CN101386575B - Preparation method of ferrous oxalate - Google Patents
Preparation method of ferrous oxalate Download PDFInfo
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- CN101386575B CN101386575B CN200810124252XA CN200810124252A CN101386575B CN 101386575 B CN101386575 B CN 101386575B CN 200810124252X A CN200810124252X A CN 200810124252XA CN 200810124252 A CN200810124252 A CN 200810124252A CN 101386575 B CN101386575 B CN 101386575B
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- oxalic acid
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- ferrous
- ammonium oxalate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229940062993 ferrous oxalate Drugs 0.000 title abstract description 6
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 title abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 81
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 22
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000000967 suction filtration Methods 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 8
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 19
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 6
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 abstract description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 3
- 229940116007 ferrous phosphate Drugs 0.000 abstract description 3
- 229910000155 iron(II) phosphate Inorganic materials 0.000 abstract description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 3
- 239000000243 solution Substances 0.000 abstract 3
- 239000012153 distilled water Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000010413 mother solution Substances 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
A preparation method of ferrous oxalate, belonging to the technical field of powder material preparation. The preparation method of the ferrous oxalate is high in purity, controllable in granularity, uniform in particles and high in conductivity. The technical key points are as follows: putting ferrous sulfate into dilute sulfuric acid, adding scrap iron, stirring, and performing suction filtration to obtain a ferrous sulfate solution; dissolving oxalic acid or/and ammonium oxalate in distilled water, stirring and heating, and performing suction filtration to obtain a mixed solution of oxalic acid or/and ammonium oxalate after dissolving; slowly adding the ferrous sulfate solution into the oxalic acid solution, keeping the temperature and stirring, standing, separating the mother solution, washing and drying to obtain ferrous oxalate powder. The ferrous oxalate prepared by the preparation method has the advantages that the particle size of the powder with the particle size of 0.5-80 mu m is completely controllable, the product purity is more than 99.0 percent, the electric conductivity is high, the electrochemical performance of the ferrous phosphate composite material is greatly improved, and the electric conductivity of the 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 products.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, and particularly crystal formation is unstable and not single, is 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 merely 1/3rd of its real density, 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 through adding easy conductive agent (like 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 guarantee the uniformity coefficient in the 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, it 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, and in copperas solution, add one or both additives in single nickel salt, copper sulfate, the sal epsom behind the suction filtration;
B) with oxalic acid or/and ammonium oxalate is dissolved in the zero(ppm) water, stirring heating is treated oxalic acid or/and after ammonium oxalate dissolved fully, suction filtration got oxalic acid solution or ammonium oxalate solution or oxalic acid and ammonium oxalate mixing solutions;
C) slowly copperas solution is joined in oxalic acid solution or ammonium oxalate 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.
Its technique effect is: the present invention combines the characteristics of ferrousphosphate lithium material; Waste iron filing in the employing industry is as raw material; And particle diameter is the powder of 0.5 μ m～80 μ m in can preparing according to different reaction conditions; Granularity is controlled fully, and product purity satisfies the source of iron requirement of lithium battery positive pole material lithium iron phosphate material fully greater than 99.0%; Electric conductivity is high, has greatly improved the chemical property of ferrous phosphate salt matrix material, and the electric conductivity of iron lithium phosphate has been improved 5 one magnitude; Not only cost is low for it, the operational path simple controllable, and also productive rate is fit to commercial scale prodn 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.
Fig. 1 is the crystallogram of the Ferrox of the present invention's preparation, adopts CuK α target emanation, λ=0.15416nm;
Description of drawings:
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 in solution, adds iron filings 10g, stir, 45 ℃ of control reaction temperature, behind the suction filtration copperas solution.11.1g oxalic acid is dissolved in the 20ml zero(ppm) 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; In copperas solution, add the single nickel salt (CP) of 1g behind the suction filtration, 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 zero(ppm) 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; In copperas solution, add copper sulfate and the 0.5g sal epsom (CP) of 0.5g behind the suction filtration, stirring makes its dissolving make the copperas solution that contains copper sulfate and sal epsom.11.1g oxalic acid is dissolved in the 20ml zero(ppm) 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 mg ion with deionized water.
Claims (1)
1. the preparation method of a 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 and in copperas solution, add one or both additives in single nickel salt, copper sulfate, the sal epsom behind the suction filtration;
B) with oxalic acid or/and ammonium oxalate is dissolved in the zero(ppm) water, stirring heating is treated oxalic acid or/and after ammonium oxalate dissolved fully, suction filtration got oxalic acid solution or ammonium oxalate solution or oxalic acid and ammonium oxalate mixing solutions;
C) slowly copperas solution is joined in oxalic acid solution or ammonium oxalate 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.
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| CN200810124252XA CN101386575B (en) | 2008-07-04 | 2008-07-04 | Preparation method of ferrous oxalate |
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Families Citing this family (11)
| 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 |
| CN102336646B (en) * | 2010-07-21 | 2016-01-13 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of Ferrox |
| 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 |
| 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 |
| 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 |
| CN105218347B (en) * | 2015-09-08 | 2017-06-13 | 厦门紫金矿冶技术有限公司 | A kind of method that copper raffinate prepares ferrous oxalate |
| 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 |
| 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 |
| CN117355498A (en) * | 2021-04-01 | 2024-01-05 | Vspc私人有限公司 | Production of iron (II) oxalate |
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| CN1948259A (en) * | 2006-10-28 | 2007-04-18 | 李传友 | Production method of ferrous oxalate special for ferrous lithium phosphate |
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