CN102701178A - Preparation method of sulfur-doped barium iron phosphate - Google Patents

Preparation method of sulfur-doped barium iron phosphate Download PDF

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Publication number
CN102701178A
CN102701178A CN2012101844978A CN201210184497A CN102701178A CN 102701178 A CN102701178 A CN 102701178A CN 2012101844978 A CN2012101844978 A CN 2012101844978A CN 201210184497 A CN201210184497 A CN 201210184497A CN 102701178 A CN102701178 A CN 102701178A
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barium
source
iron phosphate
preparation
sulfur
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CN102701178B (en
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张健
吴润秀
王晶
张雅静
李�杰
李安平
李先兰
曾令城
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曾令城
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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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

The preparation method of sulfur doping tertiary iron phosphate barium
Technical field
Sulfur doping tertiary iron phosphate barium of the present invention belongs to a kind of novel material.
Background technology
At present, still find no the report and the record of ferric phosphate barium compound.Through the retrieval of publication, 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, do not see report or sale with technology of the present invention or product yet.
Summary of the invention
The objective of the invention is to: the preparation method who proposes a kind of sulfur doping tertiary iron phosphate barium.
The preparation method of sulfur doping tertiary iron phosphate barium 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 is according to chemical formula Ba (FePO 4) 2Mol ratio metering; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 0.1-5% scope weight percent, adds alloying element; After the mixing, in ethanol medium, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry; Obtain presoma, the presoma that oven dry is obtained places in the High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere; Through 300-450 ℃ of high-temperature calcination 2-4h, promptly get sulfur doping tertiary iron phosphate barium product of the present invention;
Said 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, red stone etc.; The phosphoric acid root is: phosphoric acid, sodium phosphate salt, one of primary ammonium phosphate or Secondary ammonium phosphate;
Said alloying element source: be elemental sulfur (Sulfur).
For making each mixing of materials more even; Said ethanol medium is a tart; Its acidic ethanol liquid, available art methods is regulated acquisition, and preferred organic acid-alcohol mixeding liquid is good; Said organic acid is preferably formic acid or acetate, and said acidic ethanol liquid is preferably the alcohol mixeding liquid that contains 1-5% formic acid or 1-5% acetate.
The present invention's beneficial effect compared with prior art: sulfur doping tertiary iron phosphate barium product of the present invention, mainly as reductive agent, reductor, food deoxidizing antistaling agent; Be used as the raw materials for production of raw materials for production, manufacturing cell positive material and the battery thereof of materials of electronic components or manufacturing electronic component; Be used to smelt, the additive of alloy, glass production; It is very sufficient to have raw material, at the bottom of the production cost, and characteristics 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 surpasses 187mAh/g, and capacity decays about 0.2% approximately after 100 charge and discharge cycles; Specific storage and cyclical stability compared with prior art are greatly improved, and the production cost price is lower more than tens of times than prior art.
Embodiment
Below in conjunction with embodiment the present invention is described further, but embodiment of the present invention is not limited thereto.
Embodiment 1
Sulfur doping tertiary iron phosphate barium preparation method of the present invention is characterized in that: the raw material of its barium source, source of iron, phosphoric acid root, and according to chemical formula Ba (FePO 4) 2Mol ratio metering; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, presses 0.1-5% scope weight percent and calculates, and adds alloying element; After the mixing, in ethanol medium, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the High Temperature Furnaces Heating Apparatus; In nitrogen atmosphere,, promptly get sulfur doping tertiary iron phosphate barium product of the present invention through 300-450 ℃ of high-temperature calcination 2-4h;
Said 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, red stone etc.; The phosphoric acid root is: phosphoric acid, sodium phosphate salt, one of primary ammonium phosphate or Secondary ammonium phosphate;
Said alloying element source: be elemental sulfur (Sulfur).
For making each mixing of materials more even; Said ethanol medium is a tart; Its acidic ethanol liquid, available art methods is regulated acquisition, and preferred organic acid-alcohol mixeding liquid is good; Said organic acid is preferably formic acid or acetate, and said acidic ethanol liquid is preferably the alcohol mixeding liquid that contains 1-5% formic acid or 1-5% acetate.
Embodiment 2
Select for use: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is a raw material; According to chemical formula Ba (FePO 4) 2Mol ratio metering; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 1% (weight percent) and adds alloying element sulphur, and the sulphur source is a Sulfur; After the mixing, in anhydrous ethanol medium, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the High Temperature Furnaces Heating Apparatus; In nitrogen atmosphere,, promptly get sulfur doping tertiary iron phosphate barium product of the present invention through 300-450 ℃ of high-temperature calcination 2-4h.
Embodiment 3
Select for use: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is a raw material; According to chemical formula Ba (FePO 4) 2Mol ratio metering; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 0.5% (weight percent) and adds alloying element sulphur, and the sulphur source is a Sulfur; After the mixing, in anhydrous ethanol medium, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the High Temperature Furnaces Heating Apparatus; In nitrogen atmosphere,, promptly get sulfur doping tertiary iron phosphate barium product of the present invention through 300-450 ℃ of high-temperature calcination 2-4h.
Embodiment 4
Select for use: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is a raw material; According to chemical formula Ba (FePO 4) 2Mol ratio metering; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 0.1% (weight percent) and adds alloying element sulphur, and the sulphur source is a Sulfur; After the mixing, in anhydrous ethanol medium, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the High Temperature Furnaces Heating Apparatus; In nitrogen atmosphere,, promptly get sulfur doping tertiary iron phosphate barium product of the present invention through 300-450 ℃ of high-temperature calcination 2-4h.
Embodiment 5
Select for use: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is a raw material; According to chemical formula Ba (FePO 4) 2Mol ratio metering; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 4.5% (weight percent) and adds alloying element sulphur, and the sulphur source is a Sulfur; After the mixing, in anhydrous ethanol medium, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the High Temperature Furnaces Heating Apparatus; In nitrogen atmosphere,, promptly get sulfur doping tertiary iron phosphate barium product of the present invention through 300-450 ℃ of high-temperature calcination 2-4h.
Embodiment 6
Select for use: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is a raw material; According to chemical formula Ba (FePO 4) 2Mol ratio metering; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 3% (weight percent) and adds alloying element sulphur, and the sulphur source is a Sulfur; After the mixing, in anhydrous ethanol medium, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the High Temperature Furnaces Heating Apparatus; In nitrogen atmosphere,, promptly get sulfur doping tertiary iron phosphate barium product of the present invention through 300-450 ℃ of high-temperature calcination 2-4h.
Embodiment 7
Select for use: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is a raw material; According to chemical formula Ba (FePO 4) 2Mol ratio metering; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 1.5% (weight percent) and adds alloying element sulphur, and the sulphur source is a Sulfur; After the mixing, in ethanol medium, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the High Temperature Furnaces Heating Apparatus; In nitrogen atmosphere,, promptly get sulfur doping tertiary iron phosphate barium product of the present invention through 300-450 ℃ of high-temperature calcination 2-4h.
Embodiment 8
Select for use: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is a raw material; According to chemical formula Ba (FePO 4) 2Mol ratio metering; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 0.6% (weight percent) and adds alloying element sulphur, and the sulphur source is a Sulfur; After the mixing, in ethanol medium, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the High Temperature Furnaces Heating Apparatus; In nitrogen atmosphere,, promptly get sulfur doping tertiary iron phosphate barium product of the present invention through 300-450 ℃ of high-temperature calcination 2-4h.
Embodiment 9
Select for use: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is a raw material; According to chemical formula Ba (FePO 4) 2Mol ratio metering; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 2% (weight percent) and adds alloying element sulphur, and the sulphur source is a Sulfur; After the mixing, in containing the alcohol mixeding liquid medium of 1-5% acetate, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the High Temperature Furnaces Heating Apparatus; In nitrogen atmosphere,, promptly get sulfur doping tertiary iron phosphate barium product of the present invention through 300-450 ℃ of high-temperature calcination 2-4h.
Embodiment 10
Select for use: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is a raw material; According to chemical formula Ba (FePO 4) 2Mol ratio metering; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 1% (weight percent) and adds alloying element sulphur, and the sulphur source is a Sulfur; After the mixing, in containing the alcohol mixeding liquid medium of 1-5% formic acid, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the High Temperature Furnaces Heating Apparatus; In nitrogen atmosphere,, promptly get sulfur doping tertiary iron phosphate barium product of the present invention through 300-450 ℃ of high-temperature calcination 2-4h.
Embodiment 11
Select for use: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is a raw material; According to chemical formula Ba (FePO 4) 2Mol ratio metering; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 5% (weight percent) and adds dopant elements sulphur, and the sulphur source is a Sulfur; After the mixing, in containing the alcohol mixeding liquid medium of 1-5% formic acid, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the High Temperature Furnaces Heating Apparatus; In nitrogen atmosphere,, promptly get sulfur doping tertiary iron phosphate barium product of the present invention through 300-450 ℃ of high-temperature calcination 2-4h.
Embodiment 12
Select for use: barium carbonate (BaCO3) (99.8%), Ferrox (FeC2O4.2H2O) (99.06%), Secondary ammonium phosphate (NH4H2PO4) (98%) is a raw material; According to chemical formula Ba (FePO 4) 2Mol ratio metering; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 0.3% (weight percent) and adds alloying element sulphur, and the sulphur source is a Sulfur; After the mixing, in containing the alcohol mixeding liquid medium of 1-5% formic acid, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry, obtain presoma, the presoma that oven dry is obtained places in the High Temperature Furnaces Heating Apparatus; In nitrogen atmosphere,, promptly get sulfur doping tertiary iron phosphate barium product of the present invention through 300-450 ℃ of high-temperature calcination 2-4h.
Sulfur doping tertiary iron phosphate barium product of the present invention is mainly as reductive agent, reductor, food deoxidizing antistaling agent; The raw materials for production of materials of electronic components or manufacturing electronic component, the raw materials for production of manufacturing cell positive material and battery thereof; Be used to smelt, the additive of alloy, glass production.
It has extremely strong reducing property sulfur doping tertiary iron phosphate barium product of the present invention, and it contacts with air, gets final product oxidation by air, becomes brown or yellow by dark color; Can be widely used in reduction, the deoxidation industry production; Because its nontoxic, water insoluble and organic solvent can generally be used for food deoxidizing antistaling agent (non-food product additive), and deixis is arranged.
As cell positive material, can be used as battery material, mainly 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; Sulfur doping tertiary iron phosphate barium product to above embodiment 1-12; Test respectively: the relative barium electropotential of its charge and discharge platform is about 3.6V, and initial discharge capacity surpasses 187mAh/g, and capacity decays about 0.2% approximately after 100 charge and discharge cycles; Specific storage and cyclical stability compared with prior art are greatly improved, and the production cost price is lower more than tens of times than prior art.
Be used to smelt, the additive of alloy, glass production; Be used for smelting, alloy production additive, but the improved products performance; The additive that is used for glass production can obtain required special glass product.

Claims (3)

1. the preparation method of a sulfur doping tertiary iron phosphate barium, it 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 is according to chemical formula Ba (FePO 4) 2Mol ratio metering; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 0.1-5% scope weight percent, adds alloying element; After the mixing, in ethanol medium, rotating speed 200-800r/mimn high speed ball milling 15-20h; With 105-120 ℃ of oven dry; Obtain presoma, the presoma that oven dry is obtained places in the High Temperature Furnaces Heating Apparatus, in nitrogen atmosphere; Through 300-450 ℃ of high-temperature calcination 2-4h, promptly get sulfur doping tertiary iron phosphate barium product of the present invention;
Said 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, red stone etc.; The phosphoric acid root is: phosphoric acid, sodium phosphate salt, one of primary ammonium phosphate or Secondary ammonium phosphate;
Said alloying element source: be elemental sulfur.
2. the preparation method of sulfur doping tertiary iron phosphate barium according to claim 1 is characterized in that: said ethanol medium is a tart.
3. the preparation method of sulfur doping tertiary iron phosphate barium according to claim 1 is characterized in that: said ethanol medium is the alcohol mixeding liquid that contains 1-5% formic acid or 1-5% acetate.
CN201210184497.8A 2012-06-06 2012-06-06 Preparation method of sulfur-doped barium iron phosphate Expired - Fee Related CN102701178B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1754275A (en) * 2002-12-23 2006-03-29 A123系统公司 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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1754275A (en) * 2002-12-23 2006-03-29 A123系统公司 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)

* Cited by examiner, † Cited by third party
Title
ALEXEI A. BELILK ETAL: "Neutron powder diffraction study of the magnetic and crystal structures of SrFe2(PO4)2", 《JOURNAL OF SOLID STATE CHMISTRY》 *

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