CN101693532A - Method for preparing lithium ferrous phosphate - Google Patents
Method for preparing lithium ferrous phosphate Download PDFInfo
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- CN101693532A CN101693532A CN200910093735A CN200910093735A CN101693532A CN 101693532 A CN101693532 A CN 101693532A CN 200910093735 A CN200910093735 A CN 200910093735A CN 200910093735 A CN200910093735 A CN 200910093735A CN 101693532 A CN101693532 A CN 101693532A
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- China
- Prior art keywords
- lithium
- slurry
- ferrous phosphate
- lifepo
- lithium ferrous
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 25
- 229940116007 ferrous phosphate Drugs 0.000 title claims abstract description 23
- 229910000155 iron(II) phosphate Inorganic materials 0.000 title claims abstract description 23
- 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 23
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 14
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 13
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 238000000875 high-speed ball milling Methods 0.000 claims description 7
- IPBYARKNCJJHKZ-UHFFFAOYSA-L [Fe+2].O.[PH2](=O)[O-].[PH2](=O)[O-] Chemical compound [Fe+2].O.[PH2](=O)[O-].[PH2](=O)[O-] IPBYARKNCJJHKZ-UHFFFAOYSA-L 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
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000007669 thermal treatment Methods 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- 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 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- 239000008103 glucose 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
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229960004106 citric acid Drugs 0.000 claims description 2
- 229960001031 glucose Drugs 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229960004793 sucrose Drugs 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract 2
- 238000000498 ball milling Methods 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- RQKNQWUJROKKEQ-UHFFFAOYSA-K iron(3+);phosphate;hydrate Chemical compound [OH-].[Fe+3].OP([O-])([O-])=O RQKNQWUJROKKEQ-UHFFFAOYSA-K 0.000 abstract 1
- 239000007921 spray Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 8
- 238000007599 discharging Methods 0.000 description 6
- 230000004087 circulation Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003836 solid-state method Methods 0.000 description 5
- 208000005156 Dehydration Diseases 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000002505 iron Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015915 LiNi0.8Co0.2O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-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
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Images
Classifications
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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 lithium ferrous phosphate material by a spray drying-carbothermic reduction method. The method comprises the following steps: (1) roasting and dewatering iron phosphate hydrate for 2-12 hours at 200-600 DEG C to obtain anhydrous iron phosphate powder; (2) weighing the anhydrous iron phosphate, lithium source compounds and carbon source compounds according to a stoichiometric proportion, adding pure water and ball milling at high speed to uniformly mix so as to obtain a slurry with the solid content of 20-50 percent, wherein the mean grain size D50 of suspended solid particles in the slurry is 0.1-1 micrometer; (3) spraying and drying the obtained slurry to obtain a mixed powder precursor, and carrying out heat treatment and carbothermic reduction on the precursor at 700-900 DEG C under the protection of inert gas to obtain a lithium ferrous phosphate powder material. The lithium ferrous phosphate material prepared by the method has uniform constituents and good batch stability. The 2C discharge specific capacity of the lithium ferrous phosphate material at room temperature is larger than 130mAh/g, thus the lithium ferrous phosphate material has great application value in the field of power type lithium ion batteries.
Description
Technical field
The present invention relates to the method that a kind of spraying drying-carbothermic method prepares ferrousphosphate lithium material, belong to materials science field.
Background technology
Fast development along with electronics and information industry, a large amount of portable type electronic products such as mobile communication equipment, notebook computer, digital product have obtained widespread use, make society go up the demands for higher performance to battery especially rechargeable secondary cell: higher capacity, littler size, lighter weight and longer work-ing life.Lithium ion battery becomes the focus of people's research with its energy density height, operating voltage height, advantages such as load characteristic is good, charge velocities is fast, safety non-pollution, memory-less effect.
Positive electrode material is the important component part of lithium ion battery, mainly contains lamellated LiCoO
2, LiNiO
2, LiNi
0.8Co
0.2O
2, LiNi
1/3Co
1/3Mn
1/3O
2, spinel type LiMn
2O
4LiFePO with olivine structural
4Deng.Olivine-type LiFePO
4With its abundant raw materials, cheap, the specific storage height, good cycle, environmental pollution is little and be considered to the power-type lithium ion battery ideal positive electrode material of tool application potential.
But LiFePO
4Also has inevitable shortcoming during as positive electrode material.LiFePO
4The room temperature electronic conductivity low, can be by being improved at LiFePO4 particle surface coated with conductive material or ion doping.Lithium ion is at LiFePO
4In the speed of diffusion slow, make that battery only is adapted at discharging and recharging under the little electric current, can improve by the control product cut size.Under the same terms, particle diameter is more little, and the lithium ion velocity of diffusion is fast more, LiFePO under the then big current condition
4Specific discharge capacity is high more.
At present, LiFePO
4The synthetic method of material is a lot, comprises high temperature solid-state method, hydrothermal method, coprecipitation method, sol-gel method and microwave process for synthesizing, and wherein high temperature solid-state method is suitable for suitability for industrialized production most.Ferrox that traditional high temperature solid-state method employing price is comparatively expensive or ferrous acetate divalent iron salt and phosphoric acid salt and lithium salt compound mix, and pyroreaction makes under inert atmosphere.Consider that the divalent iron salt cost is higher, and oxidation easily in the building-up process, research in recent years turns to low cost gradually and is difficult for the trivalent iron salt of oxidation, after promptly adopting ferric oxide or tertiary iron phosphate and phosphoric acid salt and lithium salt compound to mix evenly, add carbon-source cpd or iron powder again, pyrocarbon thermal reduction or high temperature iron thermal reduction reaction make under inert atmosphere.Though the high temperature solid-state method synthesis process is simple, reactant is difficult for mixing, long reaction time, and need repeatedly sintering, synthetic product particle diameter major part is a micron order, and skewness, often contain impurity, pattern is irregular, and chemical property is also relatively poor.
Summary of the invention
The purpose of this invention is to provide a kind of with low cost, synthesis technique simple, be fit to suitability for industrialized production, product lot quantity good stability, and under room temperature and big current condition, have the preparation method of the LiFePO 4 of height ratio capacity and good circulation performance.
The present invention is the method that a kind of spraying drying-carbothermic reduction prepares ferrousphosphate lithium material, and its feature comprises the steps:
(1) hypophosphite monohydrate iron was dewatered 2~12 hours 200~600 ℃ of following roastings, obtain the anhydrous phosphoric acid iron powder body;
(2) according to amount of substance than Li: C: Fe=(1~1.05): (1~1.2): 1 takes by weighing the anhydrous iron phosphate in Li source compound, carbon-source cpd and the step (1), add pure water, the high speed ball milling mixes, obtain solid content and be 20~50% slurry, the median size D50 of suspended solids is 0.1~1 micron in the slurry;
(3) the prepared slurry of step (2) is carried out spraying drying, the powder that obtains mixing;
(4) with 700~900 ℃ of thermal treatment 6~24 hours under protection of inert gas of the resulting powder of step (3), promptly obtain ferrousphosphate lithium material of the present invention.
Described Li source compound is a kind of in Quilonum Retard, lithium hydroxide, Lithium Acetate and the lithium oxalate.
Described carbon-source cpd is one or more in sucrose, glucose, citric acid, tetramethylolmethane, vitamins C, polyoxyethylene glycol and the polyethers.
Carbon content in the described ferrousphosphate lithium material is 2~10%.
Compared to existing technology, the present invention has following advantage:
(1) makes raw material with the tertiary iron phosphate of cheapness, do not use expensive ferrous iron, not only reduced production cost, and avoided the easy oxidation of ferrous iron to generate the impurity that is difficult to remove and cause product impure;
(2) with tertiary iron phosphate as source of iron and phosphorus source, the distributing very evenly and fixed ratio of iron, phosphorus atom;
(3) adopt the high speed ball milling that iron phosphate grains is milled to submicron order, shortened the evolving path of lithium ion in iron phosphate grains;
(4) adopt a step agglomerating high temperature solid-state method, production technique is simple, and the cycle is short, and power consumption is few, and is emission-free waits pollution, is fit to large batch of suitability for industrialized production;
(5) adopt spray-dired method, the wink-dry slurry is avoided segregation in the composition drying process, and the products obtained therefrom composition is even, in batches good stability;
(6) this method realizes the even carbon dope of metal ion mixing and granule interior with comparalive ease, further improves the electroconductibility of material;
(7) the synthetic ferrousphosphate lithium material has good electrochemical as anode material for lithium-ion batteries, and at room temperature 2C multiplying power discharging specific storage is suitable as the power anode material for lithium-ion batteries greater than 130mAh/g.
Description of drawings
Fig. 1 is the prepared discharge curve of LiFePO 4 under different multiplying of embodiment one.
Fig. 2 is the prepared cycle performance curve (0.1C three circulations, 0.5C ten circulations, 1C ten circulations, 2C two hundred circulations) of LiFePO 4 under different multiplying of embodiment one.
Fig. 3 is the stereoscan photograph of the prepared LiFePO 4 of embodiment one.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further, following examples do not produce restriction to the present invention.
Embodiment one:
Get 620g hypophosphite monohydrate iron FePO
4.2H
2O temperature rise rate with 4 ℃/min in air atmosphere is raised to 550 ℃ of roasting 10hr dehydrations, gets the anhydrous phosphoric acid iron powder.Take by weighing 110g sucrose, 500g anhydrous iron phosphate and 125g Quilonum Retard (Li: C: Fe=1.02: 1.16: 1), add 1000ml water, at basket ball mill high speed ball milling mixing 2hr, rotational speed of ball-mill 1200rpm forms uniform slurry (slurry solid content 38%).The median size D50 of suspended solids is 0.5 micron in the slurry.The slurry of gained adopts and the fluidized drying mode with pneumatic spray drying device drying, and atomisation unit adopts the double-current method nozzle.Use the peristaltic pump charging, input speed is 15ml/min.The orifice gas flow produces atomizing by compressed-air actuated pressure-controlling under about 0.4MPa, the control air inlet temperature is 300 ℃, and temperature out is 120 ℃, and outlet air separates emptying through the one-level whirlpool.The mixed powder of spraying drying gained promptly obtains ferrousphosphate lithium material behind 700 ℃ of thermal treatment 20hr under the high pure nitrogen protection, the weight content that records carbon in the ferrousphosphate lithium material is 4.2%.
Ferrousphosphate lithium material, Super-P conductive carbon black, PVDF binding agent are pressed mass ratio to be mixed at 8: 1: 1, with NMP is that solvent is made uniform slurry, then with its blade coating on the aluminium foil of 20 micron thickness, after 120 ℃ of vacuum-drying, obtain anode pole piece, with the lithium paper tinsel is counter electrode, in being full of the glove box of argon gas, adorn Experimental cell, carry out charge-discharge test with continuous current, charging/discharging voltage is 2.5-4.2V, room temperature records under the 0.1C multiplying power first that reversible specific capacity is 162mAh/g, reversible specific capacity 140mAh/g under the 2C multiplying power.
Embodiment two:
Get 620g hypophosphite monohydrate iron FePO
4.2H
2O is 300 ℃ of roasting 12hr dehydrations in air atmosphere, get the anhydrous phosphoric acid iron powder.Take by weighing 120g glucose, 500g anhydrous iron phosphate and 145g lithium hydroxide (LiOH.H
2O) (Li: C: Fe=1.04: 1.2: 1), add 1500ml water, at basket ball mill high speed ball milling mixing 2hr, rotational speed of ball-mill 2000rpm, form uniform slurry (slurry solid content 34%), the median size D50 of suspended solids is 0.3 micron in the slurry.The gained slurry adopts and the fluidized drying mode with pneumatic spray drying device drying, and atomisation unit adopts the double-current method nozzle.Use the peristaltic pump charging, input speed is 10ml/min.The orifice gas flow produces atomizing by compressed-air actuated pressure-controlling under about 0.4MPa, the control air inlet temperature is 260 ℃, and temperature out is 110 ℃, and outlet air separates emptying through the one-level whirlpool.The mixed powder of spraying drying gained promptly obtains ferrousphosphate lithium material behind 750 ℃ of thermal treatment 10hr under the high pure nitrogen protection, the weight content that records carbon in the ferrousphosphate lithium material is 4.8%.
Carry out charge-discharge performance test with embodiment one: carry out charge-discharge test with continuous current, charging/discharging voltage is 2.5-4.2V, and room temperature records under the 0.1C multiplying power first that reversible specific capacity is 155mAh/g, reversible specific capacity 135mAh/g under the 2C multiplying power.
Embodiment three:
Get 620g hypophosphite monohydrate iron FePO
4.2H
2O is 450 ℃ of roasting 6hr dehydrations in air atmosphere, get the anhydrous phosphoric acid iron powder.Take by weighing 100g tetramethylolmethane, 500g anhydrous iron phosphate and 350g Lithium Acetate (CH
3COOLi.2H
2O) (Li: C: Fe=1.03: 1.11: 1), add 1000ml water, at basket ball mill high speed ball milling mixing 2hr, rotational speed of ball-mill 1500rpm, form uniform slurry (slurry solid content 49%), the median size D50 of suspended solids is 0.6 micron in the slurry.The gained slurry adopts and the fluidized drying mode with pneumatic spray drying device drying, and atomisation unit adopts the double-current method nozzle.Use the peristaltic pump charging, input speed is 10ml/min.The orifice gas flow produces atomizing by compressed-air actuated pressure-controlling under about 0.4MPa, the control air inlet temperature is 300 ℃, and temperature out is 110 ℃, and outlet air separates emptying through the one-level whirlpool.The mixed powder of spraying drying gained promptly obtains ferrousphosphate lithium material behind 800 ℃ of thermal treatment 10hr under the high pure nitrogen protection, the weight content that records carbon in the ferrousphosphate lithium material is 3.7%.
Carry out charge-discharge performance test with embodiment one: carry out charge-discharge test with continuous current, charging/discharging voltage is 2.5-4.2V, and room temperature records under the 0.1C multiplying power first that reversible specific capacity is 160mAh/g, reversible specific capacity 138mAh/g under the 2C multiplying power.
Embodiment four:
Get 620g hypophosphite monohydrate iron FePO
4.2H
2O is 600 ℃ of roasting 2hr dehydrations in air atmosphere, get the anhydrous phosphoric acid iron powder.Take by weighing 100g vitamins C, 500g anhydrous iron phosphate and 170g lithium oxalate (Li
2C
2O
4) (Li: C: Fe=1.01: 1.03: 1), add 1000ml water, at basket ball mill high speed ball milling mixing 2hr, rotational speed of ball-mill 1000rpm, form uniform slurry (slurry solid content 44%), the median size D50 of suspended solids is 1 micron in the slurry.The gained slurry adopts and the fluidized drying mode with pneumatic spray drying device drying, and atomisation unit adopts the double-current method nozzle.Use the peristaltic pump charging, input speed is 10ml/min.The orifice gas flow produces atomizing by compressed-air actuated pressure-controlling under about 0.4MPa, the control air inlet temperature is 300 ℃, and temperature out is 100 ℃, and outlet air separates emptying through the one-level whirlpool.The mixed powder of spraying drying gained promptly obtains ferrousphosphate lithium material behind 900 ℃ of thermal treatment 6hr under the high pure nitrogen protection, the weight content that records carbon in the ferrousphosphate lithium material is 3.5%.
Carry out charge-discharge performance test with embodiment one: carry out charge-discharge test with continuous current, charging/discharging voltage is 2.5-4.2V, and room temperature records under the 0.1C multiplying power first that reversible specific capacity is 150mAh/g, reversible specific capacity 133mAh/g under the 2C multiplying power.
Claims (4)
1. the preparation method of a lithium ferrous phosphate as anode material of lithium ion battery is characterized in that this method carries out according to the following steps:
(1) hypophosphite monohydrate iron was dewatered 2~12 hours 200~600 ℃ of following roastings, obtain the anhydrous phosphoric acid iron powder body;
(2) according to mol ratio Li: C: Fe=(1~1.05): (1~1.2): 1 takes by weighing the anhydrous iron phosphate in Li source compound, carbon-source cpd and the step (1), add pure water, the high speed ball milling mixes, obtain solid content and be 20~50% slurry, the median size D50 of suspended solids is 0.1~1 micron in the slurry;
(3) the prepared slurry of step (2) is carried out spraying drying, the powder that obtains mixing;
(4) with 700~900 ℃ of thermal treatment 6~24 hours under protection of inert gas of the resulting powder of step (3), promptly obtain ferrousphosphate lithium material of the present invention.
2. the preparation method of LiFePO 4 according to claim 1 is characterized in that in the step (2), and described Li source compound is a kind of in Quilonum Retard, lithium hydroxide, Lithium Acetate and the lithium oxalate.
3. the preparation method of LiFePO 4 according to claim 1 is characterized in that in the step (2), described carbon-source cpd is one or more in sucrose, glucose, citric acid, tetramethylolmethane, vitamins C, polyoxyethylene glycol and the polyethers.
4. the preparation method of LiFePO 4 according to claim 1 is characterized in that the carbon content in the described ferrousphosphate lithium material is 2~10%.
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