CN102051630A - Method for preparing superfine iron phosphate through electrolytic method - Google Patents
Method for preparing superfine iron phosphate through electrolytic method Download PDFInfo
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- CN102051630A CN102051630A CN 201010605952 CN201010605952A CN102051630A CN 102051630 A CN102051630 A CN 102051630A CN 201010605952 CN201010605952 CN 201010605952 CN 201010605952 A CN201010605952 A CN 201010605952A CN 102051630 A CN102051630 A CN 102051630A
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 55
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 19
- 229940116007 ferrous phosphate Drugs 0.000 claims abstract description 19
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims abstract description 19
- 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 claims abstract description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- 229910000640 Fe alloy Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- 239000010439 graphite Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 6
- 239000000956 alloy Substances 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000003792 electrolyte Substances 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 0.000 claims abstract 2
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000008151 electrolyte solution Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 239000005955 Ferric phosphate Substances 0.000 claims description 5
- 229940032958 ferric phosphate Drugs 0.000 claims description 5
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 4
- 235000019800 disodium phosphate Nutrition 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 3
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 230000001143 conditioned effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- -1 water-soluble hardly Substances 0.000 description 1
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a method for preparing superfine iron phosphate through an electrolytic method. The method comprises the following steps of: regulating the pH of electrolyte to 1-10 by taking a phosphoric acid or an aqueous phosphate solution as the electrolyte, iron or an iron-containing alloy as an anode and a graphite rod, copper, iron or an iron alloy as a cathode and adopting the current density of 200-5000 A/m<2>; controlling electrolysis temperature between 10 DEG C and 90 DEG C; carrying out DC or AC electrolysis to synthesize ferrous phosphate; adding an oxidizer to oxidize into iron phosphate; and filtering, washing and drying sediments to prepare superfine iron phosphate powder. The invention sufficiently utilizes the low-cost iron or iron alloy as an iron source, creatively prepares the iron phosphate by adopting the electrolytic method and has the advantages of safe and simple synthesis method, low requirement for technical equipment, easy operation, low cost, higher synthesis efficiency, finer product granule, easy industrialization realization and better social and economic benefit.
Description
(1) technical field
The present invention relates to the method that a kind of electrolytic process prepares ultra-fine tertiary iron phosphate.
(2) background technology
Tertiary iron phosphate is faint yellow or the ivory buff powder, tap density: 1.13～1.59g/cm
3, loose density 0.75～0.97g/cm
3, be dissolved in hydrochloric acid during heating, be insoluble in other acid, water-soluble hardly, acetic acid, alcohol exist with the vivianite form at occurring in nature.
At present, lithium ion battery market is fast-developing, and tertiary iron phosphate is one of raw material of preparation lithium ion battery anode material lithium iron phosphate, and the tertiary iron phosphate presoma of excellent property has decisive role to the performance of iron lithium phosphate.
The synthetic method of tertiary iron phosphate has a variety of, as mixing with DAP solution with ferrous sulfate, with the reaction solution ultrasonic radiation, obtain tertiary iron phosphate product (Hirokazu Okawa*, Junpei Yabuki, Youhei Kawamura, Ichiro Arise, Mineo Sato.Synthesis of FePO
4Cathode material for lithium ion batteries by a sonochemical method.J.materials research bulletin.2008), this method shortcoming is to production unit requirement height, energy consumption is big, and the cost height is not suitable for scale operation.
Use Iron sulfuret for another example, dilute phosphoric acid, sodium chlorate and sodium hydroxide prepared in reaction tertiary iron phosphate, reaction equation: 6FeSO
4+ 6H
3PO
4+ NaClO
3+ 12NaOH → 6FePO
42H
2O+6Na
2SO
4+ NaCl+3H
2O (Ma Guangcheng, Ding Shiwen, Li Weiping *. the synthetic and performance study .J. coatings industry .1998.12 of tertiary iron phosphate), the shortcoming of this method is the step complexity, raw material consumption is big, the cost height.
In addition, also useful sodium phosphate and ferric sulfate direct reaction, the pH value less than 2 condition under synthetic tertiary iron phosphate, this method reaction not exclusively, impurity is mutually more.
(3) summary of the invention
The object of the invention provides the method that a kind of electrolytic process prepares ultra-fine tertiary iron phosphate, and this method is simple to operate, with low cost, combined coefficient is high, product particle is thinner, is easy to realize industrialization.
The technical solution used in the present invention is:
A kind of electrolytic process prepares the method for ultra-fine tertiary iron phosphate, described method is in the plate and frame electrolyzer, is electrolytic solution with phosphoric acid or water-soluble aqueous phosphatic, is anode with iron or iron containing alloy, graphite rod, copper, iron or iron alloy are negative electrode, adopt 200～5000A/m
2Current density, regulate electrolytic solution pH to 1～10, between 10～90 ℃ of the control electrolysis temperatures, direct current or alternating current electrolysis synthesize ferrous phosphate, and reaction finishes, and night is answered in negate, add oxygenant, and ferrous phosphate is oxidized to tertiary iron phosphate, and cross that leaching precipitates, washes with water, drying, make ultra-fine ferric phosphate powder body (FePO
42H
2O).
It is one of following that the anode of described iron or iron alloy is preferably: pure iron, steel or iron alloy, described iron alloy can be any iron containing alloys.
Described electrolytic solution is recommended as the phosphatic aqueous solution of following one or more arbitrary proportions: phosphoric acid, tertiary sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate, Tripotassium phosphate, potassium primary phosphate, triammonium phosphate, primary ammonium phosphate or Secondary ammonium phosphate.
Described concentration of electrolyte is recommended as the phosphoric acid or the phosphatic aqueous solution of 0.01～8mol/L of 0.01～8mol/L.
The present invention regulates electrolytic solution, and to regulate the solution of pH be one of following: phosphate aqueous solution, aqueous sulfuric acid, aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous hydrochloric acid or ammoniacal liquor.
Oxidation of the present invention is to add oxygenant ferrous phosphate is oxidized to tertiary iron phosphate, and the add-on of oxygenant is 1: 1.5～2.5 with the mol ratio of the amount of electrons that reaction is passed through.
The oxygenant that the present invention recommends is one of following: oxygen, hydrogen peroxide or potassium permanganate; Usually used hydrogen peroxide is that concentration is 30% aqueous hydrogen peroxide solution, and used potassium permanganate is that concentration is 5% potassium permanganate solution.
Described plate and frame electrolyzer is no barrier film or diaphragm type sheet frame electrolyzer, and described diaphragm type sheet frame electrolyzer is preferably single stage type, multiple level formula or the placed in-line sheet frame electrolyzer of single stage type.
That obtain by electrolytic process of the present invention is a kind of ultra-fine tertiary iron phosphate (FePO
42H
2O), the preparation method that concrete the present invention recommends is: in multiple level formula sheet frame electrolyzer, the phosphoric acid of adding 0.5～6mol/L or the phosphatic aqueous solution of 0.5～6mol/L are anode as electrolytic solution with iron or iron containing alloy, graphite rod, copper, iron or iron alloy are negative electrode, adopt 800～3500A/m
2Current density, with electrolytic solution pH regulator to 2～7, between 20～50 ℃ of the control electrolysis temperatures, direct current or alternating current electrolysis 1～5h, synthetic ferrous phosphate, electrolytic reaction finishes, night is answered in negate, add oxygenant ferrous phosphate is oxidized to tertiary iron phosphate, cross that leaching precipitates, washes with water, 50～100 ℃ of vacuum-drying to moisture are less than 500ppm, make ultra-fine ferric phosphate powder body; Described oxygenant is one of following: oxygen, 30% hydrogen peroxide or 5% potassium permanganate solution; The add-on of oxygenant is 1: 1.5～2.5 with the mol ratio of the amount of electrons that reaction is passed through; Described drying temperature is preferably 60～80 ℃.
Reaction principle:
Anodal: 3Fe-6e
-+ 2PO
4 3-→ Fe
3(PO
4)
2
Negative pole: 2H
++ 2e
-→ H
2↑
Oxidation: Fe
3(PO
4)
2+ oxygenant → FePO
4
In the process of the synthetic ferrous phosphate of feeding direct current of the present invention or alternating current electrolysis, it is synthetic just to have ferrous phosphate when feeding electricity, reaction times requires and can freely control according to output, at any time can finish, after reaction finishes,, calculate the amount of required oxygenant according to reacting the amount of electrons of passing through according to the conservation of electrons law, after oxygenant joins reaction solution, ferrous phosphate is oxidized to faint yellow tertiary iron phosphate precipitation in moment.
According to the conservation of electrons law, the consumption method of calculation of oxygenant are:
m＝I·t/2·e·NA·M·ω％
M is the quality of oxygenant, and I is a size of current, and t is an electrolysis time, and e is an electron charge, and NA is an avogado constant, and M is the molecular mass of oxygenant, and ω % is the mass percent of oxygenant.
The present invention compared with prior art, its beneficial effect is mainly reflected in:
The present invention makes full use of cheap iron or iron alloy as source of iron, creatively adopts electrolytic process to prepare tertiary iron phosphate, synthetic method is safe and simple, technical equipment require low, operation easily, with low cost, combined coefficient is higher, product is ultra-fine ferric phosphate powder body; Particle is thinner, is easy to realize industrialization, has the good social economic benefit.
(4) description of drawings
Fig. 1 is the electron scanning micrograph behind the embodiment of the invention 1 resultant product sintering.
Fig. 2 is the XRD figure behind the embodiment of the invention 1 resultant product sintering.
(5) specific implementation method
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
The particle size of common synthetic method gained tertiary iron phosphate is between 3～5 μ m, and by contrast, gained iron phosphate grains size of the present invention is between 30～80nm, and the obvious refinement of particle reaches nano level.
Embodiment 1
In 250mL plate and frame electrolyzer, adopting the pure iron electrode is anode, graphite rod is a negative electrode, area is 5cm * 5cm, 0.1mol/L trisodium phosphate aqueous solution 200mL be electrolytic solution, dilute phosphoric acid aqueous solution conditioned reaction liquid pH with 0.5mol/L is 5, and to the logical direct current electrolysis 1h of electrolyzer, current density is 200A/m
2The groove temperature is 10 ℃, after reaction finishes, with the 1.05mL30% hydrogen peroxide ferrous phosphate is oxidized to faint yellow tertiary iron phosphate precipitation, filter electrolytic solution,, will be deposited in the vacuum drying oven with the deionized water wash precipitation, temperature is 60 ℃, and to be dried to moisture content be 350ppm, obtains the ultra-fine tertiary iron phosphate (FePO of particle size between 30～80nm
42H
2O) 0.98g sees Fig. 1 with the electron-microscope scanning (SEM) of the ultra-fine tertiary iron phosphate of gained behind 650 ℃ of sintering, and X-ray diffraction (XRD) is seen Fig. 2.
Embodiment 2
In 250mL plate and frame electrolyzer, adopting the pure iron electrode is anode and negative electrode, area is 5cm * 5cm, the mixing solutions of 1mol/L potassium dihydrogen phosphate aqueous solution 150mL and 0.3mol/L tricresyl phosphate ammonia soln 50mL is an electrolytic solution, diluted hydrochloric acid aqueous solution conditioned reaction liquid pH with 0.5mol/L is 6, to electrolyzer indirect current electrolysis 1h, current density is 5000A/m
2The groove temperature is 50 ℃, after reaction finishes, speed with 5mL/s feeds pure oxygen 1h, and ferrous phosphate is oxidized to tertiary iron phosphate, filters electrolytic solution, precipitate with deionized water wash, to be deposited in the vacuum drying oven, 80 ℃ are dried to moisture content is 500ppm, obtains the ultra-fine tertiary iron phosphate (FePO of particle size between 30～80nm
42H
2O) 20.75g.
Embodiment 3
In 250mL plate and frame electrolyzer, the employing steel electrode is an anode, copper sheet is a negative electrode, area is 5cm * 5cm, 1.0mol/L Sodium phosphate dibasic aqueous solution 200mL be electrolytic solution, dilute sulfuric acid aqueous solution conditioned reaction liquid pH with 0.8mol/L is 1, and to the logical direct current electrolysis 2.5h of electrolyzer, current density is 2200A/m
2The groove temperature is 25 ℃, after reaction finishes, with the 29mL30% hydrogen peroxide ferrous phosphate is oxidized to tertiary iron phosphate, filter electrolytic solution,, will be deposited in the vacuum drying oven with the deionized water wash precipitation, 100 ℃ are dried to moisture content is 350ppm, obtains the ultra-fine tertiary iron phosphate (FePO of particle size between 30～80nm
42H
2O) 26.3g.
Embodiment 4
In 250mL plate and frame electrolyzer, the employing ferrotianium is an anode, copper sheet is a negative electrode, area is 5cm * 5cm, 0.25mol/L DAP aqueous solution 30mL, 2.2mol/L Sodium phosphate dibasic aqueous solution 50mL, the mixing solutions of 3mol/L potassium dihydrogen phosphate aqueous solution 120mL is an electrolytic solution, aqueous sodium hydroxide solution conditioned reaction liquid pH with 0.6mol/L is 10, and to the logical direct current electrolysis 3h of electrolyzer, current density is 1000A/m
2The groove temperature is 60 ℃, after reaction finishes, with the 16mL30% hydrogen peroxide ferrous phosphate is oxidized to tertiary iron phosphate, filter electrolytic solution,, will be deposited in the vacuum drying oven with the deionized water wash precipitation, temperature is 60 ℃, and to be dried to moisture content be 200ppm, obtains particle size ultra-fine tertiary iron phosphate (FePO between 30～80nm
42H
2O) 14.26g.
Embodiment 5
In 250mL plate and frame electrolyzer, adopting ferrotianium is anode and negative electrode, area is 5cm * 5cm, the biphosphate ammonia soln 200mL of 1mol/L is an electrolytic solution, diluted hydrochloric acid aqueous solution conditioned reaction liquid pH with 0.5mol/L is 4.2, to electrolyzer indirect current electrolysis 5h, current density is 2410A/m
2The groove temperature is 90 ℃, after reaction finishes, speed with 5mL/s feeds pure oxygen 2h, and ferrous phosphate is oxidized to tertiary iron phosphate, filters electrolytic solution, precipitate with deionized water wash, to be deposited in the vacuum drying oven, 100 ℃ are dried to moisture content 200ppm, obtain the ultra-fine tertiary iron phosphate (FePO of particle size between 30～80nm
42H
2O) 45.4g.
Embodiment 6
In 250mL plate and frame electrolyzer, the employing pure iron is an anode, graphite is negative electrode, area is 5cm * 5cm, 6mol/L biphosphate ammonia soln 20mL, 2mol/L trisodium phosphate aqueous solution 130mL, 0.8mol/L potassium dihydrogen phosphate aqueous solution 10mL, 1.2mol/L the mixing solutions of Tripotassium phosphate aqueous solution 40mL is an electrolytic solution, is 8 with the dilute phosphoric acid aqueous solution of 0.6mol/L and the diluted hydrochloric acid aqueous solution of 0.5mol/L with 1: 1 mixing acid conditioned reaction liquid pH of volume ratio, to the logical direct current electrolysis 1h of electrolyzer, current density is 2500A/m
2The groove temperature is 60 ℃, after reaction finishes, (potassium permanganate quality 185g) is oxidized to tertiary iron phosphate with ferrous phosphate with mass concentration 5% potassium permanganate solution, filter electrolytic solution,, will be deposited in the vacuum drying oven with the deionized water wash precipitation, temperature is 70 ℃ and is dried to moisture content 200ppm, obtains the ultra-fine tertiary iron phosphate (FePO of particle size between 30～80nm
42H
2O) 11.1g.
Claims (10)
1. an electrolytic process prepares the method for ultra-fine tertiary iron phosphate, it is characterized in that described method is in the plate and frame electrolyzer, is electrolytic solution with phosphoric acid or water-soluble aqueous phosphatic, is anode with iron or iron containing alloy, with graphite rod, copper, iron or iron alloy is negative electrode, adopts 200～5000A/m
2Current density, regulate electrolytic solution pH to 1～10, between 10～90 ℃ of the control electrolysis temperatures, direct current or alternating current electrolysis synthesize ferrous phosphate, and reaction finishes, and extracts reaction solution, add oxygenant, and ferrous phosphate is oxidized to tertiary iron phosphate, and cross that leaching precipitates, washes with water, drying, make ultra-fine ferric phosphate powder body.
2. electrolytic process as claimed in claim 1 prepares the method for ultra-fine tertiary iron phosphate, it is characterized in that described anode is one of following: pure iron, steel or iron alloy.
3. electrolytic process as claimed in claim 1 prepares the method for ultra-fine tertiary iron phosphate, it is characterized in that described electrolytic solution is the phosphatic aqueous solution of following one or more arbitrary proportions: phosphoric acid, tertiary sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate, Tripotassium phosphate, potassium primary phosphate, triammonium phosphate, primary ammonium phosphate or Secondary ammonium phosphate.
4. electrolytic process as claimed in claim 1 prepares the method for ultra-fine tertiary iron phosphate, it is characterized in that described concentration of electrolyte is the phosphoric acid or the phosphatic aqueous solution of 0.01～8mol/L of 0.01～8mol/L.
5. electrolytic process as claimed in claim 1 prepares the method for ultra-fine tertiary iron phosphate, and the solution that it is characterized in that regulating electrolytic solution pH is one of following: phosphate aqueous solution, aqueous sulfuric acid, aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous hydrochloric acid or ammoniacal liquor.
6. electrolytic process as claimed in claim 1 prepares the method for ultra-fine tertiary iron phosphate, it is characterized in that the add-on of described oxygenant and the mol ratio of reacting the amount of electrons of passing through are 1: 1.5～2.5.
7. electrolytic process as claimed in claim 1 prepares the method for ultra-fine tertiary iron phosphate, it is characterized in that described oxygenant is one of following: oxygen, hydrogen peroxide or potassium permanganate.
8. electrolytic process as claimed in claim 1 prepares the method for ultra-fine tertiary iron phosphate, it is characterized in that described current density is 800～3500A/m
2
9. electrolytic process as claimed in claim 1 prepares the method for ultra-fine tertiary iron phosphate, it is characterized in that described plate and frame electrolyzer is no barrier film or diaphragm type sheet frame electrolyzer, and described diaphragm type is single stage type, multiple level formula or the placed in-line sheet frame electrolyzer of single stage type.
10. electrolytic process as claimed in claim 1 prepares the method for ultra-fine tertiary iron phosphate, it is characterized in that described preparation method is: in multiple level formula sheet frame electrolyzer, the phosphoric acid of adding 0.5～6mol/L or the phosphatic aqueous solution of 0.5～6mol/L are as electrolytic solution, with iron or iron containing alloy is anode, with graphite rod, copper, iron or iron alloy is negative electrode, adopts 800～3500A/m
2Current density, with electrolytic solution pH regulator to 2～7,20～50 ℃ of control electrolysis temperatures, direct current or alternating current electrolysis 1～5h, synthetic ferrous phosphate, electrolysis finishes, extract reaction solution, add oxygenant ferrous phosphate is oxidized to tertiary iron phosphate, cross leaching and precipitate, wash with water, be less than 500ppm in 50～100 ℃ of vacuum-drying to moisture again, make ultra-fine ferric phosphate powder body; Described oxygenant is one of following: oxygen, 30% hydrogen peroxide or 5% potassium permanganate solution; The add-on of oxygenant is 1: 1.5～2.5 with the mol ratio of the amount of electrons that reaction is passed through.
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| CN103094569A (en) * | 2013-01-30 | 2013-05-08 | 芜湖华欣诺电化学科技有限公司 | Anode material-nanometer vanadium iron manganese lithium phosphate of lithium ion battery and preparation method of anode material |
| CN103556169A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Dandelion-shaped iron phosphate microspheres and preparation method thereof through electrochemical anode oxidation |
| CN109252181A (en) * | 2018-09-13 | 2019-01-22 | 湖南工程学院 | A kind of method of electrolytic preparation hexafluoro sodium ferrite |
| CN111663147A (en) * | 2020-05-11 | 2020-09-15 | 湖南雅城新材料有限公司 | Process for preparing iron phosphate by electrolytic method |
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| CN103094569A (en) * | 2013-01-30 | 2013-05-08 | 芜湖华欣诺电化学科技有限公司 | Anode material-nanometer vanadium iron manganese lithium phosphate of lithium ion battery and preparation method of anode material |
| CN103556169A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Dandelion-shaped iron phosphate microspheres and preparation method thereof through electrochemical anode oxidation |
| CN103556169B (en) * | 2013-11-15 | 2016-01-20 | 哈尔滨工业大学 | A kind of taraxacum shape tertiary iron phosphate micron ball and method for preparing electrochemical anodic oxidation thereof |
| CN109252181A (en) * | 2018-09-13 | 2019-01-22 | 湖南工程学院 | A kind of method of electrolytic preparation hexafluoro sodium ferrite |
| CN111663147B (en) * | 2020-05-11 | 2021-09-03 | 湖南雅城新材料有限公司 | Process for preparing iron phosphate by electrolytic method |
| CN111663147A (en) * | 2020-05-11 | 2020-09-15 | 湖南雅城新材料有限公司 | Process for preparing iron phosphate by electrolytic method |
| CN112938919A (en) * | 2021-01-27 | 2021-06-11 | 华中科技大学 | Method for treating waste etching liquid |
| CN112938919B (en) * | 2021-01-27 | 2022-07-15 | 华中科技大学 | Treatment method of waste etching liquid |
| CN113942986A (en) * | 2021-09-27 | 2022-01-18 | 荆门市格林美新材料有限公司 | Method for recovering nickel and iron from nickel-iron alloy |
| CN114517300A (en) * | 2022-02-17 | 2022-05-20 | 北京中矿科技集团有限公司 | Method for synthesizing water treatment agent by using sulfuric acid waste liquid |
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| CN114572953A (en) * | 2022-03-17 | 2022-06-03 | 广东光华科技股份有限公司 | Method for removing metal impurities in ferrous phosphate acidic solution and application |
| CN114572953B (en) * | 2022-03-17 | 2023-08-18 | 广东光华科技股份有限公司 | Method for removing metal impurities in ferrous phosphate acidic solution and application thereof |
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