CN102701178B - Preparation method of sulfur-doped barium iron phosphate - Google Patents
Preparation method of sulfur-doped barium iron phosphate Download PDFInfo
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- CN102701178B CN102701178B CN201210184497.8A CN201210184497A CN102701178B CN 102701178 B CN102701178 B CN 102701178B CN 201210184497 A CN201210184497 A CN 201210184497A CN 102701178 B CN102701178 B CN 102701178B
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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
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- 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 invention provides a preparation method of sulfur-doped barium iron phosphate with the chemical formula of Ba(FePO4)2; the preparation method takes barium source, iron source and phosphate radical source as raw materials, and meters according to the mole ratio of the chemical formula of Ba(FePO4)2; the doped element source is calculated according to the weight of the theoretically generated barium iron phosphate, and the added doped element is calculated within the weight percent range of 0.1-5%; and the preparation method comprises the steps of: mixing, and then carrying out high speed ball-milling for 15-20h in ethanol medium; drying at 105-120 DEG C to obtain precursor; putting the dried precursor into a high temperature furnace; and in nitrogen atmosphere, carrying out high-temperature calcination at 300-450 DEG C for 2-4h to obtain the product. The sulfur-doped barium iron phosphate can be mainly used as reducing agent, deoxidant and food preservative, is used for making electronic components and raw material of batteries, and can be used for smelting, alloy, glass production additive and the like; and the preparation method has the characteristics of being enough in raw materials, low in cost, environment-friendly, free from pollution and the like.
Description
Technical field
Sulfur doping barium iron phosphate of the present invention, belongs to a kind of novel material.
Background technology
At present, report and the record of barium iron phosphate compound is not yet found that there is.Through the retrieval of publication, the investigations such as the information of internet and books and periodicals, magazine, market, do not have to find the patent documentation identical with technical products of the present invention, have no and the report of technology of the present invention or product or sale yet.
Summary of the invention
The object of the invention is to: the preparation method proposing a kind of sulfur doping barium iron phosphate.
The preparation method of sulfur doping barium iron phosphate of the present invention, is characterized in that: its chemical formula is: Ba (FePO
4) 2, the raw material of its barium source, source of iron, phosphoric acid root, according to chemical formula Ba (FePO
4) 2 mol ratio metering; Doped element source, can generate the weighing scale of barium iron phosphate by theory, calculate by 0.1-5% scope weight percent, adds doped element; After mixing, in ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 DEG C of oven dry, obtaining presoma, being placed in High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere by drying the presoma obtained, through 300-450 DEG C of high-temperature calcination 2-4h, obtain sulfur doping barium iron phosphate product of the present invention;
Described barium source is one of barium carbonate, hydrated barta, bariumchloride, nitrate of baryta, barium oxide, barium sulphide; Source of iron is Ferrox, ferrous chloride, iron trichloride, ferric oxide etc.; Phosphoric acid root is: phosphoric acid, sodium phosphate salt, one of primary ammonium phosphate or Secondary ammonium phosphate;
Described doped element source: be elemental sulfur (Sulfur).
For making each mixing of materials evenly, described ethanol medium is acid, its acidic ethanol liquid, available art methods is carried out adjustment and is obtained, preferred organic acid-alcohol mixeding liquid is good, described organic acid is preferably formic acid or acetic acid, and described acidic ethanol liquid is preferably the alcohol mixeding liquid containing 1-5% formic acid or 1-5% acetic acid.
The present invention's beneficial effect compared with prior art: sulfur doping barium iron phosphate product of the present invention, is mainly used as reductive agent, reductor, food deoxidizing antistaling agent; As materials of electronic components or manufacture the raw materials for production of electronic component, manufacture the raw materials for production of cell positive material and battery thereof; For smelting, the additive of alloy, glass production; There is raw material very sufficient, at the bottom of production cost, the feature such as environment friendly and pollution-free; As cell positive material, the relative barium electropotential of its charge and discharge platform is about 3.6V, and initial discharge capacity is more than 187mAh/g, and after 100 charge and discharge cycles, capacity about decays about 0.2%; Specific storage and cyclical stability compared with prior art, are greatly improved, and production cost price is than more than the low decades of times of prior art.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but embodiments of the present invention are not limited thereto.
Embodiment 1
Sulfur doping barium iron phosphate preparation method of the present invention, is characterized in that: the raw material of its barium source, source of iron, phosphoric acid root, according to chemical formula Ba (FePO
4) 2 mol ratio metering; Doped element source, can generate the weighing scale of barium iron phosphate by theory, calculate by 0.1-5% scope weight percent, adds doped element; After mixing, in ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 DEG C of oven dry, obtaining presoma, being placed in High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere by drying the presoma obtained, through 300-450 DEG C of high-temperature calcination 2-4h, obtain sulfur doping barium iron phosphate product of the present invention;
Described barium source is one of barium carbonate, hydrated barta, bariumchloride, nitrate of baryta, barium oxide, barium sulphide; Source of iron is Ferrox, ferrous chloride, iron trichloride, ferric oxide etc.; Phosphoric acid root is: phosphoric acid, sodium phosphate salt, one of primary ammonium phosphate or Secondary ammonium phosphate;
Described doped element source: be elemental sulfur (Sulfur).
For making each mixing of materials evenly, described ethanol medium is acid, its acidic ethanol liquid, available art methods is carried out adjustment and is obtained, preferred organic acid-alcohol mixeding liquid is good, described organic acid is preferably formic acid or acetic acid, and described acidic ethanol liquid is preferably the alcohol mixeding liquid containing 1-5% formic acid or 1-5% acetic acid.
Embodiment 2
Select: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is raw material; According to chemical formula Ba (FePO
4) 2 mol ratio metering; Doped element source, can generate the weighing scale of barium iron phosphate by theory, by 1%(weight percent) calculate and add doped element sulphur, sulphur source is Sulfur, after mixing, in anhydrous ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 DEG C of oven dry, obtaining presoma, being placed in High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere by drying the presoma obtained, through 300-450 DEG C of high-temperature calcination 2-4h, obtain sulfur doping barium iron phosphate product of the present invention.
Embodiment 3
Select: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is raw material; According to chemical formula Ba (FePO
4) 2 mol ratio metering; Doped element source, can generate the weighing scale of barium iron phosphate by theory, by 0.5%(weight percent) calculate and add doped element sulphur, sulphur source is Sulfur, after mixing, in anhydrous ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 DEG C of oven dry, obtaining presoma, being placed in High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere by drying the presoma obtained, through 300-450 DEG C of high-temperature calcination 2-4h, obtain sulfur doping barium iron phosphate product of the present invention.
Embodiment 4
Select: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is raw material; According to chemical formula Ba (FePO
4) 2 mol ratio metering; Doped element source, can generate the weighing scale of barium iron phosphate by theory, by 0.1%(weight percent) calculate and add doped element sulphur, sulphur source is Sulfur, after mixing, in anhydrous ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 DEG C of oven dry, obtaining presoma, being placed in High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere by drying the presoma obtained, through 300-450 DEG C of high-temperature calcination 2-4h, obtain sulfur doping barium iron phosphate product of the present invention.
Embodiment 5
Select: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is raw material; According to chemical formula Ba (FePO
4) 2 mol ratio metering; Doped element source, can generate the weighing scale of barium iron phosphate by theory, by 4.5%(weight percent) calculate and add doped element sulphur, sulphur source is Sulfur, after mixing, in anhydrous ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 DEG C of oven dry, obtaining presoma, being placed in High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere by drying the presoma obtained, through 300-450 DEG C of high-temperature calcination 2-4h, obtain sulfur doping barium iron phosphate product of the present invention.
Embodiment 6
Select: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is raw material; According to chemical formula Ba (FePO
4) 2 mol ratio metering; Doped element source, can generate the weighing scale of barium iron phosphate by theory, by 3%(weight percent) calculate and add doped element sulphur, sulphur source is Sulfur, after mixing, in anhydrous ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 DEG C of oven dry, obtaining presoma, being placed in High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere by drying the presoma obtained, through 300-450 DEG C of high-temperature calcination 2-4h, obtain sulfur doping barium iron phosphate product of the present invention.
Embodiment 7
Select: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is raw material; According to chemical formula Ba (FePO
4) 2 mol ratio metering; Doped element source, can generate the weighing scale of barium iron phosphate by theory, by 1.5%(weight percent) calculate and add doped element sulphur, sulphur source is Sulfur, after mixing, in ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 DEG C of oven dry, obtaining presoma, being placed in High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere by drying the presoma obtained, through 300-450 DEG C of high-temperature calcination 2-4h, obtain sulfur doping barium iron phosphate product of the present invention.
Embodiment 8
Select: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is raw material; According to chemical formula Ba (FePO
4) 2 mol ratio metering; Doped element source, can generate the weighing scale of barium iron phosphate by theory, by 0.6%(weight percent) calculate and add doped element sulphur, sulphur source is Sulfur, after mixing, in ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 DEG C of oven dry, obtaining presoma, being placed in High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere by drying the presoma obtained, through 300-450 DEG C of high-temperature calcination 2-4h, obtain sulfur doping barium iron phosphate product of the present invention.
Embodiment 9
Select: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is raw material; According to chemical formula Ba (FePO
4) 2 mol ratio metering; Doped element source, can generate the weighing scale of barium iron phosphate by theory, by 2%(weight percent) calculate and add doped element sulphur, sulphur source is Sulfur, after mixing, in the alcohol mixeding liquid medium containing 1-5% acetic acid, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 DEG C of oven dry, obtaining presoma, being placed in High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere by drying the presoma obtained, through 300-450 DEG C of high-temperature calcination 2-4h, obtain sulfur doping barium iron phosphate product of the present invention.
Embodiment 10
Select: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is raw material; According to chemical formula Ba (FePO
4) 2 mol ratio metering; Doped element source, can generate the weighing scale of barium iron phosphate by theory, by 1%(weight percent) calculate and add doped element sulphur, sulphur source is Sulfur, after mixing, in the alcohol mixeding liquid medium containing 1-5% formic acid, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 DEG C of oven dry, obtaining presoma, being placed in High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere by drying the presoma obtained, through 300-450 DEG C of high-temperature calcination 2-4h, obtain sulfur doping barium iron phosphate product of the present invention.
Embodiment 11
Select: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is raw material; According to chemical formula Ba (FePO
4) 2 mol ratio metering; Doped element source, can generate the weighing scale of barium iron phosphate by theory, by 5%(weight percent) calculate and add dopant elements sulphur, sulphur source is Sulfur, after mixing, in the alcohol mixeding liquid medium containing 1-5% formic acid, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 DEG C of oven dry, obtaining presoma, being placed in High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere by drying the presoma obtained, through 300-450 DEG C of high-temperature calcination 2-4h, obtain sulfur doping barium iron phosphate product of the present invention.
Embodiment 12
Select: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is raw material; According to chemical formula Ba (FePO
4) 2 mol ratio metering; Doped element source, can generate the weighing scale of barium iron phosphate by theory, by 0.3%(weight percent) calculate and add doped element sulphur, sulphur source is Sulfur, after mixing, in the alcohol mixeding liquid medium containing 1-5% formic acid, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 DEG C of oven dry, obtaining presoma, being placed in High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere by drying the presoma obtained, through 300-450 DEG C of high-temperature calcination 2-4h, obtain sulfur doping barium iron phosphate product of the present invention.
Sulfur doping barium iron phosphate product of the present invention, is mainly used as reductive agent, reductor, food deoxidizing antistaling agent; The raw materials for production of materials of electronic components or manufacture electronic component, manufacture the raw materials for production of cell positive material and battery thereof; For smelting, the additive of alloy, glass production.
Sulfur doping barium iron phosphate product of the present invention its there is extremely strong reducing property, it contacts with air, gets final product oxidation by air, becomes brown or yellow from dark color; Can be widely used in reduction, deoxidation industry production; Because it is nontoxic, water insoluble and organic solvent, can be general for food deoxidizing antistaling agent (non-food product additive), and have deixis.
As cell positive material, can be used as battery material, be mainly used as cell positive material; Also can be used as materials of electronic components.As cell positive material, adopt the testing apparatus of prior art and the testing method of prior art, to the sulfur doping barium iron phosphate product of above embodiment 1-12, test respectively: the relative barium electropotential of its charge and discharge platform is about 3.6V, initial discharge capacity is more than 187mAh/g, and after 100 charge and discharge cycles, capacity about decays about 0.2%; Specific storage and cyclical stability compared with prior art, are greatly improved, and production cost price is than more than the low decades of times of prior art.
For smelting, the additive of alloy, glass production; For smelting, alloy production additive, can improved products performance; For the additive of glass production, required special glass product can be obtained.
Claims (3)
1. a preparation method for sulfur doping barium iron phosphate, is characterized in that: its chemical formula is: Ba (FePO
4) 2, the raw material of its barium source, source of iron, phosphoric acid root, according to chemical formula Ba (FePO
4) 2 mol ratio metering; Doped element source, can generate the weighing scale of barium iron phosphate by theory, calculate by 0.1-5% scope weight percent, adds doped element; After mixing, in ethanol medium, rotating speed 200-800r/min high speed ball milling 15-20h, with 105-120 DEG C of oven dry, obtaining presoma, being placed in High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere by drying the presoma obtained, through 300-450 DEG C of high-temperature calcination 2-4h, obtain sulfur doping barium iron phosphate product of the present invention;
Described barium source is one of barium carbonate, hydrated barta, bariumchloride, nitrate of baryta, barium oxide, barium sulphide; Source of iron is Ferrox, ferrous chloride, iron trichloride, ferric oxide etc.; Phosphoric acid root is: phosphoric acid, sodium phosphate salt, one of primary ammonium phosphate or Secondary ammonium phosphate;
Described doped element source: be elemental sulfur.
2. the preparation method of sulfur doping barium iron phosphate according to claim 1, is characterized in that: described ethanol medium is acid.
3. the preparation method of sulfur doping barium iron phosphate according to claim 1, is characterized in that: described ethanol medium is the alcohol mixeding liquid containing 1-5% formic acid or 1-5% acetic acid.
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| CN1772604A (en) * | 2005-10-11 | 2006-05-17 | 清华大学 | Prepn process of oxygen place doped lithium ferric phosphate powder |
| CN1785823A (en) * | 2005-12-23 | 2006-06-14 | 清华大学 | Preparation method of phosphorus position partly substituted iron lithium phosphate powder |
| CN101339994A (en) * | 2008-09-01 | 2009-01-07 | 罗绍华 | Preparation of multi-position doped lithium iron phosphate positive electrode material and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1754275A (en) * | 2002-12-23 | 2006-03-29 | A123***公司 | High energy and power density electrochemical cells |
| CN1772604A (en) * | 2005-10-11 | 2006-05-17 | 清华大学 | Prepn process of oxygen place doped lithium ferric phosphate powder |
| CN1785823A (en) * | 2005-12-23 | 2006-06-14 | 清华大学 | Preparation method of phosphorus position partly substituted iron lithium phosphate powder |
| CN101339994A (en) * | 2008-09-01 | 2009-01-07 | 罗绍华 | Preparation of multi-position doped lithium iron phosphate positive electrode material and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Neutron powder diffraction study of the magnetic and crystal structures of SrFe2(PO4)2;Alexei A. Belilk etal;《Journal of Solid State Chmistry》;20080528;第2292页左栏第2段至第2293页右栏第4段 * |
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