CN100347081C - Process for preparing lithium ferrous phosphate coated with carbon - Google Patents
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- CN100347081C CN100347081C CNB2005101122115A CN200510112211A CN100347081C CN 100347081 C CN100347081 C CN 100347081C CN B2005101122115 A CNB2005101122115 A CN B2005101122115A CN 200510112211 A CN200510112211 A CN 200510112211A CN 100347081 C CN100347081 C CN 100347081C
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- iron phosphate
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 16
- 229910052744 lithium Inorganic materials 0.000 title abstract description 16
- 229940116007 ferrous phosphate Drugs 0.000 title abstract description 14
- 229910000155 iron(II) phosphate Inorganic materials 0.000 title abstract description 14
- 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 abstract description 14
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 20
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 20
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical group [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 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
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 125000000185 sucrose group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 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 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical group [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- 229910019931 (NH4)2Fe(SO4)2 Inorganic materials 0.000 description 1
- 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
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 1
- 239000006101 laboratory sample Substances 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 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
- -1 polyethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
本发明公开了一种包覆碳的磷酸亚铁锂的制备方法，以磷酸铁为原料，采用溶液中还原和高温热处理的方法制备包覆碳的磷酸亚铁锂。由此得到包覆碳的磷酸亚铁锂具有良好的晶体结构，并且在锂电池中表现出良好的电化学性能。在0.2C电流下充放电容量达到167mAh/g，接近理论值170mAh/g。该方法采用磷酸铁为原材料，原材料成本以及加工成本低，并且工艺路线简单，适合规模量产。
The invention discloses a method for preparing carbon-coated lithium ferrous phosphate. Ferrous phosphate is used as a raw material, and the carbon-coated lithium ferrous phosphate is prepared by reduction in solution and high-temperature heat treatment. The resulting carbon-coated lithium iron phosphate has a good crystal structure and exhibits good electrochemical performance in lithium batteries. The charge and discharge capacity reaches 167mAh/g at a current of 0.2C, which is close to the theoretical value of 170mAh/g. The method adopts iron phosphate as a raw material, has low raw material cost and processing cost, simple process route, and is suitable for large-scale mass production.
Description
Technical field
The present invention relates to the preparation method of a kind of preparation method's of mineral compound, particularly a kind of carbon coated LiFePO 4, it is used as the positive electrode material of lithium ion battery.
Background technology
Ferrousphosphate lithium material (LiFePO
4) have abundant raw material, outstanding advantages such as cost is low, specific storage is higher, environmentally friendly, nontoxic, Heat stability is good, become the research focus of various countries' researcher day by day, be a kind of lithium ion cell positive equivalent material of future generation that has much potentiality.The preparation method of ferrousphosphate lithium material mainly contains solid phase method, liquid phase method, microwave method and solid-liquid method mutually at present.
Solid phase method: mention among the Japanese Patent JP2000294238 Ferrox, Secondary ammonium phosphate and Quilonum Retard are carried out the ball milling mixing in acetone, and evaporate under nitrogen, thermal treatment obtains LiFePO 4 under 300-790 ℃ temperature afterwards.People such as A.K.Padhi (J.Electrochem.Soc.1997 (144): be raw material 1188),, obtain ferrousphosphate lithium material at 800 ℃ of sintering again 300-500 ℃ of pre-thermolysis with Quilonum Retard, Iron diacetate, primary ammonium phosphate.
Liquid phase method comprises sol-gel processing, coprecipitation method, hydrothermal synthesis method etc.
Sol-gel processing: by compatible Li
+, Fe
2+Or Fe
3+, PO
4 3-The aqueous solution select suitable organic agent that boils together, make it to add thermosetting colloidal sol and gel, obtain LiFePO 4 by sintering then.The existence that this method shortcoming is organic agent that boils together makes carbon content higher.
Coprecipitation method: lithium hydroxide is joined in the solution that contains ferrous ion and phosphoric acid, obtain post precipitation and make by sintering again.As with (NH
4)
2Fe (SO
4)
26H
2O, H
3PO
4, LiOH is raw material, water co-precipitation in the aqueous solution obtains throw out under the nitrogen protection, the compressing tablet roasting obtains product.
Hydrothermal synthesis method: the aqueous solution of tertiary iron phosphate, Trilithium phosphate is put into the autoclave of logical argon gas, and heating 1 hour is synthetic under 220 ℃, 2.4MPa condition.This method synthetic material electric conductivity is little, needs subsequent disposal, and needs high pressure high stable condition.
Microwave method: mention in the Chinese patent 200310121453.1 and adopt Quilonum Retard, Ferrox, primary ammonium phosphate, made the dispersion agent ball milling 4-12 hour, place crucible, put into 3-30 minute microwave oven treatment time to obtain ferrousphosphate lithium material with acetone.
For ferrousphosphate lithium material itself, the subject matter that exists comprises that electric conductivity is low at present.The method of improving the specific conductivity of LiFePO 4 concentrate on element doping and (or) surperficial coated with conductive material.
Solid reaction process is an industry member material preparation method commonly used, has for example successfully prepared LiCoO
2Material.But solid state reaction is solid/liquid/solid interface reaction basically, and reaction interface is little, so long reaction time, and needs repeatedly sintering, promptly grinds sintering again behind the sintering, and technology is loaded down with trivial details, the cycle is long.Even can not guarantee like this to react completely, in the high-temperature reaction process, may generate dystectic Trilithium phosphate Li
3PO
4With ferrous phosphate Fe
3(PO
4)
2, remaining unreacted impurity will worsen the chemical property of ferrousphosphate lithium material, and cause the consistence of material of different batches poor.And simple liquid phase reaction as sol-gel method, is beneficial to and reacts completely, but income is little, is feasible at the prepared in laboratory sample, tooling cost height during suitability for industrialized production.
Summary of the invention
Purpose of the present invention provides a kind of preparation method of LiFePO 4 of carbon coated, is raw material with the tertiary iron phosphate, and the method for reduction and high-temperature heat treatment prepares the LiFePO 4 of carbon coated in the employing solution.
The concrete preparation method of the LiFePO 4 of a kind of carbon coated of the present invention is as follows:
(1) takes by weighing tertiary iron phosphate, lithium acetate and reductive agent and mixing, the mol ratio of tertiary iron phosphate and lithium acetate is 1: 1, the mol ratio of tertiary iron phosphate and reductive agent is 2: 1 to 1: 5, add distilled water again, make the dissolving of lithium acetate and reductive agent, stir 1 to 10 hour down to evaporate to dryness at 20 ℃ to 90 ℃ then, obtain lithium iron phosphate precursor;
(2) under gas shield, lithium iron phosphate precursor was handled 0.5 to 5 hour at 300 to 800 ℃, obtain LiFePO 4;
(3) take by weighing LiFePO 4 and carbon source and mixing; the mass ratio of LiFePO 4 and carbon source is 99: 1 to 85: 15, carbon source is dissolved in the distilled water and heated and stirred is mixed to evaporate to dryness, then under gas shield; handled 0.5 to 5 hour at 500 to 800 ℃, obtain the LiFePO 4 of carbon coated.
The gas that the present invention uses is the mixed gas of argon gas, nitrogen, argon gas and hydrogen or the mixed gas of nitrogen and hydrogen, and hydrogen volume content is 2 to 50% in the mixed gas.
The carbon source that the present invention uses is sucrose, glucose, fructose or lactose.
Reductive agent used in the present invention is ethylene glycol, glycerol, urea, xitix, formaldehyde or turps.
The preparation method of the LiFePO 4 of a kind of carbon coated of the present invention has following characteristics:
It is raw material that the present invention adopts tertiary iron phosphate, in solution, pass through high-temperature heat treatment again after the reduction after, obtain the ferrous phosphate doping lithium anode material of the high-performance carbon coated that lithium ion battery uses.The LiFePO 4 of carbon coated charge/discharge capacity under the 0.2C electric current reaches 167mAh/g, near theoretical value 170mAh/g, has promptly eliminated the influence of unreacted impurity effectively.The employing tertiary iron phosphate is starting material, and material cost and tooling cost are low, and operational path is simple, the cycle is short, energy consumption is low, very suitable scale volume production.
Description of drawings
Fig. 1 is the XRD spectra of LiFePO 4 of the carbon coated of embodiment 2.
Fig. 2 is the LiFePO 4 of carbon coated of embodiment 3 preparation during as anode material for lithium-ion batteries, the charging and discharging curve of battery.
Embodiment
The following examples are to further specify of the present invention, but do not limit the scope of the invention.
(1) take by weighing tertiary iron phosphate, lithium acetate and ethylene glycol, the mol ratio of tertiary iron phosphate and lithium acetate is 1: 1, and the mol ratio of tertiary iron phosphate and ethylene glycol is 1: 1, add distilled water, make the dissolving of lithium acetate and ethylene glycol, stir 10 hours to evaporate to dryness down at 60 ℃ then, obtain lithium iron phosphate precursor.
(2) under nitrogen protection, lithium iron phosphate precursor was handled 5 hours at 650 ℃, obtain LiFePO 4.
(3) take by weighing LiFePO 4 and sucrose, the two mass ratio is 95: 5, sucrose is dissolved in the distilled water and heated and stirred is mixed to evaporate to dryness.The protection of nitrogen and volume content 5% hydrogen mixed gas was handled 3 hours at 800 ℃ down then, obtained the LiFePO 4 of carbon coated.
Embodiment 2
(1) take by weighing tertiary iron phosphate, lithium acetate and glycerol, the mol ratio of tertiary iron phosphate and lithium acetate is 1: 1, and the mol ratio of tertiary iron phosphate and glycerol is 1: 2, add distilled water, make the dissolving of lithium acetate and glycerol, stir 8 hours to evaporate to dryness down at 70 ℃ then, obtain lithium iron phosphate precursor.
(2) under argon gas and the protection of volume content 5% hydrogen mixed gas, lithium iron phosphate precursor was handled 2 hours at 500 ℃, obtained LiFePO 4.
(3) take by weighing LiFePO 4 and glucose, the two mass ratio is 90: 10, glucose is dissolved in the distilled water and heated and stirred is mixed to evaporate to dryness.The protection of argon gas and volume content 5% hydrogen mixed gas was handled 4 hours at 700 ℃ down then, obtained the LiFePO 4 of carbon coated.
Fig. 1 is the XRD spectra of the LiFePO 4 of carbon coated, and the result shows that the LiFePO 4 of carbon coated has good crystalline structure.
Embodiment 3
(1) take by weighing tertiary iron phosphate, lithium acetate and urea, the mol ratio of tertiary iron phosphate and lithium acetate is 1: 1, and the mol ratio of tertiary iron phosphate and urea is 1: 3, add distilled water, make the dissolving of lithium acetate and urea, stir 6 hours to evaporate to dryness down at 80 ℃ then, obtain lithium iron phosphate precursor.
(2) under argon gas and the protection of volume content 5% hydrogen mixed gas, lithium iron phosphate precursor was handled 3 hours at 700 ℃, obtained LiFePO 4.
(3) take by weighing LiFePO 4 and sucrose, the two mass ratio is 92: 8, sucrose is dissolved in the distilled water and heated and stirred is mixed to evaporate to dryness.The protection of argon gas and volume content 5% hydrogen mixed gas was handled 2 hours at 650 ℃ down then, obtained the LiFePO 4 of carbon coated.
Embodiment 4
The LiFePO 4 of the carbon coated that embodiment 3 is prepared and conductive agent acetylene black, caking agent ptfe emulsion uniform mixing in ethanolic soln, the mass ratio of LiFePO 4, acetylene black and caking agent is 80: 10: 10, compressing tablet makes positive pole to aluminium foil then.Adopt metallic lithium as negative pole, 1mol/L lithium hexafluoro phosphate (LiPF
6) NSC 11801 and the solution of methylcarbonate as electrolytic solution, porous polyethylene (PE) film that 20 μ m are thick is a barrier film, is assembled into lithium cell, adopts the 0.2C electric current to carry out charge-discharge test, obtain the charging and discharging curve of the ferrous phosphate doping lithium anode material of carbon coated, as shown in Figure 2.The initial charge capacity is 176mAh/g, and loading capacity is 167mAh/g, near the theoretical loading capacity 170mAh/g of ferrous phosphate doping lithium anode material.
Claims (2)
1, a kind of preparation method of LiFePO 4 of carbon coated is characterized in that the preparation method is as follows:
(1) takes by weighing tertiary iron phosphate, lithium acetate and reductive agent and mixing, the mol ratio of tertiary iron phosphate and lithium acetate is 1: 1, the mol ratio of tertiary iron phosphate and reductive agent is 2: 1 to 1: 5, add distilled water again, make the dissolving of lithium acetate and reductive agent, stir 1 to 10 hour down to evaporate to dryness at 20 ℃ to 90 ℃ then, obtain lithium iron phosphate precursor; Wherein reductive agent is ethylene glycol, glycerol, urea, xitix, formaldehyde or turps;
(2) under gas shield, lithium iron phosphate precursor was handled 0.5 to 5 hour at 300 to 800 ℃, obtain LiFePO 4;
(3) take by weighing LiFePO 4 and carbon source and mixing, the mass ratio of LiFePO 4 and carbon source is 99: 1 to 85: 15, carbon source is dissolved in the distilled water and heated and stirred is mixed to evaporate to dryness, then under gas shield, handled 0.5 to 5 hour at 500 to 800 ℃, obtain the LiFePO 4 of carbon coated; Wherein carbon source is sucrose, glucose, fructose or lactose.
2, the preparation method of the LiFePO 4 of a kind of carbon coated according to claim 1 is characterized in that gas is the mixed gas of argon gas, nitrogen, argon gas and hydrogen or the mixed gas of nitrogen and hydrogen, and hydrogen volume content is 2 to 50% in the mixed gas.
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| CN100347081C true CN100347081C (en) | 2007-11-07 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102709558A (en) * | 2012-06-08 | 2012-10-03 | 中南大学 | Method for preparing lithium iron phosphate from vivianite |
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| CN100389062C (en) * | 2006-09-07 | 2008-05-21 | 上海交通大学 | A method for preparing carbon-coated lithium iron phosphate composite material with iron phosphate |
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| FR2932396A1 (en) * | 2008-06-11 | 2009-12-18 | Centre Nat Rech Scient | PROCESS FOR THE PREPARATION OF INORGANIC OXIDES BY SOLVOTHERMAL PATHWAY |
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| CN101969118A (en) * | 2010-10-13 | 2011-02-09 | 武汉大学 | Method for synthesizing carbon-coated lithium iron phosphate of lithium ion battery cathode material |
| CN102005565B (en) * | 2010-11-06 | 2015-05-13 | 合肥国轩高科动力能源股份公司 | Method for preparing carbon-coated lithium iron phosphate nanoparticles |
| CN102134064A (en) * | 2011-04-28 | 2011-07-27 | 中国科学院新疆理化技术研究所 | Preparation method of positive material of lithium iron phosphate |
| TW201311547A (en) * | 2011-08-03 | 2013-03-16 | Murata Manufacturing Co | Iron lithium phosphate preparation method, electrode active material, and secondary battery |
| CN104347880A (en) * | 2014-10-14 | 2015-02-11 | 东莞新能源科技有限公司 | Fast-charge Li-ion battery |
| CN107195902A (en) * | 2017-06-01 | 2017-09-22 | 桂林理工大学 | A kind of trbasic zinc phosphate/carbon compound cathode materials |
| CN109148878B (en) * | 2018-09-03 | 2020-02-14 | 东莞塔菲尔新能源科技有限公司 | Method for treating residual lithium on surface of lithium-containing positive electrode material, positive electrode material and lithium ion battery |
| CN109346708B (en) * | 2018-11-20 | 2022-02-18 | 贵州大学 | Preparation method of battery-grade carbon-coated ferrous phosphate |
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| CN1401559A (en) * | 2002-10-18 | 2003-03-12 | 北大先行科技产业有限公司 | Method for preparing ferrous lithium phosphate, and lithium ion cell therewith |
| CN1564343A (en) * | 2004-03-25 | 2005-01-12 | 浙江大学 | Method of preparing positive electrode composite material of Lithium ion cell contg, ferrous phosphate lithium salt-carbon |
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| CN102709558A (en) * | 2012-06-08 | 2012-10-03 | 中南大学 | Method for preparing lithium iron phosphate from vivianite |
| CN102709558B (en) * | 2012-06-08 | 2014-04-09 | 中南大学 | Method for preparing lithium iron phosphate from vivianite |
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