CN101386405A - Lithium iron phosphate synthetic method - Google Patents
Lithium iron phosphate synthetic method Download PDFInfo
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- CN101386405A CN101386405A CNA2008101561262A CN200810156126A CN101386405A CN 101386405 A CN101386405 A CN 101386405A CN A2008101561262 A CNA2008101561262 A CN A2008101561262A CN 200810156126 A CN200810156126 A CN 200810156126A CN 101386405 A CN101386405 A CN 101386405A
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- lithium
- stainless steel
- iron phosphate
- ferrous phosphate
- phosphate lithium
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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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Abstract
The invention discloses a synthetic method for ferrous phosphate lithium, which belongs to preparation methods for anodal materials of lithium ion batteries. According to the mole ratio of (0.98-1.02):1, lithium metal powder and waterless iron phosphate are taken as raw materials in the method, are uniformly mixed in a glove box filled with dry argon, and then are put into an airtight stainless steel container; the stainless steel container is heated to 215-675 DGE C in a heating furnace, and the temperature thereof is maintained for 14-2000 minutes; when the temperature of the mixture in the stainless steel container is equal to or less than 60 DGE C, the mixture is taken out to be ground, and then is sieved by a 300 mesh sieve to get the ferrous phosphate lithium. The method has the advantages of simplicity and no environmental pollution; the ferrous phosphate lithium obtained by the method has high purity and tap density and favorable electrochemical property; compared with the existing ferrous phosphate lithium synthesized by the solid phase method, the ferrous phosphate lithium has outstanding advantages.
Description
Technical field
The present invention relates to method for preparing anode material of lithium-ion battery, particularly a kind of synthetic method of ferrousphosphate lithium material.
Background technology
The develop rapidly of lithium ion battery industry is also more and more higher to the requirement of positive electrode material, and in the positive electrode material of numerous lithium ion batteries, LiFePO 4 has cheap for manufacturing cost, and safety performance is good, good cycle, plurality of advantages such as environmentally friendly.But the synthetic difficulty of LiFePO 4, general solid phase method synthesizing lithium ferrous phosphate normally mix Quilonum Retard (or other lithium source) and Ferrox (or other source of iron), primary ammonium phosphate (or other phosphorus source) by mixer after, at Ar gas (or N
2Gas) under the protection, get in 400-800 ℃ of calcining tens of hours.These starting material often comprise other more element (non-Li, Fe, P, O element), so in calcination process, can give off a lot of gas, these gases not only pollute environment, and can reduce the tap density of product LiFePO 4, influence its performance.Also there is similar problem in other synthetic method usually as liquid-phase coprecipitation etc.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art part, provide a kind of synthetic method simple, help environmental protection, products obtained therefrom purity height, the lithium iron phosphate synthetic method that tap density is big, chemical property is good.
Technical scheme of the present invention is: selecting metallic lithium powder and anhydrous iron phosphate for use is raw material, and both materials mol ratios are (0.98～1.02): 1; Tertiary iron phosphate after the vacuum-drying is mixed with metallic lithium powder in being full of the glove box of dry argon gas, in the airtight stainless steel vessel of packing into; Stainless steel vessel is heated to 215 ℃～675 ℃ in process furnace, insulation 14～2000min stops heating, cools to the furnace≤60 ℃ the time, take out and grind, and crosses 300 mesh sieves, promptly gets LiFePO 4.
The present invention only needs two kinds of raw materials, and in encloses container, lesser temps can synthesize desired product down, and synthetic method is simple, produces hardly and pollutes, and is favourable to environmental protection.Product obtained by this method is through X ray powder grating spectrum check, and its spectrogram is consistent with LiFePO 4 standard x RD spectrogram, does not have obvious impurity peaks existence, the product purity height, tap density is big, be assembled into battery after the test shows chemical property good.
Embodiment
Further specify the present invention below by embodiment.
Example 1
In being full of the glove box of dry argon gas, take by weighing the anhydrous iron phosphate (1mol) of 150.82g 99.99% after the lithium powder (0.983mol) of 6.82g 99.9% and the vacuum-drying, two kinds of raw materials are packed into to mix in the stainless steel vibration blender, changes in the airtight tube container of stainless steel.From glove box, take out tube container, place retort furnace, 215 ℃ of constant temperature 14min, furnace cooling to 60 ℃ takes out black powder solid wherein, grinds and also crosses 300 mesh sieves, promptly obtains ferrousphosphate lithium material.This sample is through the X-ray powder diffraction spectral test, and is consistent with LiFePO 4 standard x RD spectrogram, do not have obvious impurity peaks and exists.
Getting this material of 1g, be mixed together evenly with 1.1764g 10%PTFE latex and 0.0588g graphitized carbon black, be coated on and make anode pole piece on the aluminium foil, is negative pole with the lithium sheet, LiFP0
4/ EC+DMC makes electrolytic solution, and microporous polypropylene membrane is a barrier film assembling simulated battery, and the initial discharge capacity of test material is 86.7mAh/g, circulates 20 times, and capacity rises to 87.2mAh/g.
Example 2
In being full of the glove box of dry argon gas, take by weighing the anhydrous iron phosphate (1.0mol) of lithium powder (1.017mol) and the 150.82g 99.99% after the vacuum-drying of 7.06g 99.9%, two kinds of raw materials are packed into to mix in the stainless steel vibration blender, changes in the airtight tube container of stainless steel.From glove box, take out tube container, place retort furnace, 480 ℃ of constant temperature 600min, furnace cooling to 55 ℃ takes out black powder solid wherein, grinds 300 mesh sieves, promptly obtains ferrousphosphate lithium material.This sample is through the X-ray powder diffraction spectral test, and is consistent with LiFePO 4 standard x RD spectrogram, do not have obvious impurity peaks and exists.
With example 1 method assembling simulated battery, the initial discharge capacity of test material is 110.7mAh/g, circulates 20 times, and capacity rises to 111.8mAh/g.
Example 3
In being full of the glove box of dry argon gas, take by weighing the anhydrous iron phosphate (1.0mol) of lithium powder (1mol) and the 150.82g 99.99% after the vacuum-drying of 6.94g 99.9%, two kinds of raw materials are packed into to mix in the stainless steel vibration blender, changes in the airtight tube container of stainless steel.From glove box, take out tube container, place retort furnace, 675 ℃ of constant temperature 2000min, furnace cooling to 56 ℃ takes out black powder solid wherein, grinds 300 mesh sieves, promptly obtains ferrousphosphate lithium material.This sample is through the X-ray powder diffraction spectral test, and is consistent with LiFePO 4 standard x RD spectrogram, do not have obvious impurity peaks and exists.
With example 1 method assembling simulated battery, the initial discharge capacity of test material is 136.0mAh/g, circulates 20 times, and capacity rises to 139.5mAh/g.
Claims (1)
1, a kind of lithium iron phosphate synthetic method is characterized in that:
(1) selecting metallic lithium powder and anhydrous iron phosphate for use is raw material, and both materials mol ratios are (0.98～1.02): 1;
(2) tertiary iron phosphate after the vacuum-drying is mixed with metallic lithium powder in being full of the glove box of dry argon gas, in the airtight stainless steel vessel of packing into;
(3) stainless steel vessel is heated to 215 ℃～675 ℃ in process furnace, insulation 14～2000min stops heating, cools to the furnace≤60 ℃ the time, take out and grind, and crosses 300 mesh sieves, promptly gets LiFePO 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101561262A CN101386405B (en) | 2008-09-28 | 2008-09-28 | Lithium iron phosphate synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101561262A CN101386405B (en) | 2008-09-28 | 2008-09-28 | Lithium iron phosphate synthetic method |
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| Publication Number | Publication Date |
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| CN101386405A true CN101386405A (en) | 2009-03-18 |
| CN101386405B CN101386405B (en) | 2010-09-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2008101561262A Expired - Fee Related CN101386405B (en) | 2008-09-28 | 2008-09-28 | Lithium iron phosphate synthetic method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102013475A (en) * | 2010-10-22 | 2011-04-13 | 秦波 | Method for preparing porous spherical Li(1-x)MxFe(1-y)Ny(PO4)([3+(alpha-1)x+(beta-2) y]/3)/C material |
| CN102019404A (en) * | 2010-12-23 | 2011-04-20 | 何卫东 | Technology for preparing lithium ingots in glove boxes |
| CN102205954A (en) * | 2011-03-25 | 2011-10-05 | 天津恒普科技发展有限公司 | Method for synthesizing high-density lithium iron phosphate material |
| CN102942167A (en) * | 2012-05-30 | 2013-02-27 | 浙江工业大学 | Anhydrous ferric phosphate, lithium iron phosphate prepared from the anhydrous ferric phosphate and use of the lithium iron phosphate |
| CN102969505A (en) * | 2012-12-12 | 2013-03-13 | 南京大学 | LiFePO4 precursor hollow sphere and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020192137A1 (en) * | 2001-04-30 | 2002-12-19 | Benjamin Chaloner-Gill | Phosphate powder compositions and methods for forming particles with complex anions |
| 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 |
| CN100505391C (en) * | 2007-07-20 | 2009-06-24 | 哈尔滨工业大学 | honeycomb structure spherical LiFePO4 / C composite material preparation method |
-
2008
- 2008-09-28 CN CN2008101561262A patent/CN101386405B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102013475A (en) * | 2010-10-22 | 2011-04-13 | 秦波 | Method for preparing porous spherical Li(1-x)MxFe(1-y)Ny(PO4)([3+(alpha-1)x+(beta-2) y]/3)/C material |
| CN102019404A (en) * | 2010-12-23 | 2011-04-20 | 何卫东 | Technology for preparing lithium ingots in glove boxes |
| CN102019404B (en) * | 2010-12-23 | 2013-01-30 | 重庆昆瑜锂业有限公司 | Technology for preparing lithium ingots in glove boxes |
| CN102205954A (en) * | 2011-03-25 | 2011-10-05 | 天津恒普科技发展有限公司 | Method for synthesizing high-density lithium iron phosphate material |
| CN102942167A (en) * | 2012-05-30 | 2013-02-27 | 浙江工业大学 | Anhydrous ferric phosphate, lithium iron phosphate prepared from the anhydrous ferric phosphate and use of the lithium iron phosphate |
| CN102969505A (en) * | 2012-12-12 | 2013-03-13 | 南京大学 | LiFePO4 precursor hollow sphere and preparation method thereof |
| CN102969505B (en) * | 2012-12-12 | 2015-06-17 | 南京大学 | LiFePO4 precursor hollow sphere and preparation method thereof |
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| Publication number | Publication date |
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| CN101386405B (en) | 2010-09-29 |
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Assignee: Jiangsu Shuangde Group Co., Ltd. Assignor: Jiangsu Shuangdeng Power Supply Co., Ltd. Contract fulfillment period: 2009.3.1 to 2019.3.1 Contract record no.: 2009320000270 Denomination of invention: Lithium iron phosphate synthetic method License type: Exclusive license Record date: 2009.3.10 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.3.1 TO 2019.3.1; CHANGE OF CONTRACT Name of requester: JIANGSU SHUANGDENG GROUP CO.,LTD. Effective date: 20090310 |
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Granted publication date: 20100929 Termination date: 20170928 |