CN102674305A - Preparation method of lanthanum-doped barium iron phosphate - Google Patents
Preparation method of lanthanum-doped barium iron phosphate Download PDFInfo
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- CN102674305A CN102674305A CN2012101693624A CN201210169362A CN102674305A CN 102674305 A CN102674305 A CN 102674305A CN 2012101693624 A CN2012101693624 A CN 2012101693624A CN 201210169362 A CN201210169362 A CN 201210169362A CN 102674305 A CN102674305 A CN 102674305A
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a preparation method of lanthanum-doped barium iron phosphate; the lanthanum-doped barium iron phosphate has the chemical formula of Ba(FePO4)2; raw materials including barium source, ferrum source and phosphate group source are calculated according to the molar proportion of the chemical formula of Ba(FePO4)2; the doped element source is based on the weight of the generated barium iron phosphate, and the doped element is calculated and added according to the weight percent of 0.1-5%; after mixing, enabling the mixture to be treated by high-speed ball-milling in alcohol medium for 15-20 hours, drying at 105-120 DEG C, and obtaining precursor; putting the dried precursor into a high-temperature furnace, calcining the precursor at the high temperature of 300-450 DEG C in the nitrogen atmosphere for 2-4 hours, and obtaining the product; the lanthanum-doped barium iron phosphate is mainly used as reducing agent, deoxidant and food preservative; the lanthanum-doped barium iron phosphate is also used in electronic components and a battery raw material; the lanthanum-doped barium iron phosphate is used for smelting, alloy, glass production additive and the like; and the preparation method has the characteristics of being sufficient in raw materials, low in cost, environmentally-friendly, free from pollution and the like.
Description
Technical field
Lanthanum doping phosphoric acid iron barium of the present invention belongs to a kind of novel material.
Background technology
At present, do not find to have the report and the record of tertiary iron phosphate barium compound as yet.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 lanthanum doping phosphoric acid iron barium.
The preparation method of lanthanum doping phosphoric acid iron barium of the present invention, 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) metering of 2 mol ratio; 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 lanthanum doping phosphoric acid iron 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 one of Lanthanum trichloride, lanthanum trioxide.
For making each mixing of materials more even, said ethanol medium is alkaline, its alkaline ethanol liquid, and available art methods is regulated acquisition, and preferred ammoniacal liquor-alcohol mixeding liquid is good.
The present invention's beneficial effect compared with prior art: lanthanum doping phosphoric acid iron 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
Lanthanum doping phosphoric acid iron 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) metering of 2 mol ratio; 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 lanthanum doping phosphoric acid iron 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 one of Lanthanum trichloride, lanthanum trioxide.
For making each mixing of materials more even, said ethanol medium is alkaline, its alkaline ethanol liquid, and available art methods is regulated acquisition, and preferred ammoniacal liquor-alcohol mixeding liquid is good.
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) metering of 2 mol ratio; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 1% (weight percent) and adds the alloying element lanthanum, and the lanthanum source is Lanthanum trichloride (98%); 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; Through 300-450 ℃ of high-temperature calcination 2-4h, promptly get lanthanum doping phosphoric acid iron barium product of the present invention.
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) metering of 2 mol ratio; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 0.5% (weight percent) and adds the alloying element lanthanum, and the lanthanum source is Lanthanum trichloride (98%); 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; Through 300-450 ℃ of high-temperature calcination 2-4h, promptly get lanthanum doping phosphoric acid iron barium product of the present invention.
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) metering of 2 mol ratio; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 0.1% (weight percent) and adds the alloying element lanthanum, and the lanthanum source is Lanthanum trichloride (98%); 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; Through 300-450 ℃ of high-temperature calcination 2-4h, promptly get lanthanum doping phosphoric acid iron barium product of the present invention.
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) metering of 2 mol ratio; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 4.5% (weight percent) and adds the alloying element lanthanum, and the lanthanum source is Lanthanum trichloride (98%); 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; Through 300-450 ℃ of high-temperature calcination 2-4h, promptly get lanthanum doping phosphoric acid iron barium product of the present invention.
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) metering of 2 mol ratio; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 3% (weight percent) and adds the alloying element lanthanum, and the lanthanum source is Lanthanum trichloride (98%); 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; Through 300-450 ℃ of high-temperature calcination 2-4h, promptly get lanthanum doping phosphoric acid iron barium product of the present invention.
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) metering of 2 mol ratio; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 1.5% (weight percent) and adds the alloying element lanthanum, and the lanthanum source is lanthanum trioxide (98%); 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 lanthanum doping phosphoric acid iron barium product of the present invention.
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) metering of 2 mol ratio; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 0.6% (weight percent) and adds the alloying element lanthanum, and the lanthanum source is lanthanum trioxide (98%); 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 lanthanum doping phosphoric acid iron barium product of the present invention.
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) metering of 2 mol ratio; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 2% (weight percent) and adds the alloying element lanthanum, and the lanthanum source is lanthanum trioxide (98%); 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 lanthanum doping phosphoric acid iron barium product of the present invention.
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) metering of 2 mol ratio; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 1% (weight percent) and adds the alloying element lanthanum, and the lanthanum source is lanthanum trioxide (98%); 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 lanthanum doping phosphoric acid iron barium product of the present invention.For making each mixing of materials more even, said ethanol medium is alkaline, its alkaline ethanol liquid, and available art methods is regulated acquisition, and preferred ammoniacal liquor-alcohol mixeding liquid is good.
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) metering of 2 mol ratio; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 5% (weight percent) and adds the alloying element lanthanum, and the lanthanum source is lanthanum trioxide (98%); 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 lanthanum doping phosphoric acid iron barium product of the present invention through 300-450 ℃ of high-temperature calcination 2-4h.For making each mixing of materials more even, said ethanol medium is alkaline, its alkaline ethanol liquid, and available art methods is regulated acquisition, and preferred ammoniacal liquor-alcohol mixeding liquid is good.
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) metering of 2 mol ratio; The alloying element source can generate the weight of tertiary iron phosphate barium by theory, calculates by 0.3% (weight percent) and adds the alloying element lanthanum, and the lanthanum source is lanthanum trioxide (98%); 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 lanthanum doping phosphoric acid iron barium product of the present invention.For making each mixing of materials more even, said ethanol medium is alkaline, its alkaline ethanol liquid, and available art methods is regulated acquisition, and preferred ammoniacal liquor-alcohol mixeding liquid is good.
Lanthanum doping phosphoric acid iron 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 lanthanum doping phosphoric acid iron 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; Lanthanum doping phosphoric acid iron 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 lanthanum doping phosphoric acid iron 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) metering of 2 mol ratio; 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 lanthanum doping phosphoric acid iron 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 one of Lanthanum trichloride, lanthanum trioxide.
2. the preparation method of lanthanum doping phosphoric acid iron barium according to claim 1, it is characterized in that: said ethanol medium is alkaline.
3. the preparation method of lanthanum doping phosphoric acid iron barium according to claim 1 is characterized in that: said ethanol medium is ammoniacal liquor-alcohol mixeding liquid.
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| CN2012101693624A CN102674305A (en) | 2012-05-28 | 2012-05-28 | Preparation method of lanthanum-doped barium iron phosphate |
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| CN2012101693624A CN102674305A (en) | 2012-05-28 | 2012-05-28 | Preparation method of lanthanum-doped barium iron phosphate |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800000A (en) * | 2004-12-31 | 2006-07-12 | 山西超新金属材料有限公司 | Barium metaphosphorate production process |
| CN102347486A (en) * | 2011-10-26 | 2012-02-08 | 吴润秀 | Method for preparing barium-activated lithium iron phosphate cathode material |
-
2012
- 2012-05-28 CN CN2012101693624A patent/CN102674305A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800000A (en) * | 2004-12-31 | 2006-07-12 | 山西超新金属材料有限公司 | Barium metaphosphorate production process |
| CN102347486A (en) * | 2011-10-26 | 2012-02-08 | 吴润秀 | Method for preparing barium-activated lithium iron phosphate cathode material |
Non-Patent Citations (2)
| Title |
|---|
| ALEXEI A. BELIK ET AL.: "Neutron powder diffraction study of the magnetic and crystal structures of SrFe2(PO4)2", 《JOURNAL OF SOLID STATE CHEMISTRY》 * |
| ALEXEI A. BELIK ET AL.: "SrFe2(PO4)2: Ab Initio Structure Determination with X-ray Powder Diffraction Data and Unusual Magnetic Properties", 《CHEM. MATER.》 * |
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Application publication date: 20120919 |