CN103000895A - Method for preparing nano carbon-coated lithium ferrous phosphate positive material of lithium battery - Google Patents
Method for preparing nano carbon-coated lithium ferrous phosphate positive material of lithium battery Download PDFInfo
- Publication number
- CN103000895A CN103000895A CN2012105580038A CN201210558003A CN103000895A CN 103000895 A CN103000895 A CN 103000895A CN 2012105580038 A CN2012105580038 A CN 2012105580038A CN 201210558003 A CN201210558003 A CN 201210558003A CN 103000895 A CN103000895 A CN 103000895A
- Authority
- CN
- China
- Prior art keywords
- lithium
- ratio
- preparation
- ferric
- lithium battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 83
- 239000000463 material Substances 0.000 title claims abstract description 56
- 229940116007 ferrous phosphate Drugs 0.000 title claims abstract description 45
- 229910000155 iron(II) phosphate Inorganic materials 0.000 title claims abstract description 45
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 title claims abstract description 45
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000010406 cathode material Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000005303 weighing Methods 0.000 claims description 24
- -1 hydroxylamine compound Chemical class 0.000 claims description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000011368 organic material Substances 0.000 claims description 18
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005955 Ferric phosphate Substances 0.000 claims description 14
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 14
- 229940032958 ferric phosphate Drugs 0.000 claims description 14
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 14
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- 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 12
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 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
- 239000004254 Ammonium phosphate Substances 0.000 claims description 7
- 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 7
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 7
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 7
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 6
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 6
- 235000011007 phosphoric acid Nutrition 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000002245 particle Substances 0.000 abstract description 9
- 239000007791 liquid phase Substances 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001448 ferrous ion Inorganic materials 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract 2
- 235000000396 iron Nutrition 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000011651 chromium Substances 0.000 description 8
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 235000010323 ascorbic acid Nutrition 0.000 description 7
- 229960005070 ascorbic acid Drugs 0.000 description 7
- 239000011668 ascorbic acid Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- 235000002906 tartaric acid Nutrition 0.000 description 6
- 239000011975 tartaric acid Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 229910010710 LiFePO Inorganic materials 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 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 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 2
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229940113124 polysorbate 60 Drugs 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000001630 Pyrus pyrifolia var culta Nutrition 0.000 description 1
- 240000002609 Pyrus pyrifolia var. culta Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 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 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- NQLVCAVEDIGMMW-UHFFFAOYSA-N cyclopenta-1,3-diene;cyclopentane;nickel Chemical compound [Ni].C=1C=C[CH-]C=1.[CH-]1[CH-][CH-][CH-][CH-]1 NQLVCAVEDIGMMW-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- HYBKPGXXUMMMSY-UHFFFAOYSA-N lithium iron(3+) Chemical compound [Li+].[Fe+3] HYBKPGXXUMMMSY-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a method for preparing a nano carbon-coated lithium ferrous phosphate positive material of a lithium battery and belongs to the technical field of positive materials of lithium batteries. The method comprises the steps of: firstly, preparing a nano lithium ferrous phosphate material with uniform particle size by taking cheap ferric irons as an iron source through a liquid phase reaction method and then coating the prepared nano lithium ferrous phosphate material with carbon through high temperature catalysis. Compared with the prior preparation art, the method has the advantages that the nano lithium ferrous phosphate material prepared through the liquid phase reduction method is uniform in particle size; meanwhile, the ferric irons are adopted as the iron source, so that the problem that the ferrous ions are oxidized easily is resolved; and the prepared nano lithium ferrous phosphate material is coated with the carbon through the high temperature catalysis, and therefore, the crystallinity and the electronic conductivity of the material are improved and the nano carbon-coated lithium ferrous phosphate positive material is very applicable to be used for preparing secondary lithium ion batteries with high-rate charge and discharge.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery, particularly a kind of preparation method of lithium battery nano-carbon coated lithium iron phosphate cathode material belongs to the anode material of lithium battery technical field.
Background technology
Lithium ferrous phosphate as anode material of lithium ion battery has theoretical capacity high (170mAh/g theoretical specific capacity), Stability Analysis of Structures, security performance is good, and cycle performance is excellent, the advantages such as raw material sources are extensive are considered to one of positive electrode of the most promising lithium ion power and energy-storage battery.But the conductivity that this material is low (is about 10 under the room temperature
-9S/cm) and low lithium ion diffusion coefficient cause its high rate capability poor, thereby limit its further application.
The preparation method of LiFePO 4 mainly contains high temperature solid-state method, hydro thermal method, sol-gel process, liquid-phase coprecipitation etc. at present.Such as the people such as Barker (J. Barker, M. Y. Saidi, J. L. Swoyer, Lithium iron (III) phospho-olivines prepared by a novl carbothermal reduction method.
Eletrochem. Solid-State Lett., 2003,6 (3): A53-A50.) with ferric iron (Fe
2O
3) be source of iron, LiH
2PO
4Former for lithium source and phosphorus, carbon is reducing agent and carbon source, adopts pyrocarbon thermal reduction synthetic LiFePO that prepared in Ar atmosphere
4/ C composite material.Because the irregular shape of initiation material, the synthetic material granule pattern of the method is difficult to control, and particle size is larger, and the material particle size skewness causes its high rate capability improvement effect and not obvious.
The people such as Yang (J. S. Yang, J. J. Xu, Nonaqueous sol-gel synthesis of high-performance LiFePO
4.
Eletrochem. Solid-State Lett., 2004,7 (12): A515-A518.) method with non-aqueous sol-gel has prepared LiFePO take ferrous acetate, lithium acetate and phosphoric acid as raw material
4/ C composite material, average particle size particle size is about 100-300 nm.This preparation method's advantage is that raw material is blended in intermolecular carrying out, synthesis temperature is low, roasting afterproduct particle fine size is even, the distribution of sizes narrow range, solid phase method has the advantage that hardly matches relatively, and shortcoming is: the divalence source of iron that cost commonly used is more expensive, and the lithium source consumes more, the complicated process of preparation difficulty is easily introduced Fe
3+Impurity.
Summary of the invention
The present invention is intended to solve the problem of the low conductivity of ferrousphosphate lithium material, various deficiencies for existing preparation method, the invention provides a kind of preparation method of lithium battery nano-carbon coated lithium iron phosphate cathode material, this technique can be controlled particle diameter and the phase constituent of LiFePO 4 effectively, improve electric conductivity, improve its chemical property.
In order to realize the foregoing invention purpose, its concrete technical scheme is as follows:
A kind of preparation method of lithium battery nano-carbon coated lithium iron phosphate cathode material is characterized in that: comprise following processing step:
A, be that 1-1.5:1:1 takes by weighing Li source compound, ferric iron source compound and P source compound by the mol ratio of Li:Fe:P, place in the reactor, simultaneously in reactor, add deionized water, then add reducing agent to reactor, last solution is at 2-10 hour the suspension-turbid liquid to celadon of 110-150 ℃ of lower reaction;
B, the suspension-turbid liquid of the celadon in the steps A carried out centrifuge washing with deionized water after, obtained ferrousphosphate lithium material in lower dry 6-10 hour at 60-100 ℃;
C, with the ferrousphosphate lithium material for preparing among the step B and carbon source catalyst, carbonaceous organic material; mix for ball milling after the ratio weighing of 1:0.001-0.005:0.01-1 in molar ratio; then place the inert atmosphere protection stove; at 450-750 ℃ of roasting temperature 2-16 hour, cooling obtained lithium battery nano-carbon coated lithium iron phosphate cathode material naturally.
Preferably, the present invention is in steps A, and described Li source compound is one or any ratio multiple in lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate and the lithium iodide.
Preferably, the present invention is in steps A, and described ferric iron source compound is one or any ratio multiple in ferric trichloride, ferric phosphate, ferric sulfate, di-iron trioxide, tri-iron tetroxide and the ferric nitrate.
Preferably, the present invention is in steps A, and described P source compound is one or any ratio multiple in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid, ferric phosphate and the sodium dihydrogen phosphate.
Preferably, the present invention is in steps A, and the addition of described deionized water is 50-80% for interpolation deionized water in reactor makes its compactedness.
Preferably, the present invention is in steps A, and described reducing agent is one or any ratio multiple in carboxylic acids, aldehydes, hydroxylamine compound such as hydroxylamine chloride, HAS, hutanal, tartaric acid, ascorbic acid and the formic acid.
Preferably or further, the present invention is in steps A, and the addition of described reducing agent is that the ratio of 0.2:1 is added reducing agent to reactor for the mol ratio according to Fe ion and reducing agent.
Preferably, the present invention is in step B, and described centrifuge washing is centrifuge washing 3-5 time.
Preferably, the present invention is in step C, and described carbon source catalyst is a kind of in Fe, Cr, the Ni bicyclic pentadiene compounds.
Preferably, the present invention is in step C, and described carbonaceous organic material is hydrocarbon oxygen compound or hydrocarbon.Such as glucose, one or any ratio in starch, sucrose, polyvinyl alcohol, polybutadiene, polypropylene, polystyrene, polyethylene glycol oxide, polyacrylic acid, the poly yamanashi esters multiple.
The useful technique effect that the present invention brings:
1, the present invention at first by the liquid phase reactor method take the ferric iron of cheapness as source of iron prepares evengranular nanometer ferrousphosphate lithium material, then by high-temperature catalytic prepared nanometer ferrousphosphate lithium material being carried out carbon coats, compare with existing technology of preparing, preparation method of the present invention is by the nano-lithium iron phosphate of liquid phase reduction preparation, the material granule size uniform, adopt simultaneously ferric iron source, solved the problem of the easy oxidation of ferrous ion; This preparation method carries out carbon by high-temperature catalytic to prepared nanometer ferrousphosphate lithium material and coats, and has improved degree of crystallinity and the electronic conductivity of material, is highly suitable for the lithium rechargeable battery of high power charging-discharging;
2, the present invention at first adopts the source of iron of trivalent and adds reducing agent and solved the problem of oxidation of ferrous ion in the precursor, secondly material granule can not grown up under the liquid-phase reaction condition of the first step, can access nano particle, just degree of crystallinity is imperfect, follow-up high-temperature catalytic roasting improves material degree of crystallinity on the one hand, excessively grow up by adding carbon source inhibition particle, improved on the other hand the degree of graphitization of carbon coated by C catalyst, thereby improved the electronic conductivity of material.
Description of drawings
Fig. 1 is LiFePO among the embodiment 9
4The SEM photo of material.
Fig. 2 is the prepared LiFePO of embodiment 9
4The discharge curve of material under different multiplying, voltage range 2.5-4.3V, electrolyte are 1 mol/L LiPF
6Equal-volume than ethylene carbonate (EC), dimethyl carbonic ether (DMC) solution, probe temperature is 25 ℃ ± 0.5 ℃.
Embodiment
Embodiment 1
A kind of preparation method of lithium battery nano-carbon coated lithium iron phosphate cathode material comprises following processing step:
A, be that 1:1:1 takes by weighing Li source compound, ferric iron source compound and P source compound by the mol ratio of Li:Fe:P, place in the reactor, simultaneously add deionized water in reactor, then add reducing agent to reactor, last solution is at 2 hours the suspension-turbid liquid to celadon of 110 ℃ of lower reactions;
B, the suspension-turbid liquid of the celadon in the steps A carried out centrifuge washing with deionized water after, obtained ferrousphosphate lithium material in lower dry 6 hours at 60 ℃;
C, with the ferrousphosphate lithium material for preparing among the step B and carbon source catalyst, carbonaceous organic material; mix for ball milling after the ratio weighing of 1:0.001:0.01 in molar ratio; then place the inert atmosphere protection stove; 450 ℃ of roasting temperatures 2 hours, cooling obtained lithium battery nano-carbon coated lithium iron phosphate cathode material naturally.
Embodiment 2
A kind of preparation method of lithium battery nano-carbon coated lithium iron phosphate cathode material comprises following processing step:
A, be that 1.5:1:1 takes by weighing Li source compound, ferric iron source compound and P source compound by the mol ratio of Li:Fe:P, place in the reactor, simultaneously in reactor, add deionized water, then add reducing agent to reactor, last solution is at 10 hours the suspension-turbid liquid to celadon of 150 ℃ of lower reactions;
B, the suspension-turbid liquid of the celadon in the steps A carried out centrifuge washing with deionized water after, obtained ferrousphosphate lithium material in lower dry 10 hours at 100 ℃;
C, with the ferrousphosphate lithium material for preparing among the step B and carbon source catalyst, carbonaceous organic material; mix for ball milling after the ratio weighing of 1:0.005:1 in molar ratio; then place the inert atmosphere protection stove; 750 ℃ of roasting temperatures 16 hours, cooling obtained lithium battery nano-carbon coated lithium iron phosphate cathode material naturally.
Embodiment 3
A kind of preparation method of lithium battery nano-carbon coated lithium iron phosphate cathode material comprises following processing step:
A, be that 1.25:1:1 takes by weighing Li source compound, ferric iron source compound and P source compound by the mol ratio of Li:Fe:P, place in the reactor, simultaneously in reactor, add deionized water, then add reducing agent to reactor, last solution is at 6 hours the suspension-turbid liquid to celadon of 130 ℃ of lower reactions;
B, the suspension-turbid liquid of the celadon in the steps A carried out centrifuge washing with deionized water after, obtained ferrousphosphate lithium material in lower dry 8 hours at 80 ℃;
C, with the ferrousphosphate lithium material for preparing among the step B and carbon source catalyst, carbonaceous organic material; mix for ball milling after the ratio weighing of 1:0.003:0.5 in molar ratio; then place the inert atmosphere protection stove; 600 ℃ of roasting temperatures 9 hours, cooling obtained lithium battery nano-carbon coated lithium iron phosphate cathode material naturally.
Embodiment 4
A kind of preparation method of lithium battery nano-carbon coated lithium iron phosphate cathode material comprises following processing step:
A, be that 1.38:1:1 takes by weighing Li source compound, ferric iron source compound and P source compound by the mol ratio of Li:Fe:P, place in the reactor, simultaneously in reactor, add deionized water, then add reducing agent to reactor, last solution is at 8 hours the suspension-turbid liquid to celadon of 121 ℃ of lower reactions;
B, the suspension-turbid liquid of the celadon in the steps A carried out centrifuge washing with deionized water after, obtained ferrousphosphate lithium material in lower dry 9.5 hours at 72 ℃;
C, with the ferrousphosphate lithium material for preparing among the step B and carbon source catalyst, carbonaceous organic material; mix for ball milling after the ratio weighing of 1:0.002:0.26 in molar ratio; then place the inert atmosphere protection stove; 700 ℃ of roasting temperatures 3.5 hours, cooling obtained lithium battery nano-carbon coated lithium iron phosphate cathode material naturally.
Embodiment 5
On the basis of embodiment 1-4, preferred:
In steps A, described Li source compound is one or any ratio multiple in lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate and the lithium iodide.
In steps A, described ferric iron source compound is one or any ratio multiple in ferric trichloride, ferric phosphate, ferric sulfate, di-iron trioxide, tri-iron tetroxide and the ferric nitrate.
In steps A, described P source compound is one or any ratio multiple in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid, ferric phosphate and the sodium dihydrogen phosphate.
In steps A, the addition of described deionized water is 50% for interpolation deionized water in reactor makes its compactedness.
In steps A, described reducing agent is one or any ratio multiple in carboxylic acids, aldehydes, hydroxylamine compound such as hydroxylamine chloride, HAS, hutanal, tartaric acid, ascorbic acid and the formic acid.
In steps A, the addition of described reducing agent is for being that the ratio of 0.2:1 is added reducing agent to reactor according to the mol ratio of Fe ion and reducing agent.
In step B, described centrifuge washing is centrifuge washing 3 times.
In step C, described carbon source catalyst is a kind of in Fe, Cr, the Ni bicyclic pentadiene compounds.
In step C, described carbonaceous organic material is hydrocarbon oxygen compound or hydrocarbon.
Embodiment 6
On the basis of embodiment 1-4, preferred:
In steps A, described Li source compound is one or any ratio multiple in lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate and the lithium iodide.
In steps A, described ferric iron source compound is one or any ratio multiple in ferric trichloride, ferric phosphate, ferric sulfate, di-iron trioxide, tri-iron tetroxide and the ferric nitrate.
In steps A, described P source compound is one or any ratio multiple in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid, ferric phosphate and the sodium dihydrogen phosphate.
In steps A, the addition of described deionized water is 80% for interpolation deionized water in reactor makes its compactedness.
In steps A, described reducing agent is one or any ratio multiple in carboxylic acids, aldehydes, hydroxylamine compound such as hydroxylamine chloride, HAS, hutanal, tartaric acid, ascorbic acid and the formic acid.
In steps A, the addition of described reducing agent is for being that the ratio of 0.2:1 is added reducing agent to reactor according to the mol ratio of Fe ion and reducing agent.
In step B, described centrifuge washing is centrifuge washing 5 times.
In step C, described carbon source catalyst is a kind of in Fe, Cr, the Ni bicyclic pentadiene compounds.
In step C, described carbonaceous organic material is hydrocarbon oxygen compound or hydrocarbon.
Embodiment 7
On the basis of embodiment 1-4, preferred:
In steps A, described Li source compound is one or any ratio multiple in lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate and the lithium iodide.
In steps A, described ferric iron source compound is one or any ratio multiple in ferric trichloride, ferric phosphate, ferric sulfate, di-iron trioxide, tri-iron tetroxide and the ferric nitrate.
In steps A, described P source compound is one or any ratio multiple in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid, ferric phosphate and the sodium dihydrogen phosphate.
In steps A, the addition of described deionized water is 65% for interpolation deionized water in reactor makes its compactedness.
In steps A, described reducing agent is one or any ratio multiple in carboxylic acids, aldehydes, hydroxylamine compound such as hydroxylamine chloride, HAS, hutanal, tartaric acid, ascorbic acid and the formic acid.
In steps A, the addition of described reducing agent is for being that the ratio of 0.2:1 is added reducing agent to reactor according to the mol ratio of Fe ion and reducing agent.
In step B, described centrifuge washing is centrifuge washing 4 times.
In step C, described carbon source catalyst is a kind of in Fe, Cr, the Ni bicyclic pentadiene compounds.
In step C, described carbonaceous organic material is hydrocarbon oxygen compound or hydrocarbon.
Embodiment 8
On the basis of embodiment 1-4, preferred:
In steps A, described Li source compound is one or any ratio multiple in lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate and the lithium iodide.
In steps A, described ferric iron source compound is one or any ratio multiple in ferric trichloride, ferric phosphate, ferric sulfate, di-iron trioxide, tri-iron tetroxide and the ferric nitrate.
In steps A, described P source compound is one or any ratio multiple in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid, ferric phosphate and the sodium dihydrogen phosphate.
In steps A, the addition of described deionized water is 75% for interpolation deionized water in reactor makes its compactedness.
In steps A, described reducing agent is one or any ratio multiple in carboxylic acids, aldehydes, hydroxylamine compound such as hydroxylamine chloride, HAS, hutanal, tartaric acid, ascorbic acid and the formic acid.
In steps A, the addition of described reducing agent is for being that the ratio of 0.2:1 is added reducing agent to reactor according to the mol ratio of Fe ion and reducing agent.
In step B, described centrifuge washing is centrifuge washing 4 times.
In step C, described carbon source catalyst is a kind of in Fe, Cr, the Ni bicyclic pentadiene compounds.
In step C, described carbonaceous organic material is hydrocarbon oxygen compound or hydrocarbon.
Embodiment 9
Take lithium oxalate, ferric trichloride, ammonium phosphate as the lithium source, source of iron and phosphorus source, place in the reactor by the weighing of Li:Fe:P mol ratio 1.05:1:1 proportioning, adding simultaneously deionized water in the reactor, to make its compactedness be 60%, is that the ratio of 0.2:1 is added the reducing agent hydroxylamine chloride in reactor according to the mol ratio of Fe ion and reducing agent then.Solution is at 2 hours the suspension-turbid liquid to celadon of 150 ℃ of lower reactions; Suspension-turbid liquid carries out behind 3 centrifuge washings in 80 ℃ of air dry ovens obtaining in dry 8 hours nanometer ferrousphosphate lithium material with deionized water; With prepared ferrousphosphate lithium material, carbon source catalyst ferrocene, carbonaceous organic material soluble starch, mix in ball milling after the ratio weighing proportioning of stoichiometric proportion 1:0.001:0.01, then place N
2In the atmosphere protection stove, after 8 hours, cooling obtains the ferrousphosphate lithium material of grey black naturally at 550 ℃ of roasting temperatures.Material granule is of a size of 80-120nm.Fig. 1 has provided its SEM photo.
Ferrousphosphate lithium material with example 9 gained is made electrode as follows.
Take organic solvent 1-methyl-2 pyrrolidones (NMP) as solvent, with the electrode material, conductive agent (acetylene black) and the binding agent Kynoar (PVDF) that prepare in mass ratio after the 80:10:10 mixing and stirring, being evenly coated in diameter is on the aluminum foil current collector of 14 mm, 75 ℃ of oven dry in drying box, then use the tablet press machine compacting evenly, make electrode slice to be measured.Adopt the button type simulated battery that prepared electrode slice is carried out the battery assembling.Be metal lithium sheet to electrode wherein, barrier film is Celgard 2325 composite membranes, and electrolyte is 1 mol/L LiPF
6Equal-volume than ethylene carbonate (EC), dimethyl carbonic ether (DMC) solution, battery pack is contained in the glove box that is full of argon gas and finishes.The battery that fills is done the constant current charge-discharge test between 2.5 ~ 4.2 V voltage ranges.Fig. 2 has provided in the example 9 ferrousphosphate lithium material at the discharge curve (1C=170 mAh/g) of different multiplying.
Embodiment 10
Take lithium carbonate, ferric sulfate, ammonium hydrogen phosphate as the lithium source, source of iron and phosphorus source, place in the reactor by the weighing of Li:Fe:P mol ratio 1.5:1:1 proportioning, adding simultaneously deionized water in the reactor, to make its compactedness be 50%, is that the ratio of 0.2:1 is added the reducing agent HAS in reactor according to the mol ratio of Fe ion and reducing agent then.Solution is at 5 hours the suspension-turbid liquid to celadon of 140 ℃ of lower reactions; Suspension-turbid liquid carries out behind 3 centrifuge washings in 60 ℃ of air dry ovens obtaining in dry 10 hours nanometer ferrousphosphate lithium material with deionized water; With prepared ferrousphosphate lithium material, carbon source catalyst dicyclopentadienyl nickel, carbonaceous organic material polyvinyl alcohol; mix in ball milling after the ratio weighing proportioning of stoichiometric proportion 1:0.002:1; then place Ar atmosphere protection stove; after 2 hours, cooling obtains the ferrousphosphate lithium material of grey black naturally at 750 ℃ of roasting temperatures.
Embodiment 11
Take lithium carbonate, ferric phosphate as the lithium source, source of iron and phosphorus source, place in the reactor by the weighing of Li:Fe:P mol ratio 1:1:1 proportioning, adding simultaneously deionized water in the reactor, to make its compactedness be 80%, is that the ratio of 0.2:1 is added the reducing agent ascorbic acid in reactor according to the mol ratio of Fe ion and reducing agent then.Solution is at 8 hours the suspension-turbid liquid to celadon of 120 ℃ of lower reactions; Suspension-turbid liquid carries out behind 3 centrifuge washings in 100 ℃ of air dry ovens obtaining in dry 6 hours nanometer ferrousphosphate lithium material with deionized water; With prepared ferrousphosphate lithium material, carbon source catalyst ferrocene, carbonaceous organic material polypropylene; mix in ball milling after the ratio weighing proportioning of stoichiometric proportion 1:0.004:0.05; then place Ar atmosphere protection stove; after 16 hours, cooling obtains the ferrousphosphate lithium material of grey black naturally at 450 ℃ of roasting temperatures.
Embodiment 12
Take lithium hydroxide, ferric phosphate as the lithium source, source of iron and phosphorus source, place in the reactor by the weighing of Li:Fe:P mol ratio 1.02:1:1 proportioning, adding simultaneously deionized water in the reactor, to make its compactedness be 70%, is that the ratio of 0.2:1 is added reducing agent ascorbic acid and tartaric acid in reactor according to the mol ratio of Fe ion and reducing agent then.Solution is at 8 hours the suspension-turbid liquid to celadon of 120 ℃ of lower reactions; Suspension-turbid liquid carries out behind 3 centrifuge washings in 70 ℃ of air dry ovens obtaining in dry 9 hours nanometer ferrousphosphate lithium material with deionized water; With prepared ferrousphosphate lithium material, carbon source catalyst two luxuriant chromium, carbonaceous organic material glucose; mix in ball milling after the ratio weighing proportioning of stoichiometric proportion 1:0.005:0.01; then place Ar atmosphere protection stove; after 12 hours, cooling obtains the ferrousphosphate lithium material of grey black naturally at 500 ℃ of roasting temperatures.
Embodiment 13
Take lithium oxalate, di-iron trioxide, phosphoric acid as the lithium source, source of iron and phosphorus source, place in the reactor by the weighing of Li:Fe:P mol ratio 1.2:1:1 proportioning, adding simultaneously deionized water in the reactor, to make its compactedness be 65%, is that the ratio of 0.2:1 is added the reducing agent hydroxylamine chloride in reactor according to the mol ratio of Fe ion and reducing agent then.Solution is at 10 hours the suspension-turbid liquid to celadon of 110 ℃ of lower reactions; Suspension-turbid liquid carries out behind 3 centrifuge washings in 70 ℃ of air dry ovens obtaining in dry 10 hours nanometer ferrousphosphate lithium material with deionized water; With prepared ferrousphosphate lithium material, carbon source catalyst two luxuriant chromium, carbonaceous organic material polysorbate60; mix in ball milling after the ratio weighing proportioning of stoichiometric proportion 1:0.005:0.5; then place N2 atmosphere protection stove; after 6 hours, cooling obtains the ferrousphosphate lithium material of grey black naturally at 600 ℃ of roasting temperatures.
Embodiment 14
Take lithium acetate, ferric trichloride, phosphoric acid hydrogen ammonia as the lithium source, source of iron and phosphorus source, place in the reactor by the weighing of Li:Fe:P mol ratio 1.3:1:1 proportioning, adding simultaneously deionized water in the reactor, to make its compactedness be 60%, is that the ratio of 0.2:1 is to reactor reducing agent formic acid according to the mol ratio of Fe ion and reducing agent then.Solution is at 5 hours the suspension-turbid liquid to celadon of 150 ℃ of lower reactions; Suspension-turbid liquid carries out behind 3 centrifuge washings in 80 ℃ of air dry ovens obtaining in dry 5 hours nanometer ferrousphosphate lithium material with deionized water; With prepared ferrousphosphate lithium material, carbon source catalyst two luxuriant chromium, carbonaceous organic material polysorbate60; mix in ball milling after the ratio weighing proportioning of stoichiometric proportion 1:0.005:0.5; then place Ar atmosphere protection stove; after 4 hours, cooling obtains the ferrousphosphate lithium material of grey black naturally at 700 ℃ of roasting temperatures.
Claims (10)
1. the preparation method of a lithium battery nano-carbon coated lithium iron phosphate cathode material is characterized in that: comprise following processing step:
A, be that 1-1.5:1:1 takes by weighing Li source compound, ferric iron source compound and P source compound by the mol ratio of Li:Fe:P, place in the reactor, simultaneously in reactor, add deionized water, then add reducing agent to reactor, last solution is at 2-10 hour the suspension-turbid liquid to celadon of 110-150 ℃ of lower reaction;
B, the suspension-turbid liquid of the celadon in the steps A carried out centrifuge washing with deionized water after, obtained ferrousphosphate lithium material in lower dry 6-10 hour at 60-100 ℃;
C, with the ferrousphosphate lithium material for preparing among the step B and carbon source catalyst, carbonaceous organic material; mix for ball milling after the ratio weighing of 1:0.001-0.005:0.01-1 in molar ratio; then place the inert atmosphere protection stove; at 450-750 ℃ of roasting temperature 2-16 hour, cooling obtained lithium battery nano-carbon coated lithium iron phosphate cathode material naturally.
2. the preparation method of a kind of lithium battery nano-carbon coated lithium iron phosphate cathode material according to claim 1, it is characterized in that: in steps A, described Li source compound is one or any ratio multiple in lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate and the lithium iodide.
3. the preparation method of a kind of lithium battery nano-carbon coated lithium iron phosphate cathode material according to claim 1, it is characterized in that: in steps A, described ferric iron source compound is one or any ratio multiple in ferric trichloride, ferric phosphate, ferric sulfate, di-iron trioxide, tri-iron tetroxide and the ferric nitrate.
4. the preparation method of a kind of lithium battery nano-carbon coated lithium iron phosphate cathode material according to claim 1, it is characterized in that: in steps A, described P source compound is one or any ratio multiple in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid, ferric phosphate and the sodium dihydrogen phosphate.
5. the preparation method of a kind of lithium battery nano-carbon coated lithium iron phosphate cathode material according to claim 1 is characterized in that: in steps A, to make its compactedness be 50-80% to the addition of described deionized water in order to add deionized water in reactor.
6. the preparation method of a kind of lithium battery nano-carbon coated lithium iron phosphate cathode material according to claim 1, it is characterized in that: in steps A, described reducing agent is one or any ratio multiple in carboxylic acids, aldehydes, the hydroxylamine compound.
7. according to claim 1 or the preparation method of 6 described a kind of lithium battery nano-carbon coated lithium iron phosphate cathode materials, it is characterized in that: in steps A, the addition of described reducing agent is for being that the ratio of 0.2:1 is added reducing agent to reactor according to the mol ratio of Fe ion and reducing agent.
8. the preparation method of a kind of lithium battery nano-carbon coated lithium iron phosphate cathode material according to claim 1, it is characterized in that: in step B, described centrifuge washing is centrifuge washing 3-5 time.
9. the preparation method of a kind of lithium battery nano-carbon coated lithium iron phosphate cathode material according to claim 1 is characterized in that: in step C, described carbon source catalyst is a kind of in Fe, Cr, the Ni bicyclic pentadiene compounds.
10. the preparation method of a kind of lithium battery nano-carbon coated lithium iron phosphate cathode material according to claim 1, it is characterized in that: in step C, described carbonaceous organic material is hydrocarbon oxygen compound or hydrocarbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210558003.8A CN103000895B (en) | 2012-12-20 | 2012-12-20 | A kind of preparation method of lithium battery nano-carbon coated lithium iron phosphate cathode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210558003.8A CN103000895B (en) | 2012-12-20 | 2012-12-20 | A kind of preparation method of lithium battery nano-carbon coated lithium iron phosphate cathode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103000895A true CN103000895A (en) | 2013-03-27 |
| CN103000895B CN103000895B (en) | 2015-09-16 |
Family
ID=47929212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210558003.8A Active CN103000895B (en) | 2012-12-20 | 2012-12-20 | A kind of preparation method of lithium battery nano-carbon coated lithium iron phosphate cathode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103000895B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103247778A (en) * | 2013-04-26 | 2013-08-14 | 北大先行科技产业有限公司 | High-power lithium iron phosphate positive pole material and manufacturing method thereof |
| CN103265001A (en) * | 2013-05-02 | 2013-08-28 | 杭州电子科技大学 | Method for preparing carbon-coated lithium iron phosphate from basic lithium iron phosphate |
| CN109346708A (en) * | 2018-11-20 | 2019-02-15 | 贵州大学 | A kind of preparation method of the carbon-coated ferrous phosphate of LITHIUM BATTERY |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008088573A1 (en) * | 2006-06-12 | 2008-07-24 | The Regents Of University Of California | Optimization of carbon coatings |
| CN101475157A (en) * | 2009-01-21 | 2009-07-08 | 武汉大学 | Preparation of lithium iron phosphate nano composite microsphere |
| CN101572305A (en) * | 2009-05-31 | 2009-11-04 | 浙江大学 | Preparation method of LiFePO*/C cathode material with high rate performance |
-
2012
- 2012-12-20 CN CN201210558003.8A patent/CN103000895B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008088573A1 (en) * | 2006-06-12 | 2008-07-24 | The Regents Of University Of California | Optimization of carbon coatings |
| CN101475157A (en) * | 2009-01-21 | 2009-07-08 | 武汉大学 | Preparation of lithium iron phosphate nano composite microsphere |
| CN101572305A (en) * | 2009-05-31 | 2009-11-04 | 浙江大学 | Preparation method of LiFePO*/C cathode material with high rate performance |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103247778A (en) * | 2013-04-26 | 2013-08-14 | 北大先行科技产业有限公司 | High-power lithium iron phosphate positive pole material and manufacturing method thereof |
| CN103247778B (en) * | 2013-04-26 | 2015-12-23 | 北大先行科技产业有限公司 | A kind of high-power lithium iron phosphate positive pole material and preparation method thereof |
| CN103265001A (en) * | 2013-05-02 | 2013-08-28 | 杭州电子科技大学 | Method for preparing carbon-coated lithium iron phosphate from basic lithium iron phosphate |
| CN109346708A (en) * | 2018-11-20 | 2019-02-15 | 贵州大学 | A kind of preparation method of the carbon-coated ferrous phosphate of LITHIUM BATTERY |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103000895B (en) | 2015-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103109399B (en) | A kind of containing lithium salts-graphene composite material and preparation method thereof | |
| CN101315981B (en) | Lithium iron phosphate anode material for lithium ion battery and modification method | |
| CN101582498A (en) | Method for preparing nanometer ferrous phosphate lithium /carbon composite material | |
| CN102623708A (en) | Preparation method of lithium vanadium phosphate (Li3V2(PO4)3)/graphene composite material for positive electrode of lithium ion battery | |
| CN103000893B (en) | A kind of spray pyrolysis preparation method of lithium battery manganese-lithium phosphate anode material | |
| CN102227024B (en) | Lithium iron phosphate anode material for power lithium ion battery and preparation method thereof | |
| CN102244233B (en) | Method for preparing composite cathode material of graphene-like doped-cladded lithium titanate | |
| CN104638242A (en) | Method for synthesizing lithium ion battery cathode material lithium iron phosphate through in situ polymerizing and cladding | |
| CN102074687A (en) | Hydrothermal synthesis method for preparing nano-scale carbon-coated lithium iron phosphate | |
| CN103594708B (en) | One is appraised at the current rate iron-based composite positive pole and preparation method thereof | |
| CN104752693A (en) | Preparation method for lithium ion battery anode material lithium iron phosphate/graphene compound | |
| CN102437311A (en) | Lithium iron phosphate composite material, its preparation method and application | |
| CN112397698B (en) | Composite conductive agent coated lithium iron phosphate material and preparation method and application thereof | |
| CN102082264A (en) | Method for preparing presoma of active electrode material of nano-lithium ion battery and application thereof | |
| CN103137970A (en) | Porous manganese phosphate lithium-carbon composite material and preparation method | |
| CN105261744A (en) | Preparation method of porous vanadium manganese oxide anode material | |
| CN103022487B (en) | A kind of preparation method of nanometer manganese lithium phosphate anode material of lithium battery | |
| CN105226267A (en) | Three dimensional carbon nanotubes modifies spinel nickel lithium manganate material and its preparation method and application | |
| CN102347476A (en) | Lithium iron phosphate/carbon composite anode material prepared by catalytic graphitization method, and preparation method thereof | |
| CN102324519A (en) | High-conductivity ferrous phosphate lithium cathode material for lithium ion battery and preparation method thereof | |
| CN102267692B (en) | Self-sacrificing template method for preparing nanoscale lithium ferrous phosphate | |
| CN103000895B (en) | A kind of preparation method of lithium battery nano-carbon coated lithium iron phosphate cathode material | |
| CN102593462A (en) | Method for preparing lithium iron phosphate by coating carbon | |
| WO2023226550A1 (en) | Preparation method for high-conductivity lithium iron phosphate and use thereof | |
| CN109980221A (en) | A kind of anode material for high-voltage lithium ion and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180425 Address after: 610000 18 West core road, hi-tech West District, Chengdu, Sichuan Patentee after: Dongfang Electric Co., Ltd. Address before: 610036 Shu Han Road, Jinniu District, Chengdu, Sichuan Province, No. 333 Patentee before: Dongfang Electric Corporation |