CN100450920C - Method for preparing powder of lithium iron phosphate - Google Patents
Method for preparing powder of lithium iron phosphate Download PDFInfo
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- CN100450920C CN100450920C CNB2006101367386A CN200610136738A CN100450920C CN 100450920 C CN100450920 C CN 100450920C CN B2006101367386 A CNB2006101367386 A CN B2006101367386A CN 200610136738 A CN200610136738 A CN 200610136738A CN 100450920 C CN100450920 C CN 100450920C
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
This invention relates to a method for synthesizing anode material lithium iron phosphate for lithium-ion batteries by high tecf12 micropowder can be used as filler for epoxy resin to prepare packaging material for large and ultra-large scale integrated circuit, or for other high-quality electronic devices.
Description
Technical field
The invention belongs to a kind of preparation method of anode material for lithium-ion batteries, particularly a kind of by leading to protection of inert gas to the improvement of reaction system the direct method of synthetic LiFePO 4 of anode material.
Background technology
The LiFePO of olivine structural
4Have raw material sources extensive, cheap, as the anode material for lithium-ion batteries high-temperature behavior good and by the people for being a kind of comparatively ideal lithium ion secondary power battery anode material.
At present synthetic LiFePO
4Method mainly contain high temperature solid-state method, hydrothermal method, sol-gel method, liquid-phase oxidation reduction method, solid phase microwave method.
The high temperature solid-state method that is widely adopted at present is with ferrous oxalate or acetate, mixes with ammonium hydrogen phosphate and lithium salts, obtains product through high-temperature calcination then under inert atmosphere argon gas or nitrogen protection.This method needs continual feeding rare gas element to protect and makes that the product of preparation can be not oxidized.
Needn't feed protective gas though hydrothermal method belongs to the liquid phase reaction environment but be only limited to a spot of powder preparing, if will enlarge its preparation amount, be subject to many limitations, particularly large-scale high temperature high voltage resistant DESIGN OF REACTOR manufacture difficulty is big, and cost is also high.
Sol-gel method presoma dry shrinkage is big, the suitability for industrialized production difficulty is big, synthesis cycle is longer.Metal alkoxide costs an arm and a leg in addition, and the solvent of alkoxide is poisonous usually.
Vitamins C acid, H have been used in the liquid-phase oxidation method of reducing
2O
2, LiI, etc. Chemicals, thereby increased the cost of product and the complicacy of technology, therefore also be not suitable for industrial production.
Summary of the invention
At the problems referred to above of anode material for lithium ion battery iron lithium phosphate, the invention provides a kind of lithium iron phosphate preparation method of novelty, it is raw material that lithium source and phosphorus source adopt self-control to contain adulterated monometallic.Secondly the present invention has adopted brand-new reaction system and has avoided the use of a large amount of rare gas elementes, thereby has greatly reduced production cost of products.The present invention is simple for process, and prepared iron lithium phosphate physicals and chemical property are good, are suitable for suitability for industrialized production.
A kind of preparation method of LiFePO 4 powder mainly comprises:
Adopting lithium salts, molysite, phosphoric acid salt, doped element and conductive agent is raw material, with lithium salts, molysite, doped metal ion (Me
N+) and phosphoric acid salt according to the mol ratio lithium: iron: Me
N+: phosphoric acid is 1.0: x: (1-x): 1.0, x=0.80-0.99 wherein, raw material mixes through ball milling, and the add-on of the presoma of conductive agent or conductive agent is the 5-40% of iron lithium phosphate growing amount, and the presoma that mixes is after press is pressed into piece, cover the carbon dust of 2-3 centimetre of thickness of one deck, place retort furnace, temperature of reaction is 300-800 ℃, and the reaction times is 6-12 hour, be cooled to room temperature, make iron phosphate powder.
Described lithium salts comprises: one or more in Quilonum Retard, lithium hydroxide, lithium nitrate, lithium chloride, the monometallic;
Described molysite comprises: one or more in Ferrox, ferric oxide, ferrous sulfate, the tertiary iron phosphate;
Described phosphoric acid salt comprises: one or more in ammonium hydrogen phosphate, primary ammonium phosphate, tertiary iron phosphate, the monometallic;
Described doped element is one or more in the elements such as nickel, manganese, zinc, titanium, magnesium, aluminium, zirconium, niobium, chromium and rare earth.
Described conductive agent is one or more in acetylene black, crystalline flake graphite, sucrose, glucose, the polyvinyl alcohol.
The principal reaction that reaction system of the present invention takes place is following (with Fe
2O
3, LiH
2PO
4With carbon dust be example):
Along with constantly the raise reaction that at first takes place of temperature of reaction system is that residual oxygen reacts and generates carbon oxides CO in the material boat
2, and then generate CO, in the insulating process in the system reducing gas (CO) more than needed will have very strong reducing atmosphere to the reactant maintenance system that plays a protective role, make carbothermic reduction reaction that (temperature is higher than 750 degrees centigrade) can take place.Carbon dust that covers in the temperature-fall period and corundum sheet will come product and isolate from outer air, avoid the oxidation of temperature-fall period.
The present invention is by carrying out briquetting to reactant, can be so that the air content in the reactant presoma significantly reduces, and make synthetic material and carbon dust separate easily, can further avoid contacting of presoma and air by on the briquetting body, covering carbon dust, by on the charging crucible, adding a cover the consumption that the corundum sheet can further reduce carbon dust, that is to say in final calcinate so just can guarantee that the thing of reactant is the iron lithium phosphate of olivine structural mutually as long as chlamydate carbon dust exists.Having avoided using in conventional high-temperature solid phase method or the common carbothermic reduction reaction solid phase method primary ammonium phosphate or ammonium hydrogen phosphate to produce ammonia as raw material is unfavorable for environment protection and has long problem of reaction times.
Reaction system of the present invention changes strong reducing property atmosphere into by traditional inert atmosphere, reduces production costs greatly without the inert gas flow protection, and the iron lithium phosphate purity height of preparation, chemical property and physicals are good.
Description of drawings
Fig. 1 is a reactive system sketch of the present invention; Wherein: 1-corundum sheet, 2-ground corundum crucible, 3-carbon dust, the block presoma of 4-;
Fig. 2 is the prepared LiFePO of embodiment
4The XRD figure of/C matrix material;
Fig. 3 is the prepared LiFePO that contains of embodiment
4The initial charge graphic representation of/C matrix material (test condition: carry out under room temperature (20 ℃) by the test of battery, with the metal lithium sheet is negative pole, positive plate is by the electrode materials powder of 80% (mass ratio), 10% acetylene black, 10% caking agent (tetrafluoroethylene, PTFE) compacting forms, and electrolytic solution is the LiPF of 1mol/l
6/ (EC+DME).Barrier film adopts Celgard 2400 films, and charge-discharge magnification is 0.2C.Battery is made in being filled with the glove box of high-purity argon gas.)
Fig. 4 is the prepared LiFePO of embodiment 1
4The cycle performance figure of/C matrix material.
Embodiment
Embodiment 1: with monometallic 10.58 grams, ferric oxide 8.025 grams add sucrose 4.72 grams simultaneously, carrying out ball milling together mixes, drying, briquetting, after block presoma is placed ground corundum material boat, on block presoma, cover the carbon dust of 2-3 cm thick again, to expect that boat places the retort furnace temperature controlling point to begin to heat up, reaction conditions is 700 ℃, and the reaction times is 12 hours, treating then vacuum oven cools off to room temperature, sample is taken out, make LiFePO
4/ C matrix material.
Embodiment 2: with lithium carbonate containing 3.71 grams, and Ferrox 18 grams, NiO 0.37 gram, primary ammonium phosphate 11.52 grams, the mixture of sucrose 3.2 grams is through high-energy ball milling, drying, briquetting, after block presoma is placed ground corundum material boat, on block presoma, cover the carbon dust of 2-3 cm thick again, will expect that boat places the retort furnace temperature controlling point to begin intensification, reaction conditions is 750 ℃, reaction times is 10 hours, treats then that vacuum oven cools off to room temperature sample is taken out, and makes LiFePO
4/ C matrix material.
Claims (6)
1. the preparation method of a LiFePO 4 powder is characterized in that: adopting lithium salts, molysite, phosphoric acid salt, doped element and conductive agent is raw material, with lithium salts, molysite, doped metal ion and phosphoric acid salt according to the mol ratio lithium: iron: Me
N+: phosphoric acid is 1.0: x: (1-x): 1.0, x=0.80-0.99 wherein, raw material mixes through ball milling, and the add-on of the presoma of conductive agent or conductive agent is the 5-40% of iron lithium phosphate growing amount, and the presoma that mixes is after press is pressed into piece, cover the carbon dust of 2-3 centimetre of thickness of one deck, place retort furnace, temperature of reaction is 300-800 ℃, and the reaction times is 6-12 hour, be cooled to room temperature, make iron phosphate powder.
2. according to the preparation method of the described LiFePO 4 powder of claim 1, it is characterized in that: described lithium salts comprises: one or more in Quilonum Retard, lithium hydroxide, the monometallic.
3. according to the preparation method of the described LiFePO 4 powder of claim 1, it is characterized in that: described molysite comprises: one or more in Ferrox, ferric oxide, the ferrous sulfate.
4. according to the preparation method of the described LiFePO 4 powder of claim 1, it is characterized in that: described phosphoric acid salt comprises: one or more in ammonium hydrogen phosphate, primary ammonium phosphate, tertiary iron phosphate, the monometallic.
5. according to the preparation method of the described LiFePO 4 powder of claim 1, it is characterized in that: described doped element is one or more in nickel, manganese, zinc, titanium, magnesium, the aluminium.
6. according to the preparation method of the described LiFePO 4 powder of claim 1, it is characterized in that: described conductive agent is one or more in acetylene black, crystalline flake graphite, sucrose, the glucose.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101367386A CN100450920C (en) | 2006-11-24 | 2006-11-24 | Method for preparing powder of lithium iron phosphate |
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|---|---|---|---|
| CNB2006101367386A CN100450920C (en) | 2006-11-24 | 2006-11-24 | Method for preparing powder of lithium iron phosphate |
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| CN1958441A CN1958441A (en) | 2007-05-09 |
| CN100450920C true CN100450920C (en) | 2009-01-14 |
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|---|---|---|---|
| CNB2006101367386A Expired - Fee Related CN100450920C (en) | 2006-11-24 | 2006-11-24 | Method for preparing powder of lithium iron phosphate |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090131680A (en) * | 2007-07-31 | 2009-12-29 | 비와이디 컴퍼니 리미티드 | Method for preparing lithium iron phosphate as positive electrode active material for lithium ion secondary battery |
| CN101546831B (en) * | 2008-03-28 | 2012-09-26 | 潘树明 | Lithium ion battery anode material composite lithium iron phosphate and four-step synthesis and preparation process thereof |
| CN101638226B (en) * | 2009-08-28 | 2012-08-29 | 浙江贝能新材料科技有限公司 | Preparation method of spherical lithium iron phosphate |
| CN102092700A (en) * | 2010-11-22 | 2011-06-15 | 新乡市金光能源材料科技有限公司 | Method for preparing lithium material dopted with ferrous phosphate |
| CN105514357B (en) * | 2014-09-24 | 2018-05-29 | 比亚迪股份有限公司 | A kind of anode material of lithium battery LiM1-xNxPO4/ C and preparation method thereof |
| CN107154494A (en) * | 2017-05-26 | 2017-09-12 | 河南圣起机械集团有限公司 | A kind of preparation method of lithium iron phosphate positive material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785800A (en) * | 2005-12-23 | 2006-06-14 | 清华大学 | Preparation method of rare earth doped iron lithium phosphate powder |
| CN1803592A (en) * | 2005-12-23 | 2006-07-19 | 清华大学 | Method for preparing lithium enriched lithium ion phosphate powder |
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- 2006-11-24 CN CNB2006101367386A patent/CN100450920C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785800A (en) * | 2005-12-23 | 2006-06-14 | 清华大学 | Preparation method of rare earth doped iron lithium phosphate powder |
| CN1803592A (en) * | 2005-12-23 | 2006-07-19 | 清华大学 | Method for preparing lithium enriched lithium ion phosphate powder |
Non-Patent Citations (2)
| Title |
|---|
| 新型锂离子电池正极材料的研究进展. 唐致远等.化工进展，第23卷第8期. 2004 |
| 新型锂离子电池正极材料的研究进展. 唐致远等.化工进展，第23卷第8期. 2004 * |
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