CN102683675B - Germanium, barium doped iron lithium phosphate nano anode material and preparation method thereof - Google Patents
Germanium, barium doped iron lithium phosphate nano anode material and preparation method thereof Download PDFInfo
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- CN102683675B CN102683675B CN201110418651.9A CN201110418651A CN102683675B CN 102683675 B CN102683675 B CN 102683675B CN 201110418651 A CN201110418651 A CN 201110418651A CN 102683675 B CN102683675 B CN 102683675B
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- 229910052788 barium Inorganic materials 0.000 title claims abstract description 23
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 22
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 16
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010405 anode material Substances 0.000 title claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011858 nanopowder Substances 0.000 abstract description 2
- 239000010406 cathode material Substances 0.000 abstract 1
- 229910000398 iron phosphate Inorganic materials 0.000 abstract 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 abstract 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 17
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 3
- 235000019838 diammonium phosphate Nutrition 0.000 description 3
- 229940062993 ferrous oxalate Drugs 0.000 description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical group [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 2
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013021 LiCoC Inorganic materials 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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
Abstract
Germanium of the present invention, barium mixes iron phosphate nano cathode material and preparation method thereof, it is characterized in that: its lithium source, source of iron, phosphoric acid root, germanium source, the raw material in barium source, after the mixing of 1mol Li: 0.00002-0.00005mol Ge: 0.0003-0.003mol Ba: 1mol Fe: 1mol P ratio, in 5-120 DEG C of sealing stirred reactor, reaction 0.5-24 hour, filter, washing, nanometer presoma is obtained after oven dry, be placed in high temperature furnace by drying the presoma obtained, in blanket of nitrogen, through 500-750 DEG C of high-temperature calcination 16-24h, obtain and of the present inventionly mix lithium iron phosphate nano powder positive electrode, its particle size is in 30-85nm scope, its first discharge capacity greatly improve, reach more than 160.21mAh/g, production cost can fall more than ten times.
Description
Technical field
Germanium of the present invention, barium doped iron lithium phosphate nano anode material preparation method, belong to a kind of anode material of lithium battery preparation method, particularly a kind of lithium iron phosphate battery positive material preparation method.
Background technology
Nano material refers to the material having at least one dimension to be in nanoscale scope (1-100nm) or to be made up of as elementary cell them in three dimensions, nanoscale structures material, referred to as nano material (nanometer material), refers to that the size of its construction unit is between 1 nanometer ~ 100 nanometer range.Because its size is close to the coherence length of electronics, great changes will take place because the strong relevant self-organizing brought makes character for its character.Further, its yardstick is close to the wavelength of light, and add that it has the special effects on large surface, therefore its characteristic showed, such as fusing point, magnetic, optics, heat conduction, conductive characteristic etc., be often different from the character that this material shows when integrality.The lithium iron phosphate positive material of doping vario-property, conductivity can be improved by doping, high-rate charge-discharge capability also improves, and inhibits the effect of capacity attenuation to a certain extent.Doping approach can improve, improve lithium ion anode material performance, has been generally acknowledged a kind of feasible mode.Through publication retrieval, record relevant lithium battery nano anode material patent application 3 at present, it is: 00134039.5 1 kinds of lithium ion cell nano anode material LiCoC of Chemistry &. Chemical Engineering College, Lanzhou Univ.
2preparation method; Tsing-Hua University; 200610011712.9 rare earth doped carbon clad type nanometer anode material LiFePO4s of Shanxi Prov. Glass & Ceramic Sciences Research Inst. and preparation method thereof; The continuous hydrothermal synthetic method of 200710037314.9 lithium ion cell nano anode materials of Shanghai Communications University.
Summary of the invention
The object of the invention is to: based on the structural limitations of the lithium iron phosphate positive material (LiFePO4) of prior art, there is its poorly conductive and the low deficiency of lithium ion diffusion coefficient, now propose a kind of germanium, barium doped iron lithium phosphate nano anode material and preparation method thereof.
The present invention can improve in view of doping approach, improve lithium ion anode material performance, has been generally acknowledged a kind of feasible mode.According to the chemical property of barium/lithium, electric property, crystal structure characteristic is the feature of the most akin element:
Barium is element the most active in alkaline-earth metal, because it is very active, and easily oxidized, should be kept in kerosene and atoleine.
Ionization energy 5.212 electron-volts, the first ionization energy 502.9kJ/mol;
Crystal structure: structure cell is body centred cubic cell, each structure cell contains 2 metallic atoms;
Cell parameter: a=502.8pm; B=502.8pm; C=502.8pm; α=90 °; β=90 °; γ=90 °.
Lithium, metallic element, can react with a large amount of inorganic reagent and organic reagent.With all energy chemical combination such as oxygen, nitrogen, sulphur, due to easily oxidated and dimmed, and density ratio kerosene is little, therefore should deposit in atoleine.
Ionization energy 5.392 electron-volts, the first ionization energy 520.2kJ/mol;
Crystal structure: structure cell is body centred cubic cell, each structure cell contains 2 metallic atoms;
Cell parameter: a=351pm; B=351pm; C=351pm; α=90 °; β=90 °; γ=90 °.
Think that barium should be easy to lithium position chanza most.The present invention be undertaken testing by barium doping, in the situation of adulterate with barium, can add 1-2 other element individual again, form 2 yuan or 3 yuan of doping, to obtain the good anode material of lithium battery of performance, it makes its performance of nanoscale product will be more outstanding.
Germanium of the present invention, barium doped iron lithium phosphate nano anode material, is characterized in that: its particle size is in 30-85nm scope, and its chemical composition or chemical general formula can be expressed as: LiGexBayFePO4, x=0.00002-0.00005, y=0.0003-0.003; Wherein the mol ratio of Li, Ge, Ba, Fe, P is: 1mol Li: 0.00002-0.00005mol Ge: 0.0003-0.003mol Ba: 1mol Fe: 1mol P.
Germanium of the present invention, barium doped iron lithium phosphate nano anode material preparation method, it is characterized in that: its lithium source, source of iron, phosphoric acid root, germanium source, the raw material in barium source, after the mixing of 1mol Li: 0.00002-0.00005mol Ge: 0.0003-0.003mol Ba: 1mol Fe: 1mol P ratio, in 5-120 DEG C of sealing stirred reactor, reaction 0.5-24 hour, filter, washing, nanometer presoma is obtained after oven dry, be placed in high temperature furnace by drying the presoma obtained, in blanket of nitrogen, through 500-750 DEG C of high-temperature calcination 16-24h, obtain doping of the present invention ginseng lithium iron phosphate nano powder positive electrode, its particle size is in 30-85nm scope, its lithium source is lithium carbonate, one of lithium hydroxide or lithium dihydrogen phosphate, source of iron is ferrous oxalate, phosphoric acid root is one of ammonium dihydrogen phosphate or diammonium hydrogen phosphate, germanium source is germanium oxide GeO2, barium source is brium carbonate, barium hydroxide, barium chloride, barium nitrate, barium monoxide, one of barium sulphide.
The present invention's beneficial effect compared with prior art: germanium of the present invention, barium doped iron lithium phosphate nano anode material preparation method, gained powder positive electrode, granularity in 30-85nm scope, its first discharge capacity greatly improve, reach more than 160.21mAh/g, production cost can fall more than ten times.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but embodiments of the present invention are not limited thereto.
Embodiment 1
Germanium of the present invention, barium activation lithium iron phosphate positive material preparation method, its lithium source can be used: the lithium salts such as lithium carbonate, lithium hydroxide or lithium dihydrogen phosphate, source of iron can be used: ferrous oxalate etc., phosphoric acid root can be used: ammonium dihydrogen phosphate or diammonium hydrogen phosphate etc., germanium source is germanium oxide GeO2 etc., and barium source can be used: the barium salts such as brium carbonate, barium hydroxide, barium chloride, barium nitrate, barium monoxide, barium sulphide.
Select: lithium carbonate (Li2CO3) (99.73%), germanium oxide GeO2 (99.8%), brium carbonate (BaCO3) (99.8%), ferrous oxalate (FeC2O4.2H2O) (99.06%), diammonium hydrogen phosphate (NH4H2PO4) (98%) is raw material; After the mixing of 1mol Li: 0.00002-0.00005mol Ge: 0.0003-0.003mol Ba: 1mol Fe: 1mol P ratio, in 5-120 DEG C of sealing stirred reactor, reaction 0.5-24 hour, nanometer presoma is obtained after filtration, washing, oven dry, be placed in high temperature furnace, in blanket of nitrogen, through 500-750 DEG C of high-temperature calcination 16-24h by drying the presoma obtained, obtain doped iron lithium phosphate nanometer powder positive electrode of the present invention, its particle size is in 30-85nm scope.
Embodiment 2
Li2CO3 (99.73%), GeO2 (99.8%), BaCO3 (99.8%), FeC2O4.2H2O (99.06%), NH4H2PO4 (98%) raw material, after the mixing of 1mol Li: 0.00002mol Ge: 0.0003mol Ba: 1mol Fe: 1mol P ratio, in 5-120 DEG C of sealing stirred reactor, reaction 0.5-24 hour, filter, washing, nanometer presoma is obtained after oven dry, be placed in high temperature furnace by drying the presoma obtained, in blanket of nitrogen, through 500-750 DEG C of high-temperature calcination 16-24h, obtain doped iron lithium phosphate nanometer powder positive electrode of the present invention, its particle size is in 30-85nm scope.
Embodiment 3
Li2CO3 (99.73%), GeO2 (99.8%), BaCO3 (99.8%), FeC2O4.2H2O (99.06%), NH4H2PO4 (98%) raw material, after the mixing of 1mol Li: 0.00004mol Ge: 0.001mol Ba: 1mol Fe: 1mol P ratio, in 20-30 DEG C of sealing stirred reactor, react 20 hours, filter, washing, nanometer presoma is obtained after oven dry, be placed in high temperature furnace by drying the presoma obtained, in blanket of nitrogen, through 500-750 DEG C of high-temperature calcination 16-24h, obtain doped iron lithium phosphate nanometer powder positive electrode of the present invention.
Embodiment 4
Li2CO3 (99.73%), GeO2 (99.8%), BaCO3 (99.8%), FeC2O4.2H2O (99.06%), NH4H2PO4 (98%) raw material, after the mixing of 1mol Li: 0.00005mol Ge: 0.003mol Ba: 1mol Fe: 1mol P ratio, in 50-80 DEG C of sealing stirred reactor, react 5 hours, filter, washing, nanometer presoma is obtained after oven dry, be placed in high temperature furnace by drying the presoma obtained, in blanket of nitrogen, through 500-750 DEG C of high-temperature calcination 16-24h, obtain doped iron lithium phosphate nanometer powder positive electrode of the present invention.
Embodiment 5
Li2CO3 (99.73%), GeO2 (99.8%), BaCO3 (99.8%), FeC2O4.2H2O (99.06%), NH4H2PO4 (98%) raw material, after the mixing of 1mol Li: 0.00004mol Ge: 0.001mol Ba: 1mol Fe: 1mol P ratio, in 100-120 DEG C of sealing stirred reactor, react 0.5 hour, filter, washing, nanometer presoma is obtained after oven dry, be placed in high temperature furnace by drying the presoma obtained, in blanket of nitrogen, through 500-750 DEG C of high-temperature calcination 16-24h, obtain doped iron lithium phosphate nanometer powder positive electrode of the present invention.
Adopt the testing equipment of prior art and the method for testing of prior art, to the doped iron lithium phosphate nanometer powder positive electrode of above embodiment 1-5, carrying out test result is: particle size is in 30-85nm scope, and discharge capacity reaches more than 160.21mAh/g first.
Claims (2)
1. germanium, a barium doped iron lithium phosphate nano anode material, is characterized in that: its particle size is in 30-85nm scope, and its chemical composition or chemical general formula can be expressed as: LiGe
xba
yfePO
4, x=0.00002-0.00005, y=0.0003; Wherein the mol ratio of Li, Ge, Ba, Fe, P is: 1mol Li: 0.00002-0.00005mol Ge: 0.0003mol Ba: 1mol Fe: 1mol P.
2. a germanium, barium doped iron lithium phosphate nano anode material preparation method, it is characterized in that: its lithium source, source of iron, phosphoric acid root, germanium source, the raw material in barium source, after the mixing of 1mol Li: 0.00002-0.00005mol Ge: 0.0003mol Ba: 1mol Fe: 1mol P ratio, in 5-120 DEG C of sealing stirred reactor, reaction 0.5-24 hour, filter, washing, nanometer presoma is obtained after oven dry, be placed in high temperature furnace by drying the presoma obtained, in blanket of nitrogen, through 500-750 DEG C of high-temperature calcination 16-24h, obtain doped iron lithium phosphate nanometer powder positive electrode, its particle size is in 30-85nm scope.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431147A (en) * | 2003-02-17 | 2003-07-23 | 郑绵平 | Wet chemistry method for preparing lithium iron phosphate |
| CN1457111A (en) * | 2003-03-18 | 2003-11-19 | 黄穗阳 | Lithium cell positive electrode materials and preparing method thereof |
| CN101582498A (en) * | 2009-06-18 | 2009-11-18 | 东北师范大学 | Method for preparing nanometer ferrous phosphate lithium /carbon composite material |
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| KR100913178B1 (en) * | 2007-11-22 | 2009-08-19 | 삼성에스디아이 주식회사 | Active material for rechargeable lithium battery and rechargeable lithium battery |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431147A (en) * | 2003-02-17 | 2003-07-23 | 郑绵平 | Wet chemistry method for preparing lithium iron phosphate |
| CN1457111A (en) * | 2003-03-18 | 2003-11-19 | 黄穗阳 | Lithium cell positive electrode materials and preparing method thereof |
| CN101582498A (en) * | 2009-06-18 | 2009-11-18 | 东北师范大学 | Method for preparing nanometer ferrous phosphate lithium /carbon composite material |
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