CN101969119A - Method for preparing iron phosphate material with composite structure - Google Patents
Method for preparing iron phosphate material with composite structure Download PDFInfo
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- CN101969119A CN101969119A CN2010105150685A CN201010515068A CN101969119A CN 101969119 A CN101969119 A CN 101969119A CN 2010105150685 A CN2010105150685 A CN 2010105150685A CN 201010515068 A CN201010515068 A CN 201010515068A CN 101969119 A CN101969119 A CN 101969119A
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- ferric phosphate
- iron phosphate
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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
Abstract
The invention discloses a method for preparing an iron phosphate material with composite structure. The method comprises the following steps of: preparing aqueous solution of iron phosphate with molar concentration of between 0.1 and 10M by dissolving solid iron phosphate in nitric acid with concentration of between 1 and 20 percent; preparing suspension with concentration of between1 and 10 percent by dispersing a carbon material with nanostructure in water; adding an organic solvent in an amount which is 0.01 to 1 percent based on the total weight of the suspension to serve as a wetting agent so as to increase the dispersion effect; mixing solution of iron phosphate and carbon suspension according to the proportion of iron to carbon of 100:0.1-5; and performing spray drying to dry and volatize the nitric acid to prepare the material with iron phosphate/nano carbon composite structure. The method realizes a composite cross structure of the iron phosphate material and is suitable for manufacturing high-performance iron lithium phosphate positive material; and the crystal grains of the positive material are small and the positive material has a high intrinsic conductive phase, so that the material has high multiplying power and low-temperature performance.
Description
Technical field
The present invention relates to a kind of phosphate, specifically a kind of preparation method with composite construction ferric phosphate/material with carbon element has effectively improved the high rate capability and the cryogenic property of material.
Background technology
LiFePO 4 material has become the first-selected positive electrode of power lithium-ion battery in recent years.Therefore, LiFePO 4 material has the performance of fail safe, stability and long circulation life that other positive electrode do not possess.Utilize ferric phosphate to be the synthetic LiFePO4 of raw material, have capacity height, short, the steady performance of sintering time, become day by day synthesis route widely.For example disclosed patent documentation in the lithium iron phosphate preparation method that CN 1581537, CN 1753216, CN 1958440, CN 1958441 and CN 1884053 are proposed, all adopts ferric phosphate as main synthesis material.
The ferric phosphate material that tradition is made has higher purity and stable component ratio.Thereby in building-up process, ferric phosphate can at first dewater and become anhydrous iron phosphate, with lithium ion and the reaction of carbon covering, generates the LiFePO 4 material that carbon coats then.But in sintering process, the ferric phosphate crystal grain can be grown up gradually, finally becomes micron-sized LiFePO4 particle.As everyone knows, in the LiFePO4 lithium ion diffusivity a little less than, in micron-sized LiFePO4 crystal grain the migration relatively the difficulty.Therefore caused the high rate capability of LiFePO 4 material and cryogenic property bad.Trace it to its cause, the big crystal grain of complete ferric phosphate is the principal element that causes above problem.From the technology of present each manufacturer,, can't tackle the problem at its root if continue to use traditional ferric phosphate material and synthesis technique.Therefore, must be improved and perfect.
Summary of the invention
In view of the above-mentioned state of the art, the invention provides a kind of composite construction ferric phosphate preparation methods, have and can prevent growing up of in the manufacture process of LiFePO4 single grain.On the yardstick of nanometer or sub-micron, realize the compound chi structure of ferric phosphate material, thereby in LiFePO4 manufacture process subsequently, make the LiFePO4 that has mixed structure on the microcosmic, thereby reduce the diffusion length of lithium ion significantly, increase the high magnification and the cryogenic property of LiFePO 4 material.
Composite construction ferric phosphate preparation methods of the present invention is:
At first use the ferric phosphate of the nitric acid dissolve solid of 1-20% concentration, make the aqueous solution of ferric phosphate molar concentration 0.1～10M, then, the suspension-turbid liquid that the material with carbon element water of nanostructure is disperseed to make 1-10% concentration, the organic solvent that adds suspension-turbid liquid total weight 0.01-1% is as wetting agent, again with liquor ferri phosphatis and carbon suspension liquid according to ferric phosphate: after the mixed of carbon=100: 0.1-5, carry out spray drying, the nitric acid volatilization that is dried obtains having ferric phosphate/material of Nano Carbon structure.
In the present invention, the material with carbon element of related nanostructure is to select any of acetylene black, CNT (carbon nano-tube), Graphene for use.
In the present invention, the organic solvent of indication is to select any of absolute ethyl alcohol, acetone, ether, N-methyl pyrrolidone for use.
In a word, the invention has the beneficial effects as follows: the composite construction ferric phosphate material that utilizes the present invention to make, nano-sized carbon is evenly distributed between the ferric phosphate, in LiFePO4 building-up process subsequently, has stoped the formation of the big crystal grain of LiFePO 4 material effectively.A crystal grain of LiFePO 4 material is reduced to below 0.2 micron from the 2-3 micron, and-20 degree 0.5C discharge capacities are brought up to about 50% from about 30%, have greatly improved the cryogenic property of LiFePO 4 material.Material 5C discharge voltage plateau is brought up to 3.01V from 2.95V, has effectively improved the high-rate discharge ability of material.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
With the nitric acid dissolve 18.6g solid phosphoric acid iron of 1 liter of 1% concentration, make the aqueous solution of ferric phosphate molar concentration 0.1M.Then, with 0.0186g acetylene black, use the wetting increase dispersion effect of absolute ethyl alcohol of 0.186mg earlier, add the 1.85g aqueous dispersion then, make the suspension-turbid liquid of 1% concentration, then liquor ferri phosphatis and carbon suspension liquid are all mixed, this moment, ferric phosphate and carbon weight ratio were 100: 0.1, liquid carries out spray drying, obtains having ferric phosphate/material of Nano Carbon structure.
Embodiment 2
Nitric acid dissolve 1860Kg solid phosphoric acid iron with 1 cubic metre of 20% concentration, make the aqueous solution of ferric phosphate molar concentration 10M, then, with the 93Kg CNT (carbon nano-tube), wetting with the acetone of 0.93Kg earlier, add the 836Kg aqueous dispersion then, make the suspension-turbid liquid of 10% concentration, then liquor ferri phosphatis and carbon suspension liquid are all mixed, this moment, ferric phosphate and carbon weight ratio were 100: 5, liquid carries out spray drying, obtains having ferric phosphate/material of Nano Carbon structure.
Embodiment 3
Nitric acid dissolve 930Kg solid phosphoric acid iron with 5 cubic metre of 5% concentration, make the aqueous solution of ferric phosphate molar concentration 1M, then, with 9.3Kg acetylene black, wetting with the N-methyl pyrrolidone of 0.4653Kg earlier, add the 176.2Kg aqueous dispersion then, make the suspension-turbid liquid of 5% concentration, then liquor ferri phosphatis and carbon suspension liquid are all mixed, this moment, ferric phosphate and carbon weight ratio were 100: 1, liquid carries out spray drying, obtains having ferric phosphate/material of Nano Carbon structure.
Claims (3)
1. composite construction ferric phosphate preparation methods, its process is: the ferric phosphate of at first using the nitric acid dissolve solid of 1-20% concentration, make the aqueous solution of ferric phosphate molar concentration 0.1～10M, then, the suspension-turbid liquid that the material with carbon element water of nanostructure is disperseed to make 1-10% concentration, the organic solvent that adds suspension-turbid liquid total weight 0.01-1% is as wetting agent, with liquor ferri phosphatis and carbon suspension liquid according to ferric phosphate: after the mixed of carbon=100: 0.1-5, carry out spray drying, the nitric acid volatilization that is dried obtains having ferric phosphate/material of Nano Carbon structure.
2. a composite construction ferric phosphate preparation methods is characterized in that, the material with carbon element of described nanostructure is any of acetylene black, CNT (carbon nano-tube), Graphene.
3. a composite construction ferric phosphate preparation methods is characterized in that, described organic solvent is any of absolute ethyl alcohol, acetone, ether, N-methyl pyrrolidone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105150685A CN101969119B (en) | 2010-10-21 | 2010-10-21 | Method for preparing iron phosphate material with composite structure |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010105150685A CN101969119B (en) | 2010-10-21 | 2010-10-21 | Method for preparing iron phosphate material with composite structure |
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| CN101969119A true CN101969119A (en) | 2011-02-09 |
| CN101969119B CN101969119B (en) | 2013-07-10 |
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| CN2010105150685A Expired - Fee Related CN101969119B (en) | 2010-10-21 | 2010-10-21 | Method for preparing iron phosphate material with composite structure |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106564867A (en) * | 2016-10-09 | 2017-04-19 | 华南理工大学 | Method for preparing iron phosphate material by adding reducing organic matters |
| CN112687860A (en) * | 2020-12-28 | 2021-04-20 | 大连博融新材料有限公司 | Surface-coated ternary cathode material, and preparation method and application thereof |
-
2010
- 2010-10-21 CN CN2010105150685A patent/CN101969119B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 陈嘉甫，谭光薰: "《磷酸盐的生产与应用》", 31 December 1989, 成都科技大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106564867A (en) * | 2016-10-09 | 2017-04-19 | 华南理工大学 | Method for preparing iron phosphate material by adding reducing organic matters |
| CN112687860A (en) * | 2020-12-28 | 2021-04-20 | 大连博融新材料有限公司 | Surface-coated ternary cathode material, and preparation method and application thereof |
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| CN101969119B (en) | 2013-07-10 |
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