CN102683676B - Copper, barium doped iron lithium phosphate nano anode material and preparation method thereof - Google Patents
Copper, barium doped iron lithium phosphate nano anode material and preparation method thereof Download PDFInfo
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- CN102683676B CN102683676B CN201110418654.2A CN201110418654A CN102683676B CN 102683676 B CN102683676 B CN 102683676B CN 201110418654 A CN201110418654 A CN 201110418654A CN 102683676 B CN102683676 B CN 102683676B
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Abstract
Copper of the present invention, barium mixes iron phosphate nano cathode material preparation method, it is characterized in that: its lithium source, source of iron, phosphoric acid root, copper source, the raw material in barium source, after the mixing of 1mol Li: 0.00002-0.00005mol Cu: 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
Copper 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 (nanometermaterial), 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 copper, 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.
Copper of the present invention, barium mix iron phosphate nano cathode material, it is characterized in that: its particle size is in 30-85nm scope, and its chemical composition or chemical general formula can be expressed as: LiCuxBayFePO
4, x=0.00002-0.00005, y=0.0003-0.003; Wherein the mol ratio of Li, Cu, Ba, Fe, P is: 1mol Li:0.00002-0.00005mol Cu:0.0003-0.003mol Ba:1mol Fe:1mol P.
Copper of the present invention, barium mixes iron phosphate nano cathode material preparation method, it is characterized in that: its lithium source, source of iron, phosphoric acid root, copper source, the raw material in barium source, after the mixing of 1mol Li:0.00002-0.00005mol Cu: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 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, copper source is basic copper carbonate, one of Kocide SD, 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: copper 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
Copper of the present invention, barium doped iron lithium phosphate nano anode 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., copper source is basic copper carbonate Cu2 (OH) 2CO3, Kocide SD Cu (OH) 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%), Kocide SD Cu (OH) (AR), 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 Cu:0.0003 mono-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
By Li2CO3 (99.73%), Kocide SD Cu (OH) (AR), BaCO3 (99.8%), FeC2O4.2H2O (99.06%), NH4H2PO4 (98%) raw material, after the mixing of 1mol Li:0.00002mol Cu:0.0003mol Ba:1mol Fe:1mol P ratio, in 5-10 DEG C of sealing stirred reactor, react 24 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 3
By Li2CO3 (99.73%), Kocide SD Cu (OH) (AR), BaCO3 (99.8%), FeC2O4.2H2O (99.06%), NH4H2PO4 (98%) raw material, after the mixing of 1mol Li:0.00004mol Cu: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
By Li2CO3 (99.73%), Kocide SD Cu (OH) (AR), BaCO3 (99.8%), FeC2O4.2H2O (99.06%), NH4H2PO4 (98%) raw material, after the mixing of 1mol Li:0.00005mol Cu: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
By Li2CO3 (99.73%), Kocide SD Cu (OH) (AR), BaCO3 (99.8%), FeC2O4.2H2O (99.O6%), NH4H2PO4 (98%) raw material, after the mixing of 1mol Li:0.00002mol Cu:0.0003mol 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. copper, 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: LiCuxBayFePO
4, x=0.00002-0.00005, y=0.0003; Wherein the mol ratio of Li, Cu, Ba, Fe, P is: 1mol Li: 0.00002-0.00005mol Cu: 0.0003mol Ba: 1mol Fe: 1mol P.
2. a copper, barium doped iron lithium phosphate nano anode material preparation method, it is characterized in that: its lithium source, source of iron, phosphoric acid root, copper source, the raw material in barium source, after the mixing of 1mol Li: 0.00002-0.00005mol Cu: 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 copper, barium doped iron lithium phosphate nanometer powder positive electrode, its particle size is in 30-85nm scope.
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CN1431147A (en) * | 2003-02-17 | 2003-07-23 | 郑绵平 | Wet chemistry method for preparing lithium iron phosphate |
CN101393982A (en) * | 2008-10-28 | 2009-03-25 | 南京海泰纳米材料有限公司 | Method for producing carbon coated nano stage lithium iron phosphate by precipitation |
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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CN1431147A (en) * | 2003-02-17 | 2003-07-23 | 郑绵平 | Wet chemistry method for preparing lithium iron phosphate |
CN101393982A (en) * | 2008-10-28 | 2009-03-25 | 南京海泰纳米材料有限公司 | Method for producing carbon coated nano stage lithium iron phosphate by precipitation |
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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Effective date of registration: 20180928 Address after: 314000 room five, 22 building, Zhifu center, 966 Xiuzhou Road, Xiuzhou, Jiaxing, Zhejiang. Patentee after: Zhejiang Yuan Zhi new material Co.,Ltd. Address before: 542800 the Guangxi Zhuang Autonomous Region Hezhou eight step area construction east road Xiyuan Lane 40 Patentee before: Zhang Yajing |
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