CN101386575A - Method for preparing iron oxalate - Google Patents
Method for preparing iron oxalate Download PDFInfo
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- CN101386575A CN101386575A CNA200810124252XA CN200810124252A CN101386575A CN 101386575 A CN101386575 A CN 101386575A CN A200810124252X A CNA200810124252X A CN A200810124252XA CN 200810124252 A CN200810124252 A CN 200810124252A CN 101386575 A CN101386575 A CN 101386575A
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Abstract
The present invention discloses a method for preparing ferrous oxalate, which belongs to the technical field of powdered material preparation. The aim of the invention is to provide a preparation method of ferrous oxalate which is high in purity, controllable in granularity, even in grain size, and high in conductivity. The method comprises the following steps of locating ferrous sulfate into dilute sulphuric acid, adding scrap iron with stirring, and obtaining a ferrous sulfate solution after suction filtration; dissolving oxalic acid or/and ammonium oxalate in distilled water with stirring and heating, and obtaining a mixed solution of oxalic acid or/and ammonium oxalate through suction filtration after dissolution; and, slowly adding the ferrous sulfate solution into oxalic acid solution, keeping the temperature, stirring, separating ferrous sulfate from the original synthetic solution after keeping stand, and obtaining ferrous oxalate powder through washing and drying. The ferrous oxalate prepared by the preparation method is a powder with a medium grain diameter of between 0.5 and 80 mu m. The granularity is completely controllable. The product purity is greater than 99.0 percent. The conductivity is high. The electrochemical performance of the ferrous phosphate salt composite material is largely improved. The conductivity of lithium iron phosphate is improved by 5 orders of magnitude.
Description
Technical field
The present invention relates to a kind of preparation method of Ferrox, belong to technical field of powdered material preparation.
Background technology
Ferrox is widely used in the production of pottery, glass, sensitive materials as a kind of industrial chemicals, especially is used for preparing the source of iron of the first-selected positive electrode material LiFePO 4 of lithium that is used for power cell in addition.Lithium ion battery is as the green high-capacity battery, numerous advantages such as have that voltage height, energy density are big, good cycle, self-discharge are little, memory-less effect and working range are wide are widely used on mobile phone, notebook computer, digital camera and other a large amount of emerging IT product.In addition, aspect power truck, power tool, automobile 42V battery, photovoltaic energy storage macrocell, also begin progressively to substitute traditional lead-acid cell.Most important part is a positive electrode material in the production lithium ion battery material therefor, as a kind of novel anode material for lithium-ion batteries, iron lithium phosphate is because its raw material sources are extensive, with low cost, safe, environmentally friendly, be particularly suitable for high-power electric appliance with power cells such as battery and automobiles, can substitute traditional lead-acid cell significantly.
At present, the method for preparing ferrous phosphate lithium battery be with Ferrox as source of iron, primary ammonium phosphate is as the phosphorus source, Quilonum Retard is as the lithium source.But, existing Ferrox can not satisfy the requirement of the high-quality phosphoric acid molysite of preparation, because it exists purity low, size distribution is inhomogeneous, particularly crystal formation is unstable and not single, be oblique side, monocline and triclinic mixing crystal formation, in the production process of LiFePO 4, raw-material physics pattern has great influence to finished product, so, adopt the ferrous phosphate salt material pattern of existing Ferrox preparation poor, the LiFePO 4 powder tapping density that makes is lower, and commercially available material is lower than 1.2g/cm at present
3, be 1/3rd of its real density only, cause energy capacity of battery density lower.In addition, iron lithium phosphate also has a shortcoming to be that its lower electronic conductivity (is about 10
-8S/cm), mainly carry out metal ion mixing by adding easy conductive agent (as carbon black, copper powder, high temperature pyrolysis carbon coated) at present, methods such as synthetic sodium rice particle have been alleviated the influence of low electrical conductivity.But the method for its doped metal ion mainly is to sneak into some oxide compounds in the batch mixing stage, because the material of reaction is more, is difficult to the uniformity coefficient in the assurance mixing process.
Summary of the invention
The object of the present invention is to provide a kind of high purity that has, controllable granularity, uniform particles, preparation method of ferrous oxalate.
Its technical scheme is: a kind of preparation method of Ferrox is characterized in that its method steps:
A) ferrous sulfate is placed dilute sulphuric acid, add iron filings, stir, 15 ℃～100 ℃ of control reaction temperature get copperas solution behind the suction filtration;
B) with oxalic acid or/and ammonium oxalate is dissolved in the distilled water, stir, heating and temperature control is at 15 ℃～100 ℃, treats oxalic acid or/and after ammonium oxalate dissolved fully, suction filtration gets oxalic acid or/and the ammonium oxalate mixing solutions;
C) slowly copperas solution is joined in oxalic acid solution or oxalic acid and the ammonium oxalate mixing solutions, temperature of reaction is 0-65 ℃, behind the insulated and stirred 45min, and static 10～30min; After mother liquor separates, obtain the Ferrox powder through washing and drying.
In the above-mentioned copperas solution, be added with additive.
Its technique effect is: the present invention is in conjunction with the characteristics of ferrousphosphate lithium material, adopt industrial waste iron filing as raw material, and particle diameter is the powder of 0.5 μ m～80 μ m in can preparing according to different reaction conditionss, granularity is controlled fully, product purity satisfies the source of iron requirement of lithium battery positive pole material lithium iron phosphate material fully greater than 99.0%; The electric conductivity height has greatly improved the chemical property of ferrous phosphate salt matrix material, and the electric conductivity of iron lithium phosphate has been improved 5 orders of magnitude; Not only cost is low for it, the operational path simple controllable, and also productive rate is fit to commercial scale production greater than 95%.Simultaneously, successfully metal-doped notion is incorporated in the middle of the raw-material modification, its product can be widely used in pottery, glass, and sensitive materialss etc. especially can satisfy the requirement of suitability for industrialized production phosphoric acid molysite positive electrode material to source of iron.
Description of drawings:
Fig. 1 is the crystallogram of the Ferrox of the present invention's preparation, adopts CuK α target emanation, λ=0.15416nm;
Fig. 2 is the Electronic Speculum SEM figure of the Ferrox of the present invention's preparation;
Fig. 3 is the size distribution curve figure of the Ferrox of the present invention's preparation;
Fig. 4 schemes for the EDS that press the prepared Ferrox doped compound of embodiment 2;
Fig. 5 schemes for the EDS that press the prepared Ferrox doped compound of embodiment 3;
Fig. 6 is the chemical property figure (voltage range 2.0V～4.0V, discharge-rate 0.1C do negative pole with the lithium sheet) that does the LiFePO 4 of lithium electricity raw material preparing by embodiment 2 prepared Ferrox doped compounds.
Embodiment
Embodiment 1.Get 27.9g technical grade ferrous sulfate, it is dissolved in 200ml concentration is in 50% the dilute sulphuric acid, slowly adds iron filings 10g in solution, stir, 45 ℃ of control reaction temperature, behind the suction filtration copperas solution.11.1g oxalic acid is dissolved in the 20ml distilled water, be heated with stirring to 45 the degree, treat that oxalic acid dissolves fully after, behind the suction filtration oxalic acid solution.Then the speed of copperas solution with 0.1L/min is joined in the oxalic acid solution, temperature of reaction is 65 degree, behind the insulated and stirred 45min, and static 10～30min.Mother liquor is separated, wash twice after drying with deionized water and obtain faint yellow Ferrox powder.Its size-grade distribution and chemical property are seen Fig. 1, Fig. 2, Fig. 3.
Embodiment 2.Get 27.9g technical grade ferrous sulfate, it is dissolved in 200ml concentration is in 50% the dilute sulphuric acid, slowly in solution, add iron filings 10g, stir, 50 ℃ of control reaction temperature, add the single nickel salt (chemical pure) of 1g behind the suction filtration in copperas solution, stirring makes its dissolving make the copperas solution that contains the single nickel salt composition.5.55g oxalic acid and 6.26g ammonium oxalate are dissolved in the 20ml distilled water, be heated with stirring to 60 the degree, treat that oxalic acid and ammonium oxalate dissolve fully after, suction filtration gets oxalic acid and ammonium oxalate mixing solutions.The copperas solution that will contain the single nickel salt composition then joins in oxalic acid and the ammonium oxalate solution with the speed of 0.2L/min, and temperature of reaction is 60 degree, behind the insulated and stirred 60min, and static 10～30min.Mother liquor is separated, wash the Ferrox composite powder (seeing Fig. 4,6) that twice after drying obtains faint yellow doping nickel ion with deionized water.
Embodiment 3.Get 41.9g technical grade ferrous sulfate, it is dissolved in 300ml concentration is in 50% the dilute sulphuric acid, slowly in solution, add iron filings 15g, stir, 50 ℃ of control reaction temperature, add copper sulfate and the 0.5g sal epsom (chemical pure) of 0.5g behind the suction filtration in copperas solution, stirring makes its dissolving make the copperas solution that contains copper sulfate and sal epsom.11.1g oxalic acid is dissolved in the 20ml distilled water, be heated with stirring to 65 the degree, treat that oxalic acid dissolves fully after, suction filtration gets oxalic acid solution.The copperas solution that will contain copper sulfate and sal epsom then joins in the oxalic acid solution with the speed of 0.2L/min, and temperature of reaction is 50 ℃, behind the insulated and stirred 60min, and static 10～30min.Mother liquor is separated, wash the Ferrox composite powder (see figure 5) that twice after drying obtains faint yellow copper doped magnesium ion with deionized water.
Claims (3)
1, a kind of preparation method of Ferrox is characterized in that its method steps:
A) ferrous sulfate is placed dilute sulphuric acid, add iron filings, stir, 45 ℃ of control reaction temperature get copperas solution behind the suction filtration;
B) with oxalic acid or/and ammonium oxalate is dissolved in the distilled water, stirring heating is treated oxalic acid or/and after ammonium oxalate dissolved fully, suction filtration gets oxalic acid or/and the ammonium oxalate mixing solutions;
C) slowly copperas solution is joined in oxalic acid solution or oxalic acid and the ammonium oxalate mixing solutions, temperature of reaction is 0-65 ℃, behind the insulated and stirred 45min, and static 10～30min; After mother liquor separates, obtain the Ferrox powder through washing and drying.
2, the preparation method of a kind of Ferrox according to claim 1 is characterized in that: in the described copperas solution, be added with additive.
3, the preparation method of a kind of Ferrox according to claim 2 is characterized in that: described additive is one or both in single nickel salt, copper sulfate, the sal epsom.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811952A (en) * | 2010-03-31 | 2010-08-25 | 朱辰 | Production method of doped ferrous oxalate |
| CN102336646A (en) * | 2010-07-21 | 2012-02-01 | 宁波杉杉新材料科技有限公司 | Preparation method of ferrous oxalate |
| CN102675083A (en) * | 2011-03-18 | 2012-09-19 | 上海杉杉科技有限公司 | Preparation method of ferrous oxalate |
| CN102942471A (en) * | 2012-11-22 | 2013-02-27 | 山东默锐科技有限公司 | Preparation method of oxalate |
| CN101717331B (en) * | 2009-11-26 | 2013-04-17 | 攀钢集团钢铁钒钛股份有限公司 | Method for preparing iron oxalate |
| CN103408417A (en) * | 2013-07-18 | 2013-11-27 | 合肥亚龙化工有限责任公司 | Preparation method for nanoscale ferrous oxalate |
| CN103601634A (en) * | 2013-10-23 | 2014-02-26 | 宁波晟腾新材料有限公司 | Preparation method for ultrafine impurity-doped ferrous oxalate special for lithium iron phosphate |
| CN105218347A (en) * | 2015-09-08 | 2016-01-06 | 厦门紫金矿冶技术有限公司 | A kind of copper raffinate prepares the method for high-purity oxalic acid ferrous iron |
| CN105237425A (en) * | 2015-11-12 | 2016-01-13 | 中南大学 | Method for mother solution pretreatment and cyclic utilization in chain type ferrous glycine complex synthesis |
| CN106356532A (en) * | 2016-10-19 | 2017-01-25 | 山东三秋新能源科技有限公司 | Production technique for nanometer anhydrous ferrous oxalate |
| WO2022204752A1 (en) * | 2021-04-01 | 2022-10-06 | Vspc Pty Ltd. | Production of iron (ii) oxalate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100488937C (en) * | 2006-10-28 | 2009-05-20 | 李传友 | Production method of ferrous oxalate special for ferrous lithium phosphate |
-
2008
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717331B (en) * | 2009-11-26 | 2013-04-17 | 攀钢集团钢铁钒钛股份有限公司 | Method for preparing iron oxalate |
| CN101811952A (en) * | 2010-03-31 | 2010-08-25 | 朱辰 | Production method of doped ferrous oxalate |
| CN102336646A (en) * | 2010-07-21 | 2012-02-01 | 宁波杉杉新材料科技有限公司 | Preparation method of ferrous oxalate |
| CN102675083A (en) * | 2011-03-18 | 2012-09-19 | 上海杉杉科技有限公司 | Preparation method of ferrous oxalate |
| CN102942471B (en) * | 2012-11-22 | 2015-08-26 | 山东默锐科技有限公司 | Prepare the method for oxalate |
| CN102942471A (en) * | 2012-11-22 | 2013-02-27 | 山东默锐科技有限公司 | Preparation method of oxalate |
| CN103408417A (en) * | 2013-07-18 | 2013-11-27 | 合肥亚龙化工有限责任公司 | Preparation method for nanoscale ferrous oxalate |
| CN103601634A (en) * | 2013-10-23 | 2014-02-26 | 宁波晟腾新材料有限公司 | Preparation method for ultrafine impurity-doped ferrous oxalate special for lithium iron phosphate |
| CN103601634B (en) * | 2013-10-23 | 2015-06-17 | 宁波晟腾新材料有限公司 | Preparation method for ultrafine impurity-doped ferrous oxalate special for lithium iron phosphate |
| CN105218347A (en) * | 2015-09-08 | 2016-01-06 | 厦门紫金矿冶技术有限公司 | A kind of copper raffinate prepares the method for high-purity oxalic acid ferrous iron |
| CN105237425A (en) * | 2015-11-12 | 2016-01-13 | 中南大学 | Method for mother solution pretreatment and cyclic utilization in chain type ferrous glycine complex synthesis |
| CN105237425B (en) * | 2015-11-12 | 2017-12-01 | 中南大学 | Mother liquor pretreatment and circulation utilization method in a kind of chain type complex of ferrous glycine synthesis |
| CN106356532A (en) * | 2016-10-19 | 2017-01-25 | 山东三秋新能源科技有限公司 | Production technique for nanometer anhydrous ferrous oxalate |
| CN106356532B (en) * | 2016-10-19 | 2018-09-28 | 山东三秋新能源科技有限公司 | A kind of production technology of nanoscale anhydrous oxalic acid ferrous iron |
| WO2022204752A1 (en) * | 2021-04-01 | 2022-10-06 | Vspc Pty Ltd. | Production of iron (ii) oxalate |
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| CN101386575B (en) | 2012-06-20 |
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Owner name: HEFEI GUOXUAN HIGH-TECH POWER ENERGY CO., LTD. Free format text: FORMER NAME: HEFEI GUOXUAN HIGH-TECH POWER ENERGY CO., LTD. |
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