of primary particles is 200-300 nm, and the particle size of secondary aggregates is 10-15 mu m.
2. The method according to claim 1, wherein the molar ratio of lithium source to iron phosphate, li, is p=1, (1.0-1.1), preferably 1, (1.0-1.02); the mass of the carbon source is 5-15% of that of the ferric phosphate.
3. The method of claim 1, wherein the lithium source is one or more of lithium phosphate, lithium carbonate, lithium hydroxide, dilithium phosphate, and lithium dihydrogen phosphate.
4. The method of claim 1, wherein the carbon source is one or more of sucrose, glucose, crystal sugar, cellulose, phenolic resin, polyethylene glycol, polyvinylpyrrolidone, starch, polyvinyl alcohol, an ionic cellulose gum carbon source, and an inorganic carbon source; wherein the inorganic carbon source is one or more of graphite, carbon nano tube and graphene; the ionic cellulose gum carbon source is one or more of gelatin, acacia, alginic acid gum and sodium carboxymethyl cellulose.
5. The method of claim 1, wherein the iron phosphate solution has a solids content of 30% to 50%.
6. The method of claim 1, wherein the additive is at least one of titanium dioxide, tetrabutyl titanate, magnesium oxide, magnesium hydroxide, zinc oxide, zirconium dioxide, vanadium pentoxide, and ammonium metavanadate.
7. The method of claim 1, wherein the solvent added in all steps is at least one of water and an organic solvent, and the organic solvent is one of methanol, ethanol and acetone.
8. The method of claim 1, wherein the classifying grinding comprises crushing by a coarse grinding mill, and controlling the size of the slurry to be 700-800 nm; then fine masking is carried out by using a fine grinding sand mill, and the granularity of the slurry is controlled to be 200-500 nm; the median diameter D50 of the sizing agent after graded grinding is less than or equal to 300nm.
9. The method of claim 1, wherein the spray dryer selected for spray drying is a centrifugal dryer, a pressure dryer, a fluid dryer, or other type of special dryer; the air inlet temperature of the spray is 200-280 ℃, the air outlet temperature of the spray is 60-110 ℃, and the median particle diameter D50 of the spray is 8-15 mu m.
10. The method of claim 1, wherein the sintering conditions are elevated at an elevated temperature rate of 1-10 ℃/min from room temperature to 200-350 ℃ and maintained for 1-5 hours; heating to 400-500 ℃, and preserving heat for 3-7 h; heating to 700-800 deg.c and maintaining for 5-15 hr; the sintering mode is one of roller kiln, pusher kiln, tubular furnace, box furnace, bell furnace and muffle furnace.
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