CN108298513A - A kind of preparation method of high-purity spherical shape battery-grade iron phosphate - Google Patents

A kind of preparation method of high-purity spherical shape battery-grade iron phosphate Download PDF

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Publication number
CN108298513A
CN108298513A CN201711482602.5A CN201711482602A CN108298513A CN 108298513 A CN108298513 A CN 108298513A CN 201711482602 A CN201711482602 A CN 201711482602A CN 108298513 A CN108298513 A CN 108298513A
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China
Prior art keywords
phosphate
ferric phosphate
mixed solution
ferric
purity
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CN201711482602.5A
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Chinese (zh)
Inventor
刘俊才
李健
宫东杰
张仁国
王永松
岳有涛
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Guizhou Only High New Energy Technology Co Ltd
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Guizhou Only High New Energy Technology Co Ltd
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Priority to CN201711482602.5A priority Critical patent/CN108298513A/en
Publication of CN108298513A publication Critical patent/CN108298513A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C01P2006/82—Compositional purity water content

Abstract

The invention discloses a kind of preparation methods of high-purity spherical shape battery-grade iron phosphate, include the following steps：Configure the mixed solution of trivalent iron salt, mixed solution and a concentration of 0.1 0.3mol/L sodium carbonate will be slowly pumped into proportion in the magnetic agitation container equipped with bottom liquid, mixed liquor adjusts pH value by instilling sodium carbonate, the ferric phosphate mixed material of uniform-spherical is made in heating stirring precipitation simultaneously, ferric phosphate after filtration washing low temperature drying obtains the anhydrous iron phosphate of high-purity after 400 700 DEG C of high-temperature process.The main content of ferric phosphate produced by the present invention is high, content of beary metal is low, compactness is high, consistency is good.

Description

A kind of preparation method of high-purity spherical shape battery-grade iron phosphate
Technical field
The invention belongs to electrochemical power source technical field of material, and in particular to arrive a kind of high-purity spherical shape LITHIUM BATTERY phosphorus The preparation method of sour iron.
Background technology
It is typically all directly to use that existing technique, which prepares ferric phosphate,；Iron chloride or ferric nitrate or ferrous sulfate solution are through dioxygen It is directly added into phosphoric acid after water oxygen or is prepared by solvable phosphate.The impurity such as its sulfate radical, potassium, sodium, magnesium, manganese and heavy metal (Pb, Ni, Co etc.) content is higher, and these impurity will have a direct impact on or reduce the battery capacity of ferric phosphate lithium cell, multiplying power discharging etc. Performance.Theoretically, these impurity are more lower better.Sulfate radical, potassium, sodium equal size are reachable in the ferric phosphate of prior art synthesis 500~5000ppm or so, beavy metal impurity (Fe, Co, Ni, Pb, Cd, Cr etc.) content reach 100ppm or so or higher, even if It is the ferric phosphate of SILVER REAGENT, sulfate radical, potassium, sodium equal size are also in 500ppm or so.With general cleaner, even if can be by sulfuric acid Root, potassium, sodium equal size and beavy metal impurity (Co, Ni, Pb etc.) content reduce, but the ferric phosphate product purity prepared is still not Height, and microstructure does not have the excellent chemical property for being applicable in battery material.Also it is irregular on pattern, shakes relatively low, It is extremely difficult to 1.0g/cm3Above requirement often can also introduce more impurity elements in product.Thus the ferric phosphate synthesized Lithium gram volume is relatively low, and multiplying power discharging property is poor, and product quality is that the battery level iron oxalate product of LiFePO4 requirement is not achieved It is required that, thus cannot also meet ferric phosphate lithium cell raw materials for production requirement.
The main component of organic molysite is carbon, hydrogen, oxygen and iron, using organic salt iron as the source of iron for making ferric phosphate, phosphorus For sour iron in low pH ranges after synthesis of detergent, remaining organic acid, can by being changed into carbon dioxide and steam after high temperature sintering Effectively reduce content of beary metal in ferric phosphate.
Invention content
The purpose of the present invention is to provide a kind of main content height, the battery-grade iron phosphates that content of beary metal is low, compactness is high Preparation method.
A kind of preparation method of high-purity spherical shape battery-grade iron phosphate of the present invention, includes the following steps：
(1) mixed solution of trivalent iron salt, wherein Fe are configured3+The molar ratio of source and phosphorus source is 1:1.2-1.5, Fe3+ Source and crystal control agent molar ratio are 10:0.5-2；
(2) speed by mixed solution and 0.1-0.3mol/L sodium carbonate with flow for 100-200ml/h is slowly dropped into dress Have in the magnetic agitation container that the phosphoric acid solution of pH=1.5 ± 0.2 is bottom liquid, mixed solution pH value is controlled by instilling sodium carbonate 1.0-2.0, mixed solution drips off or mixed material volume reaches at reaction vessel 2/3rds, stops being pumped into, and continues to stir 0.5-2 hours, the ferric phosphate mixed material being tentatively nucleated；
(3) ferric phosphate mixed material is heated to 60-95 DEG C, continues stirring and obtains being nucleated complete phosphoric acid for 0.5-2 hours Iron precipitates FePO4·2H2O；
(4) the ferric phosphate precipitation after filtration washing low temperature drying, after 400-700 DEG C of high-temperature process, obtains height The anhydrous phosphoric acid of purity；
Wherein step (1) described Fe3+Source is the one or two or more kinds in organic molysite ironic citrate or ferric lactate；
Wherein step (1) phosphorus source is the one or two or more kinds in phosphoric acid, ammonium dihydrogen phosphate or diammonium hydrogen phosphate；
Wherein step (1) described crystal control agent is parents' conjugated polymer carboxymethyl cellulose, polyvinyl alcohol or poly- second One or two or more kinds in glycol.
Compared with prior art, the present invention there is apparent advantageous effect, as can be known from the above technical solutions:It makes through the invention The main content >=99.5%, S of ferric phosphate, Na≤30ppm, Pb, Cd, Cr heavy metal≤10ppm, Ca, Mg, Al, Ni, Mn are equal ≤ 50ppm, final grain diameter D50 maintain 5-8um, tap density >=1.2g/cm, iron phosphorus ratio 0.99-1.0, raw material sources Extensively, at low cost, preparation process is succinct, has some superiority, and good basis is laid for industrialization..
Specific implementation mode
Embodiment 1：
A kind of preparation method of high-purity spherical shape battery-grade iron phosphate, includes the following steps：
(1) mixed solution of trivalent iron salt is configured, the wherein molar ratio of ironic citrate and phosphoric acid is 1:1.2, citric acid Iron and sodium carboxymethylcellulose molar ratio are 10:2；
(2) mixed solution and 0.3mol/L sodium carbonate are slowly dropped into for the speed of 100ml/h equipped with pH=with flow 1.5,30ml phosphoric acid solution is to control mixed solution pH value 1.8 in the magnetic agitation container of bottom liquid by instilling sodium carbonate, mix Conjunction solution drips off or mixed material volume reaches at reaction vessel 2/3rds, stops being pumped into, and continues stirring 0.5 hour, obtains The ferric phosphate mixed material being tentatively nucleated；
(3) ferric phosphate mixed material is heated to 85 DEG C, continues stirring and obtains within 2 hours being nucleated complete ferric phosphate precipitation (FePO4·2H2O)；
(4) the ferric phosphate precipitation after filtration washing low temperature drying, after 700 DEG C of high-temperature process, obtains high-purity Anhydrous phosphoric acid.
Embodiment 2：
A kind of preparation method of high-purity spherical shape battery-grade iron phosphate, includes the following steps：
(1) mixed solution of trivalent iron salt is configured, the wherein molar ratio of ferric lactate and diammonium hydrogen phosphate is 1:1.05 breast Sour iron and polyethylene glycol molar ratio are 10:1.4；
(2) mixed solution and 0.2mol/L sodium carbonate are slowly dropped into for the speed of 150ml/h equipped with pH=with flow 1.3,50ml ammonium dibasic phosphate solution is to control mixed solution pH value by instilling sodium carbonate in the magnetic agitation container of bottom liquid 1.5, mixed solution drips off or mixed material volume reaches at reaction vessel 2/3rds, stops being pumped into, and continues stirring 1 hour 20 Point, the ferric phosphate mixed material being tentatively nucleated；
(3) ferric phosphate mixed material is heated to 78 DEG C, continue 15 points of stirring 1 hour it is heavy to complete ferric phosphate is nucleated Form sediment (FePO4·2H2O)；
(4) the ferric phosphate precipitation after filtration washing low temperature drying, after 550 DEG C of high-temperature process, obtains high-purity Anhydrous iron phosphate.
Embodiment 3：
A kind of preparation method of high-purity spherical shape battery-grade iron phosphate, includes the following steps：
(1) mixed solution of trivalent iron salt is configured, the wherein molar ratio of ferric lactate and ammonium dihydrogen phosphate is 1:1.2, breast Sour iron and sodium carboxymethylcellulose molar ratio are 10:1.6；
(2) speed by mixed solution and a concentration of 0.1mol/L sodium carbonate with flow for 200ml/h, which is slowly dropped into, is equipped with The ammonium dihydrogen phosphate of pH=1.7,40ml are to control mixed solution by instilling sodium carbonate in the magnetic agitation container of bottom liquid PH value 1.0, mixed solution drips off or mixed material volume reaches at reaction vessel 2/3rds, stops being pumped into, and it is small to continue stirring 2 When, the ferric phosphate mixed material that is tentatively nucleated；
(3) ferric phosphate mixed material is heated to 64 DEG C, continues stirring and obtains within 0.5 hour being nucleated complete ferric phosphate precipitation (FePO4·2H2O)；
(4) the ferric phosphate precipitation after filtration washing low temperature drying, after 400 DEG C of high-temperature process, obtains high-purity Anhydrous iron phosphate.
By above-described embodiment 1-3, ferric phosphate related data such as following table obtained
The above described is only a preferred embodiment of the present invention, being not intended to limit the present invention in any form, appoint What is made by the above technical examples according to the technical essence of the present invention any simple without departing from technical solution of the present invention content Modification, equivalent variations and modification, in the range of still falling within technical solution of the present invention.

Claims (1)

1. a kind of preparation method of high-purity spherical shape battery-grade iron phosphate, includes the following steps：
（1）Configure the mixed solution of trivalent iron salt, wherein Fe3+The molar ratio of source and phosphorus source is 1:1.2-1.5, Fe3+Source and crystalline substance Shape controlling agent molar ratio ratio is 10:0.5-2；
（2）Speed by mixed solution and 0.1-0.3mol/L sodium carbonate with flow for 100-200ml/h is slowly pumped into equipped with pH= 1.5 ± 0.2 phosphoric acid solution is during which to control mixed solution pH value by instilling sodium carbonate in the magnetic agitation container of bottom liquid 1.0-2.0, mixed solution drips off or mixed material volume reaches at reaction vessel 2/3rds, stops being pumped into, and continues to stir 0.5-2 hours, the ferric phosphate mixed material being tentatively nucleated；
（3）Ferric phosphate mixed material is heated to 60-95 DEG C, continues stirring and obtain within 0.5-2 hour being nucleated complete ferric phosphate to sink Shallow lake FePO4•2H2O；
（4）Ferric phosphate precipitation after filtration washing low temperature drying, after 400-700 DEG C of high-temperature process, obtains high-purity Anhydrous iron phosphate；
Wherein step（1）The Fe3+Source is the one or two or more kinds in organic molysite ironic citrate or ferric lactate；
Wherein step（1）Phosphorus source is the one or two or more kinds in phosphoric acid, ammonium dihydrogen phosphate or diammonium hydrogen phosphate；
Wherein step（1）The crystal control agent is parents' conjugated polymer carboxymethyl cellulose, polyvinyl alcohol or polyethylene glycol In one or two or more kinds.
CN201711482602.5A 2017-12-29 2017-12-29 A kind of preparation method of high-purity spherical shape battery-grade iron phosphate Pending CN108298513A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109205584A (en) * 2018-10-09 2019-01-15 湖南雅城新材料有限公司 A kind of preparation method of high-speed rail phosphorus than ferric phosphate
CN110451472A (en) * 2019-09-11 2019-11-15 李旭意 The preparation method of anhydrous iron phosphate in a kind of organic system
CN110562946A (en) * 2019-08-08 2019-12-13 安徽昶源新材料股份有限公司 Battery-grade anhydrous iron phosphate with sheet structure and preparation method thereof
CN110911680A (en) * 2019-11-22 2020-03-24 贵州唯特高新能源科技有限公司 Preparation method of Ti and V element composite doped lithium iron phosphate
CN112938921A (en) * 2021-04-07 2021-06-11 贵州唯特高新能源科技有限公司 Method for preparing iron phosphate

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109205584A (en) * 2018-10-09 2019-01-15 湖南雅城新材料有限公司 A kind of preparation method of high-speed rail phosphorus than ferric phosphate
CN110562946A (en) * 2019-08-08 2019-12-13 安徽昶源新材料股份有限公司 Battery-grade anhydrous iron phosphate with sheet structure and preparation method thereof
CN110451472A (en) * 2019-09-11 2019-11-15 李旭意 The preparation method of anhydrous iron phosphate in a kind of organic system
CN110911680A (en) * 2019-11-22 2020-03-24 贵州唯特高新能源科技有限公司 Preparation method of Ti and V element composite doped lithium iron phosphate
CN112938921A (en) * 2021-04-07 2021-06-11 贵州唯特高新能源科技有限公司 Method for preparing iron phosphate

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Application publication date: 20180720