CN101814601B - Method for preparing zinc-doped zinc oxide-coated lithium iron phosphate - Google Patents
Method for preparing zinc-doped zinc oxide-coated lithium iron phosphate Download PDFInfo
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- CN101814601B CN101814601B CN2010101220320A CN201010122032A CN101814601B CN 101814601 B CN101814601 B CN 101814601B CN 2010101220320 A CN2010101220320 A CN 2010101220320A CN 201010122032 A CN201010122032 A CN 201010122032A CN 101814601 B CN101814601 B CN 101814601B
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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
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Abstract
The invention discloses a method for preparing zinc-doped zinc oxide-coated lithium iron phosphate. The lithium iron phosphate consists of zinc-doped LiFePO4 particles and ZnO particles on surfaces of zinc-doped LiFePO4 particles. The method comprises the following steps of: uniformly mixing and stirring the zinc-doped LiFePO4 particles and ZnO particle precursors; drying the mixture at the temperature of between 80 and 100 DEG C; and sintering the mixture at the temperature of between 500 and 600 DEG C for 4 to 5 hours in inert atmosphere. The method has simple required technology and equipment and easy operation, and can realize preparation of the lithium iron phosphate with a novel composition structure.
Description
Technical field
The present invention relates to field of electronic materials, specifically is the preparation of the LiFePO4 of a kind of zinc doping and zinc oxide coating.
Background technology
LiFePO4 (LiFePO
4) can be used to make the positive electrode of lithium ion battery, thought that extensively possibly replace existing positive electrode future.LiFePO4 has the more stable state of oxidation, higher in theory capacity, and security performance is good, and high-temperature behavior is good, has simultaneously plurality of advantages such as nontoxic, pollution-free, raw material wide material sources, low price again.But, LiFePO
4The key issue that exists is that conductivity is very low.In theory, the doping metals cation is a kind of method that can improve the inherent electric conductivity of material.Because, Zn
2+And Fe
2+Ionic radius is close, at LiFePO
4In a small amount of doping of zinc do not influence its crystal structure and form and the lattice volume is increased, thereby for the embedding of lithium ion with take off embedding and bigger space is provided, the diffusion of raising lithium ion.In addition, at the LiFePO of the zinc that mixes
4The surface coats n N-type semiconductor N zinc oxide (ZnO) particle, is prone to realize good combination between particle and the surface coated ZnO, few defective, and n N-type semiconductor N ZnO is that electric transmission provides the path, can improve electric conductivity.
Summary of the invention
The purpose of this invention is to provide the preparation of the LiFePO4 of a kind of zinc doping and zinc oxide coating.
The following technical scheme of the concrete employing of the present invention:
The preparation of the LiFePO4 that a kind of zinc doping and zinc oxide coat.This LiFePO4 is by the LiFePO of doping zinc
4Particle, the LiFePO of doping zinc
4The ZnO particle of particle surface is formed.
This LiFePO4 is by the LiFePO of doping zinc
4Particle, the LiFePO of doping zinc
4The ZnO particle of particle surface is formed,
At first, the LiFePO of preparation doping zinc
4Particle:
Lithium carbonate, ferrous oxalate, zinc oxide and ammonium dihydrogen phosphate are pressed the atom number than Li: (Fe+Zn): PO
4=1: mix at 1: 1, wherein the ratio of the amount of substance of ferrous oxalate and zinc oxide was not less than 49: 1, after the mixing; Under inert atmosphere, ball milling 12～24h is behind the ball milling; 400～450 ℃ of calcining 8～12h under inert atmosphere, 700～800 ℃ of sintering 12～16h under inert atmosphere;
Secondly, the LiFePO of preparation doping zinc
4The ZnO particle precursor of particle surface:
Zinc acetate solved homogeneously in 25～70 ℃ the EGME and MEA mixed liquor, zinc acetate concentration is that the ratio of the amount of substance of 0.3～0.8mol/L, MEA and zinc acetate is 1: 1 in the solution of dissolving back;
At last, the LiFePO of doping zinc
4The ZnO particle of particle surface is made through following method: with the LiFePO of doping zinc
4Particle mixes, stirs with ZnO particle precursor, then 80～100 ℃ of oven dry, subsequently under inert atmosphere through 500～600 ℃ of sintering 4～5h.
The LiFePO of described doping zinc
4Grain diameter is in the scope of hundreds of nanometer to tens micron
The LiFePO of described doping zinc
4The ZnO grain diameter of particle surface is in the nano-grade size scope.
The present invention relates to field of electronic materials, specifically is the preparation of the LiFePO4 of a kind of zinc doping and zinc oxide coating.Technology of the presently claimed invention, equipment are simple, easy to operate, can realize the preparation of the LiFePO4 of novel composition structure.
Description of drawings
Fig. 1 is the schematic cross-section of the LiFePO4 of zinc doping of the present invention and zinc oxide coating;
Below in conjunction with accompanying drawing content of the present invention is done further explain.
The specific embodiment mode
Referring to shown in Figure 1, the LiFePO of 101-doping zinc
4Particle, the LiFePO of 102-doping zinc
4The ZnO particle of particle surface.This LiFePO4 is by the LiFePO of doping zinc
4Particle 101, the LiFePO of doping zinc
4The ZnO particle 102 of particle surface is formed.
Lithium carbonate, ferrous oxalate, zinc oxide and ammonium dihydrogen phosphate are pressed the atom number than Li: (Fe+Zn): PO
4=1: mix at 1: 1, wherein the ratio of the amount of substance of ferrous oxalate and zinc oxide is 49: 1.After the mixing, under inert atmosphere, ball milling 24h.Behind the ball milling, 400 ℃ of calcining 10h under inert atmosphere.After the calcining, 750 ℃ of sintering 15h process the LiFePO of doping zinc under inert atmosphere
4Particle 101.
70 ℃ of mixing, the ratio of the amount of substance that mixed zinc acetate concentration is 0.3～0.8mol/L, MEA and zinc acetate is 1: 1 with zinc acetate, EGME and monoethanolamine solution.Then with the LiFePO of this mixed liquor and doping zinc
4Particle mixes stirring.100 ℃ of oven dry, under inert atmosphere, pass through room temperature to 550 ℃ sintering 4～5h subsequently then, process the LiFePO of doping zinc
4The ZnO nano particle 102 of particle surface.
Claims (1)
1. the method preparing phosphate iron lithium that coats of zinc doping and zinc oxide is characterized in that this LiFePO4 is by the LiFePO of doping zinc
4Particle, the LiFePO of doping zinc
4The ZnO particle of particle surface is formed,
At first, the LiFePO of preparation doping zinc
4Particle:
Lithium carbonate, ferrous oxalate, zinc oxide and ammonium dihydrogen phosphate are pressed the atom number than Li: (Fe+Zn): PO
4=1: mix at 1: 1, wherein the ratio of the amount of substance of ferrous oxalate and zinc oxide was not less than 49: 1, after the mixing; Under inert atmosphere, ball milling 12～24h is behind the ball milling; 400～450 ℃ of calcining 8～12h under inert atmosphere, 700～800 ℃ of sintering 12～16h under inert atmosphere;
Secondly, the LiFePO of preparation doping zinc
4The ZnO particle precursor of particle surface:
Zinc acetate solved homogeneously in 25～70 ℃ the EGME and MEA mixed liquor, zinc acetate concentration is that the ratio of the amount of substance of 0.3～0.8mol/L, MEA and zinc acetate is 1: 1 in the solution of dissolving back;
At last, with the LiFePO of doping zinc
4Particle mixes, stirs with ZnO particle precursor, then 80～100 ℃ of oven dry, subsequently under inert atmosphere through 500～600 ℃ of sintering 4～5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101220320A CN101814601B (en) | 2010-03-11 | 2010-03-11 | Method for preparing zinc-doped zinc oxide-coated lithium iron phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101220320A CN101814601B (en) | 2010-03-11 | 2010-03-11 | Method for preparing zinc-doped zinc oxide-coated lithium iron phosphate |
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| Publication Number | Publication Date |
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| CN101814601A CN101814601A (en) | 2010-08-25 |
| CN101814601B true CN101814601B (en) | 2012-07-04 |
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| CN2010101220320A Expired - Fee Related CN101814601B (en) | 2010-03-11 | 2010-03-11 | Method for preparing zinc-doped zinc oxide-coated lithium iron phosphate |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106065493B (en) * | 2016-07-29 | 2018-10-23 | 中山大学 | A kind of high resistivity single-crystal zinc-oxide and its preparation method and application |
| US10672940B2 (en) | 2016-07-29 | 2020-06-02 | Sun Yat-Sen University | High-resistivity single crystal zinc oxide wafer based radiation detector and preparation method and use thereof |
| CN108539132B (en) * | 2018-01-26 | 2021-05-11 | 澳洋集团有限公司 | Preparation method of zinc oxide composite lithium iron phosphate cathode material |
| CN109494371B (en) * | 2018-11-15 | 2021-04-09 | 合肥国轩高科动力能源有限公司 | Nano-tube-shaped LiFePO of lithium ion battery4Preparation method of film material |
| CN109935803B (en) * | 2018-11-28 | 2021-04-27 | 万向一二三股份公司 | Preparation method of lithium iron phosphate cathode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792780A (en) * | 2005-10-27 | 2006-06-28 | 复旦大学 | Zinc ion mixed olivine structure LiFePo4 and its preparation process and application |
| CN1921187A (en) * | 2006-08-30 | 2007-02-28 | 新乡市中科科技有限公司 | Ferrous phosphate doping lithium anode material and preparation process |
| CN101222044A (en) * | 2007-12-06 | 2008-07-16 | 南开大学 | Novel conductive agent doping/coating lithium iron phosphate material and its production method |
-
2010
- 2010-03-11 CN CN2010101220320A patent/CN101814601B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792780A (en) * | 2005-10-27 | 2006-06-28 | 复旦大学 | Zinc ion mixed olivine structure LiFePo4 and its preparation process and application |
| CN1921187A (en) * | 2006-08-30 | 2007-02-28 | 新乡市中科科技有限公司 | Ferrous phosphate doping lithium anode material and preparation process |
| CN101222044A (en) * | 2007-12-06 | 2008-07-16 | 南开大学 | Novel conductive agent doping/coating lithium iron phosphate material and its production method |
Non-Patent Citations (1)
| Title |
|---|
| H.Liu,et al..Influence of Zn Doping on Novel Cathode Material LiFePO4.《复旦学报（自然科学版）》.2005,第44卷(第5期),877-878. * |
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| CN101814601A (en) | 2010-08-25 |
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