CN1974411A - Process of producing lithium iron phosphate precursor with ferrous sulfate as side product of titanium white production - Google Patents
Process of producing lithium iron phosphate precursor with ferrous sulfate as side product of titanium white production Download PDFInfo
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- CN1974411A CN1974411A CNA2006101369023A CN200610136902A CN1974411A CN 1974411 A CN1974411 A CN 1974411A CN A2006101369023 A CNA2006101369023 A CN A2006101369023A CN 200610136902 A CN200610136902 A CN 200610136902A CN 1974411 A CN1974411 A CN 1974411A
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- ferrous sulfate
- lithium
- iron phosphate
- phosphate
- lithium iron
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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 present invention relates to process of producing lithium iron phosphate precursor for producing positive pole material of lithium ion cell with ferrous sulfate as the side product of titanium white production. By using the ferrous sulfate as material, and through depurating, adding some beneficial elements for raising the yield of lithium iron phosphate, deposting and vacuum drying the precipitate, and roasting, ferric oxide as the lithium iron phosphate precursor for producing positive pole material of lithium ion cell is obtained. The present invention has the advantages of simple technological process, low production cost and high product purity, and is suitable for comprehensive utilization of ferrous sulfate as the side product of titanium white production while providing material for producing lithium iron phosphate precursor.
Description
Technical field: the present invention relates to a kind of method of producing the lithium ion battery anode material lithium iron phosphate presoma, particularly a kind of method of producing the used molysite presoma of lithium ion battery anode material lithium iron phosphate with wet chemical method from the titanium white ferrous sulfate as side product.
Technical background:
Lithium-ion-power cell has possessed the ability that extensively comes into the market now, the famine of cobalt resource causes the high of cobalt price, make lithium cobalt oxygen be difficult to satisfy the demand of popular lithium-ion-power cell, and specific storage is low and the high-temperature behavior difference becomes puzzlement lithium manganese oxygen and carries out an industrialized gordian technique difficult problem. as the iron lithium phosphate (LiFePO of olivine-type
4) since have cheap, thermally-stabilised good, environmentally safe and become the most potential a kind of lithium-ion-power cell material.But aspects such as, light specific gravity but not high as purity in many aspects as the main precursor raw material molysite of producing lithium ion battery anode material lithium iron phosphate, product performance instability are restricting the extensive chemical industry production of iron lithium phosphate.
China mainly adopts Titanium White Production By Sulfuric Acid Process at present, 4 tons of ferrous sulfate of the about by-product of 1 ton of titanium white of the every production of this method, titanium white by product ferrous sulfate in 2005 reaches 2,500,000 tons according to statistics, though someone is used to do iron catalyst, water purification agent, pigment etc. with the titanium white ferrous sulphate of byproduct, the quantity of treatable titanium white ferrous sulphate of byproduct seldom.The major impurity of titanium white ferrous sulphate of byproduct is titanium, magnesium, manganese, zinc etc.; their existence strictness has limited the comprehensive utilization of ferrous sulphate of byproduct; and titanium, magnesium, manganese etc. be incorporated in the chemical property that can improve lithium ion battery anode material lithium iron phosphate in some sense; therefore only need through simple removal of impurities; in removal of impurities, specially introduce simultaneously some correctabilities again and modify the lithium ion battery anode material lithium iron phosphate doped element, can obtain being suitable for the molysite raw material that the extensive chemical industry of iron lithium phosphate is produced.
Summary of the invention:
For defectives such as the production cost height that overcomes existing iron lithium phosphate raw material molysite, unstable product quality, the invention provides a kind of method of producing ferric lithium phosphate precursor from the titanium white ferrous sulfate as side product, it is raw material that this method adopts titanium white ferrous sulfate as side product cheap and easy to get, pass through purification and impurity removal, add micro-beneficial element, post precipitation with drying precipitate, roasting obtains being suitable for the molysite raw material of lithium ion battery anode material lithium iron phosphate large-scale industrial production.
A kind of method of producing ferric lithium phosphate precursor from the titanium white ferrous sulfate as side product, adopting the by-product ferrous sulfate during in the production process of titanium pigment is raw material, by purification and impurity removal, remove the impurity element that some are unfavorable for improving the lithium ion battery anode material lithium iron phosphate performance, add the beneficial element that some can improve lithium ion battery anode material lithium iron phosphate simultaneously, add precipitation agent and oxygenant, precipitation obtains the battery material presoma at last.
Described byproduct ferrous sulfate of titanium dioxide refers to the by product iron vitriol or the ferrous sulfate hydrate that obtain in production process of titanium pigment.
Technological process mainly comprises:
(1) ferrous sulfate as side product is used deionized water dissolving down at 40-80 ℃, the pH value of adjusting solution with ammoniacal liquor is 3.0-6.0, adds an amount of hydrogen peroxide, makes metal ion co-precipitation such as the sedimentary while manganese of iron partial hydrolysis, zinc, leaves standstill, filters;
(2) the control pH value of filtrate is at 0-5.5, and adding is of value to the element M e that improves the iron lithium phosphate performance, comprises in the element soluble salts such as manganese, zinc, titanium, magnesium, aluminium, zirconium, niobium, chromium and rare earth one or more;
(3) add oxygenant and precipitation agent, with sodium hydroxide control pH value 0-10.5, reacted 1-5 hour, filtration, washing to the barium chloride solution with 30% detect the sulfate radical-free ion, will be deposited in the presoma product that 50-120 ℃ of following vacuum-drying obtains lithium ion battery anode material lithium iron phosphate.
The precipitation agent that adds is one or more in the phosphoric acid salt of phosphoric acid, triammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate and alkali metallic sodium, potassium, lithium, for obtaining ferric lithium phosphate precursor, need oxidation of divalent is become ferric iron, the available oxygenant has one or more in hydrogen peroxide, hypochlorous acid, clorox, the sodium chlorate.
Can not pollute and endanger in the whole process of production of the present invention, benefit environmental protection to ecotope and HUMAN HEALTH; Technology is simple, production rate is fast, plant efficiency is high, be fit to scale operation, metal recovery rate height, and cost is low.
Embodiment
Embodiment 1: get 500 gram ferrous sulfate as side product and use deionized water dissolving down at 60 ℃, the pH value of adjusting solution with ammoniacal liquor is 3.5, adds the 5ml hydrogen peroxide, leaves standstill, filters; Under 80 ℃, adding concentration is 85% phosphoric acid 350ml in filtrate; No ferrous ion exists in the solution to detecting with red prussiate of potash to add sodium chlorate at last, the sodium hydroxide that adds 150 grams, reacted 3 hours, filtration, washing to the barium chloride solution with 30% detect the sulfate radical-free ion, will be deposited in 80 ℃ of following vacuum-dryings and obtain lithium ion battery anode material lithium iron phosphate presoma product tertiary iron phosphate.
Embodiment 2: get 500 gram ferrous sulfate as side product and use deionized water dissolving down at 60 ℃, the pH value of adjusting solution with ammoniacal liquor is 3.5, adds the 5ml hydrogen peroxide, leaves standstill, filters; Under 80 ℃, adding concentration is 85% phosphoric acid 300ml and 50 gram chromium sulphates in filtrate; No ferrous ion exists in the solution to detecting with red prussiate of potash to add an amount of hydrogen peroxide at last, add 150 gram sodium hydroxide, reacted 3 hours, filtration, washing to the barium chloride solution with 30% detect the sulfate radical-free ion, will be deposited in the lithium ion battery anode material lithium iron phosphate presoma product tertiary iron phosphate that 80 ℃ of following vacuum-dryings obtain mixing chromium.
Embodiment 3: get 500 gram ferrous sulfate as side product and use deionized water dissolving down at 60 ℃, the pH value of adjusting solution with ammoniacal liquor is 3.5, adds the 5ml hydrogen peroxide, leaves standstill, filters; Under 80 ℃, adding concentration is 85% phosphatase 24 00ml and 80 gram single nickel salts in filtrate; No ferrous ion exists in the solution to detecting with red prussiate of potash to add an amount of sodium chlorate at last, the sodium hydroxide that adds 200 grams, reacted 4 hours, filtration, washing to the barium chloride solution with 30% detect the sulfate radical-free ion, will be deposited in the lithium ion battery anode material lithium iron phosphate presoma product tertiary iron phosphate that 80 ℃ of following vacuum-dryings obtain mixing nickel.
Embodiment 4: get 500 gram ferrous sulfate as side product and use deionized water dissolving down at 60 ℃, the pH value of adjusting solution with ammoniacal liquor is 3.5, adds the 5ml hydrogen peroxide, leaves standstill, filters; Under 80 ℃, adding concentration is 85% phosphoric acid 350ml and 50 gram lanthanum nitrates in filtrate; No ferrous ion exists in the solution to detecting with red prussiate of potash to add an amount of sodium chlorate at last, the sodium hydroxide that adds 150 grams, reacted 3 hours, filtration, washing to the barium chloride solution with 30% detect the sulfate radical-free ion, will be deposited in the lithium ion battery anode material lithium iron phosphate presoma product tertiary iron phosphate that 80 ℃ of following vacuum-dryings obtain mixing lanthanum.
Embodiment 5: get 500 gram ferrous sulfate as side product and use deionized water dissolving down at 60 ℃, the pH value of adjusting solution with ammoniacal liquor is 3.5, adds the 5ml hydrogen peroxide, leaves standstill, filters; Under 80 ℃, in filtrate, add concentration and be 85% phosphoric acid 350ml and 50 gram magnesium chlorides, 50 gram titanium chlorides; No ferrous ion exists in the solution to detecting with red prussiate of potash to add an amount of sodium chlorate at last, the sodium hydroxide that adds 200 grams, reacted 3 hours, filtration, washing to the barium chloride solution with 30% detect the sulfate radical-free ion, will be deposited in the lithium ion battery anode material lithium iron phosphate presoma product tertiary iron phosphate that 80 ℃ of following vacuum-dryings obtain mixing magnesium, titanium.
Claims (7)
1. method of producing ferric lithium phosphate precursor from the titanium white ferrous sulfate as side product, it is characterized in that: adopting the by-product ferrous sulfate during in the production process of titanium pigment is raw material, by purification and impurity removal, remove the impurity element that some are unfavorable for improving the lithium ion battery anode material lithium iron phosphate performance, add the beneficial element that some can improve lithium ion battery anode material lithium iron phosphate simultaneously, add precipitation agent and oxygenant, precipitation obtains the battery material presoma at last.
2. method according to claim 1 is characterized in that: described byproduct ferrous sulfate of titanium dioxide refers to the by product iron vitriol or the ferrous sulfate hydrate that obtain in production process of titanium pigment.
3. method according to claim 1, it is characterized in that: described purification and impurity removal is meant: at first ferrous sulfate as side product is used deionized water dissolving down at 40-80 ℃, the pH value of adjusting solution with ammoniacal liquor is 3.0-6.0, add an amount of hydrogen peroxide and make metal ion co-precipitation such as the sedimentary while manganese of iron partial hydrolysis, zinc, leave standstill, filter, the filtrate after being purified.
4. method according to claim 1 is characterized in that: described beneficial element refers to: one or more in the elements such as manganese, zinc, titanium, magnesium, aluminium, zirconium, niobium, chromium and rare earth.
5. method according to claim 1 is characterized in that: described precipitation agent refers to one or more in the phosphoric acid salt of phosphoric acid, triammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate and alkali metallic sodium, potassium, lithium.
6. method according to claim 1 is characterized in that: described oxygenant refers to one or more in hydrogen peroxide, hypochlorous acid, sodium chlorate, the clorox.
7. method according to claim 4 is characterized in that: described beneficial element is simple substance element, soluble sulphate, solubility nitrate or soluble salt hydrochlorate.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2006101369023A CN1974411A (en) | 2006-12-19 | 2006-12-19 | Process of producing lithium iron phosphate precursor with ferrous sulfate as side product of titanium white production |
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| CNA2006101369023A CN1974411A (en) | 2006-12-19 | 2006-12-19 | Process of producing lithium iron phosphate precursor with ferrous sulfate as side product of titanium white production |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100595949C (en) * | 2008-02-26 | 2010-03-24 | 郑州瑞普生物工程有限公司 | Method for making positive material positive ferric phosphate of lithium battery |
| CN108821255A (en) * | 2018-07-11 | 2018-11-16 | 方嘉城 | A kind of preparation method of ferric phosphate |
| CN110937586A (en) * | 2018-09-25 | 2020-03-31 | 杭州长凯能源科技有限公司 | Circular economy process for preparing materials |
| CN115403021A (en) * | 2022-09-08 | 2022-11-29 | 云南纳诺电子新材料有限公司 | Method for preparing lithium iron phosphate from titanium dioxide byproduct ferrous sulfate |
| CN115818605A (en) * | 2022-12-22 | 2023-03-21 | 曲靖市德方纳米科技有限公司 | Iron phosphate dihydrate, preparation method thereof and preparation method of lithium iron phosphate cathode material |
-
2006
- 2006-12-19 CN CNA2006101369023A patent/CN1974411A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100595949C (en) * | 2008-02-26 | 2010-03-24 | 郑州瑞普生物工程有限公司 | Method for making positive material positive ferric phosphate of lithium battery |
| CN108821255A (en) * | 2018-07-11 | 2018-11-16 | 方嘉城 | A kind of preparation method of ferric phosphate |
| CN110937586A (en) * | 2018-09-25 | 2020-03-31 | 杭州长凯能源科技有限公司 | Circular economy process for preparing materials |
| CN110937586B (en) * | 2018-09-25 | 2023-09-22 | 杭州长凯能源科技有限公司 | Circular economic process for preparing material |
| CN115403021A (en) * | 2022-09-08 | 2022-11-29 | 云南纳诺电子新材料有限公司 | Method for preparing lithium iron phosphate from titanium dioxide byproduct ferrous sulfate |
| CN115818605A (en) * | 2022-12-22 | 2023-03-21 | 曲靖市德方纳米科技有限公司 | Iron phosphate dihydrate, preparation method thereof and preparation method of lithium iron phosphate cathode material |
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