CN102709560A - Method for preparing high-machinability lithium iron phosphate cathode material - Google Patents
Method for preparing high-machinability lithium iron phosphate cathode material Download PDFInfo
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- CN102709560A CN102709560A CN2012101987825A CN201210198782A CN102709560A CN 102709560 A CN102709560 A CN 102709560A CN 2012101987825 A CN2012101987825 A CN 2012101987825A CN 201210198782 A CN201210198782 A CN 201210198782A CN 102709560 A CN102709560 A CN 102709560A
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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 20
- 238000000034 method Methods 0.000 title abstract description 7
- 239000010406 cathode material Substances 0.000 title abstract 2
- 238000005096 rolling process Methods 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000000227 grinding Methods 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000012216 screening Methods 0.000 claims abstract description 12
- 238000005303 weighing Methods 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000001694 spray drying Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000080 wetting agent Substances 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims description 18
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 15
- 239000010405 anode material Substances 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 9
- 229940062993 ferrous oxalate Drugs 0.000 claims description 8
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 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 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 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
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 229940031993 lithium benzoate Drugs 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 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
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 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
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000010981 drying operation Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 11
- 239000002243 precursor Substances 0.000 abstract 4
- 238000003825 pressing Methods 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000009736 wetting Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- -1 lithium-iron-phosphate compound Chemical class 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a high-machinability lithium iron phosphate cathode material. The method comprises the following steps of: preparing a mixture: weighing a lithium source compound, an iron source compound and a phosphorus source compound which are taken as raw materials according to a molar ratio of phosphorus : iron : lithium of 1:1:(1-1.05), adding a wetting agent into the mixture, mixing the mixture fully and then placing the mixture into a ball mill for ball-milling, then taking the mixture out and performing spray-drying to obtain a precursor, rolling the precursor under the pressure of 1,000 to 4,000PSI for 1 to 8 hours by using rolling equipment, and then taking the precursor out and placing the precursor into a powder pressing machine for pressing; and synthesizing the lithium iron phosphate: heating the sheet-like mixture to the temperature of 700 to 900 DEG C in air, calcining the mixture for 2 to 30 hours continuously to obtain a product, and performing coarse grinding, fine grinding, screening, carbon covering, mixing and drying on the product to obtain a target product. The method is simple and easy to control, and pollution-free industrial production can be realized easily.
Description
Technical field
The invention belongs to the preparing technical field of anode material for lithium-ion batteries, be specifically related to a kind of preparation method of high working property ability lithium iron phosphate positive material.
Background technology
The new forms of energy research and development are important foundations of human social, and along with development of human society, people are more and more strong to the new forms of energy demand of efficient, environmental protection, economy.Lithium ion battery can be widely used in a plurality of industry fields such as energy storage device, electric tool class, light-weight electric vehicle, fixed power supply, military equipment as one of important chemical power source.Especially extensive energy-storage battery and the development need high-energy-density of electrokinetic cell, high safety, environmental protection and cheap positive electrode.
Ferric phosphate reason with olivine structural is because advantages such as its raw material sources are abundant, cost is low, environmentally friendly, security performance is high, specific capacity is high, discharge platform is steady, thermal stability and cycle performance excellence are the positive electrodes of lithium dynamical battery first-selection.At present, LiFePO4 has been widely used on the large-sized power plants such as mobile phone, notebook computer, digital camera and photovoltaic energy-storage battery.In LiFePO4 preparation technology in the past, how to improve the specific surface of material and the processing characteristicies such as compacted density of pole piece is a difficult problem always, has restricted its development.
Summary of the invention
The object of the invention is exactly to the above-mentioned deficiency that oneself has technology to exist, and a kind of preparation method with lithium iron phosphate positive material of high working property ability is provided, so that realize commercially producing of LiFePO4.
Technical scheme of the present invention is: the preparation method of lithium ion battery anode material lithium iron phosphate may further comprise the steps:
The preparation of mixture: adopting Li source compound, Fe source compound and P source compound is raw material; In phosphorus: iron: the lithium mol ratio is ratio weighing Li source compound, Fe source compound and the P source compound of 1:1:1 ~ 1.05; Adding wetting agent fully mixes and is placed on ball milling in the ball mill; Take out spray-dried processing, the presoma that obtains takes out after rolling 1 ~ 8h under the pressure of rolling apparatus at 1000 ~ 4000PSI again, places the powder compressing machine compressing tablet;
Synthesizing iron lithium phosphate: flaky mixture is heated to 700 ~ 900 ℃ in air atmosphere, and continues calcining 2 ~ 30h down at 700 ~ 900 ℃, the product that obtains is again through coarse crushing; Fine powder is broken, screening, surface modification (carbon coating); Operations such as combination drying finally obtain the target product LiFePO4.
Adopt the mode of wet ball grinding that Li source compound, Fe source compound, P source compound are mixed in the step (1), the ball milling time is controlled at 24 ~ 50h.
Need after fully rolling 2 ~ 6h under the pressure of rolling apparatus at 1500 ~ 3000PSI, to take out again through the presoma after wet ball grinding and the spray drying in the said step (1), place the powder compressing machine compressing tablet.
Wetting agent is at least a in ethanol, acetone, the high purity water in the said step (1).
Mixture is after wet ball grinding and spray drying in the said step (1), and the presoma that obtains still needs fully to roll grinding through rolling apparatus.
Adopt the continous way heating means to be warming up to 800 ~ 850 ℃ to mixture in the said step (2), heating rate is 10 ~ 20 ℃/min.
Said Li source compound is to be selected from lithium hydroxide, lithium oxalate, lithium acetate, lithium carbonate, tert-butyl alcohol lithium, lithium benzoate, lithium formate, four water citric acid lithiums, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate and the lithium oxalate one or more.
Said Fe source compound is to be selected from one or more of ferric nitrate, ferrous oxalate, di-iron trioxide, ferrous oxide.
Said P source compound is one or more in phosphoric acid, ammonium phosphate, phosphorus pentoxide, ammonium dihydrogen phosphate, the diammonium hydrogen phosphate.
Said raw material carbon source is a graphite, one or more in glucose, sucrose, citric acid, starch, methylcellulose, carboxymethyl cellulose, ethyl cellulose, polyacrylamide, polyvinyl alcohol, the polyethylene glycol.
The invention has the beneficial effects as follows: the preparation method of this lithium ion battery anode material lithium iron phosphate of the present invention, technology is simple and easy to control, is easy to realize the suitability for industrialized production that cleans.This preparation method is at the raw material wet ball grinding, after the spray drying, also increased the step that rolling apparatus rolls grinding; The particle diameter and the chemical composition of LiFePO4 have been controlled effectively; Have more reasonably specific surface (m2/g) and compacted density (g/cm3), and processing characteristics is excellent, the LiFePO 4 material energy density of acquisition is high; Electric property is good, good stability.The LiFePO 4 material that utilizes the present invention to prepare has very high practical value, is with a wide range of applications as cell positive material.
Description of drawings
Fig. 1 is a process chart of the present invention.
Embodiment
In order to understand the present invention better, below in conjunction with embodiment the present invention is done further explanation, but the scope that the present invention requires to protect is not limited to the scope that embodiment explains.
Embodiment 1
With chemical pure ammonium dihydrogen phosphate; Ferrous oxalate; Lithium carbonate is the ratio weighing of 1:1:1.05 in molar ratio and mixes, and adds the abundant wetting mixing of adequate amount of ethanol and is placed on ball milling 24h in the planetary ball mill, takes out spray-dried processing; The presoma that obtains takes out compressing tablet again after fully rolling grinding 2h under the pressure of rolling apparatus at 1500psi.Flaky mixture is heated to 900 ℃ in air atmosphere, and continues calcining 3h down at 900 ℃, the product that obtains is again through coarse crushing, and fine powder is broken, screening, and surface modification (carbon coating), operations such as combination drying finally obtain the target product LiFePO4.
Embodiment 2
With chemical pure ammonium dihydrogen phosphate; Ferrous oxalate; Lithium carbonate is the ratio weighing of 1:1:1.05 in molar ratio and mixes, and adds the abundant wetting mixing of adequate amount of ethanol and is placed on ball milling 24h in the planetary ball mill, takes out spray-dried processing; The presoma that obtains takes out compressing tablet again after fully rolling grinding 4h under the pressure of rolling apparatus at 1500psi.Flaky mixture is heated to 900 ℃ in air atmosphere, and continues calcining 3h down at 900 ℃, the product that obtains is again through coarse crushing, and fine powder is broken, screening, and surface modification (carbon coating), operations such as combination drying finally obtain the target product LiFePO4.
Embodiment 3
With chemical pure ammonium dihydrogen phosphate; Ferrous oxalate; Lithium carbonate is the ratio weighing of 1:1:1.05 in molar ratio and mixes, and adds the abundant wetting mixing of adequate amount of ethanol and is placed on ball milling 24h in the planetary ball mill, takes out spray-dried processing; The presoma that obtains takes out compressing tablet again after fully rolling grinding 6h under the pressure of rolling apparatus at 1500psi.Flaky mixture is heated to 900 ℃ in air atmosphere, and continues calcining 3h down at 900 ℃, the product that obtains is again through coarse crushing, and fine powder is broken, screening, and surface modification (carbon coating), operations such as combination drying finally obtain the target product LiFePO4.
Embodiment 4
With chemical pure ammonium dihydrogen phosphate; Ferrous oxalate; Lithium carbonate is the ratio weighing of 1:1:1.05 in molar ratio and mixes, and adds the abundant wetting mixing of adequate amount of ethanol and is placed on ball milling 24h in the planetary ball mill, takes out spray-dried processing; The presoma that obtains takes out compressing tablet again after fully rolling grinding 6h under the pressure of rolling apparatus at 2000psi.Flaky mixture is heated to 900 ℃ in air atmosphere, and continues calcining 3h down at 900 ℃, the product that obtains is again through coarse crushing, and fine powder is broken, screening, and surface modification (carbon coating), operations such as combination drying finally obtain the target product LiFePO4.
Embodiment 5
With chemical pure ammonium dihydrogen phosphate; Ferrous oxalate; Lithium carbonate is the ratio weighing of 1:1:1.05 in molar ratio and mixes, and adds the abundant wetting mixing of adequate amount of ethanol and is placed on ball milling 24h in the planetary ball mill, takes out spray-dried processing; The presoma that obtains takes out compressing tablet again after fully rolling grinding 6h under the pressure of rolling apparatus at 2500psi.Flaky mixture is heated to 900 ℃ in air atmosphere, and continues calcining 3h down at 900 ℃, the product that obtains is again through coarse crushing, and fine powder is broken, screening, and surface modification (carbon coating), operations such as combination drying finally obtain the target product LiFePO4.
Embodiment 6
With chemical pure ammonium dihydrogen phosphate; Ferrous oxalate; Lithium carbonate is the ratio weighing of 1:1:1.05 in molar ratio and mixes, and adds the abundant wetting mixing of adequate amount of ethanol and is placed on ball milling 24h in the planetary ball mill, takes out spray-dried processing; The presoma that obtains takes out compressing tablet again after fully rolling grinding 5h under the pressure of rolling apparatus at 3000psi.Flaky mixture is heated to 900 ℃ in air atmosphere, and continues calcining 3h down at 900 ℃, the product that obtains is again through coarse crushing, and fine powder is broken, screening, and surface modification (carbon coating), operations such as combination drying finally obtain the target product LiFePO4.
Embodiment 7
With chemical pure phosphoric acid; Di-iron trioxide; Lithium hydroxide is the ratio weighing of 1:1:1.05 in molar ratio and mixes, and adds the abundant wetting mixing of adequate amount of ethanol and is placed on ball milling 24h in the planetary ball mill, takes out spray-dried processing; The presoma that obtains takes out compressing tablet again after fully rolling grinding 2h under the pressure of rolling apparatus at 2000psi.Flaky mixture is heated to 900 ℃ in air atmosphere, and continues calcining 3h down at 900 ℃, the product that obtains is again through coarse crushing, and fine powder is broken, screening, and surface modification (carbon coating), operations such as combination drying finally obtain the target product LiFePO4.
Embodiment 8
With chemical pure phosphorus pentoxide; Ferric nitrate; Lithium acetate is the ratio weighing of 1:1:1.05 in molar ratio and mixes, and adds the abundant wetting mixing of adequate amount of ethanol and is placed on ball milling 24h in the planetary ball mill, takes out spray-dried processing; The presoma that obtains takes out compressing tablet again after fully rolling grinding 4h under the pressure of rolling apparatus at 2500psi.Flaky mixture is heated to 900 ℃ in air atmosphere, and continues calcining 3h down at 900 ℃, the product that obtains is again through coarse crushing, and fine powder is broken, screening, and surface modification (carbon coating), operations such as combination drying finally obtain the target product LiFePO4.
Embodiment 9
With chemical pure ammonium dihydrogen phosphate; Ferrous oxide; Phosphoric acid hydrogen two lithiums are the ratio weighing of 1:1:1.05 in molar ratio and mix, and add the abundant wetting mixing of adequate amount of ethanol and are placed on ball milling 24h in the planetary ball mill, take out spray-dried processing; The presoma that obtains takes out compressing tablet again after fully rolling grinding 6h under the pressure of rolling apparatus at 3000psi.Flaky mixture is heated to 900 ℃ in air atmosphere, and continues calcining 3h down at 900 ℃, the product that obtains is again through coarse crushing, and fine powder is broken, screening, and surface modification (carbon coating), operations such as combination drying finally obtain the target product LiFePO4.
Modified model lithium-iron-phosphate compound and lithium ion battery negative material elemental metals lithium with method for preparing; With the Kynoar solution that is dissolved in the N-methyl pyrrolidone is the pole plate binding agent; Process the positive plate and the negative plate of lithium ion battery respectively; With the microporous polypropylene membrane is electrode diaphragm; With the volume ratio dimethyl carbonate: the 1M lithium hexafluoro phosphate of dimethyl carbonate: ethylene carbonate=1:1:1 is that electrolyte is assembled into lithium ion battery, and the correlated performance of battery is carried out testing result, sees the following form:
The lithium ion anode material performance table of embodiment preparation
Table one difference rolls the time to the material property influence relatively
Annotate: " processing characteristics " mainly is meant the compacted density of the specific surface and the pole piece of material.
The different rolling pressures of table two to the material property influence relatively
| Embodiment | Pressure (psi) | Active material ratio (%) |
| Embodiment three | 1500 | 93 |
| Embodiment four | 2000 | 94 |
| Embodiment five | 2500 | 95 |
| Embodiment six | 3000 | 96 |
Claims (10)
1. the preparation method of a lithium ion battery anode material lithium iron phosphate is characterized in that may further comprise the steps:
The preparation of mixture: adopting Li source compound, Fe source compound and P source compound is raw material; In phosphorus: iron: the lithium mol ratio is ratio weighing Li source compound, Fe source compound and the P source compound of 1:1:1 ~ 1.05; Adding wetting agent fully mixes and is placed on ball milling in the ball mill; Take out spray-dried processing, the presoma that obtains takes out after rolling 1 ~ 8h under the pressure of rolling apparatus at 1000 ~ 4000PSI again, places the powder compressing machine compressing tablet;
Synthesizing iron lithium phosphate: flaky mixture is heated to 700 ~ 900 ℃ in air atmosphere, and continues calcining 2 ~ 30h down at 700 ~ 900 ℃, the product that obtains is again through coarse crushing, and fine powder is broken, screening, and carbon coats, and the combination drying operation obtains the target product LiFePO4.
2. according to the preparation method of the said lithium ion battery anode material lithium iron phosphate of claim 1, it is characterized in that said Li source compound is to be selected from lithium hydroxide, lithium acetate, lithium oxalate, lithium carbonate, tert-butyl alcohol lithium, lithium benzoate, lithium formate, four water citric acid lithiums, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate and the lithium oxalate one or more.
3. according to the preparation method of the said lithium ion battery anode material lithium iron phosphate of claim 1, it is characterized in that said Fe source compound is to be selected from one or more of ferric nitrate, ferrous oxalate, di-iron trioxide, ferrous oxide.
4. according to the preparation method of the said lithium ion battery anode material lithium iron phosphate of claim 1, it is characterized in that said P source compound is one or more in phosphoric acid, ammonium phosphate, phosphorus pentoxide, ammonium dihydrogen phosphate, the diammonium hydrogen phosphate.
5. according to the preparation method of the said lithium ion battery anode material lithium iron phosphate of claim 1; It is characterized in that said raw material carbon source is a graphite, one or more in glucose, sucrose, citric acid, starch, methylcellulose, carboxymethyl cellulose, ethyl cellulose, polyacrylamide, polyvinyl alcohol, the polyethylene glycol.
6. according to the preparation method of one of claim 1-5 said lithium ion battery anode material lithium iron phosphate; It is characterized in that needing after fully rolling 2 ~ 6h under the pressure of rolling apparatus at 1500 ~ 3000PSI, to take out again through the presoma after wet ball grinding and the spray drying in the said step (1), place the powder compressing machine compressing tablet.
7. according to the preparation method of one of claim 1-6 said lithium ion battery anode material lithium iron phosphate; It is characterized in that adopting in the said step (1) mode of wet ball grinding that Li source compound, Fe source compound, P source compound are mixed, the ball milling time is controlled at 24 ~ 50h.
8. according to the preparation method of one of claim 1-6 said lithium ion battery anode material lithium iron phosphate, it is characterized in that wetting agent is at least a in ethanol, acetone, the high purity water in the said step (1).
9. according to the preparation method of one of claim 1-6 said lithium ion battery anode material lithium iron phosphate, it is characterized in that mixture is after wet ball grinding and spray drying in the said step (1), the presoma that obtains still needs fully to roll grinding through rolling apparatus.
10. according to the preparation method of one of claim 1-6 said lithium ion battery anode material lithium iron phosphate, it is characterized in that adopting the continous way heating means to be warming up to 800 ~ 850 ℃ to mixture in the said step (2), heating rate is 10 ~ 20 ℃/min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103618083A (en) * | 2013-11-16 | 2014-03-05 | 河南福森新能源科技有限公司 | Production method of high-capacity high-compaction lithium iron phosphate anode material |
| CN106744778A (en) * | 2016-12-28 | 2017-05-31 | 湖北金泉新材料有限责任公司 | A kind of method that molten-salt growth method prepares lithium iron phosphate cathode material |
| CN109686962A (en) * | 2019-01-21 | 2019-04-26 | 新奥石墨烯技术有限公司 | Prepare method, the anode, battery of iron phosphate compound anode material of lithium |
| CN113860281A (en) * | 2021-09-26 | 2021-12-31 | 桂林理工大学 | Method for preparing lithium iron phosphate as positive electrode material of lithium ion battery by using polymeric ferric sulfate as iron source |
| CN115385321A (en) * | 2022-09-08 | 2022-11-25 | 锂源(深圳)科学研究有限公司 | Flaky lithium iron phosphate positive electrode material and hydrothermal method preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519198A (en) * | 2009-04-16 | 2009-09-02 | 丁建民 | Method for preparing cathode material of lithium iron phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101519198A (en) * | 2009-04-16 | 2009-09-02 | 丁建民 | Method for preparing cathode material of lithium iron phosphate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103618083A (en) * | 2013-11-16 | 2014-03-05 | 河南福森新能源科技有限公司 | Production method of high-capacity high-compaction lithium iron phosphate anode material |
| CN103618083B (en) * | 2013-11-16 | 2015-11-18 | 河南福森新能源科技有限公司 | The production method of high-capacity high-compaction lithium iron phosphate anode material |
| CN106744778A (en) * | 2016-12-28 | 2017-05-31 | 湖北金泉新材料有限责任公司 | A kind of method that molten-salt growth method prepares lithium iron phosphate cathode material |
| CN109686962A (en) * | 2019-01-21 | 2019-04-26 | 新奥石墨烯技术有限公司 | Prepare method, the anode, battery of iron phosphate compound anode material of lithium |
| CN113860281A (en) * | 2021-09-26 | 2021-12-31 | 桂林理工大学 | Method for preparing lithium iron phosphate as positive electrode material of lithium ion battery by using polymeric ferric sulfate as iron source |
| CN115385321A (en) * | 2022-09-08 | 2022-11-25 | 锂源(深圳)科学研究有限公司 | Flaky lithium iron phosphate positive electrode material and hydrothermal method preparation method thereof |
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