CN101807697A - Method for synthesizing lithium iron phosphate with full substitute structure - Google Patents

Method for synthesizing lithium iron phosphate with full substitute structure Download PDF

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Publication number
CN101807697A
CN101807697A CN201010159642A CN201010159642A CN101807697A CN 101807697 A CN101807697 A CN 101807697A CN 201010159642 A CN201010159642 A CN 201010159642A CN 201010159642 A CN201010159642 A CN 201010159642A CN 101807697 A CN101807697 A CN 101807697A
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lithium
phosphate
ion
synthetic method
ferrous
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谷亦杰
陈蕴博
张钊
陈林
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JIANGSU C &E MATERIALS RESEARCH INSTITUTE Co Ltd
Jiangsu University
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JIANGSU C &E MATERIALS RESEARCH INSTITUTE Co Ltd
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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 discloses a method for synthesizing lithium iron phosphate with a full substitute structure, and relates to lithium ion battery anode materials. The method comprises the following steps: uniformly mixing lithium salt, ferric salt and phosphate in a molar ratio of lithium ions to ferric ions to phosphate ions of (0.8-1.2): (0.8-1.2): (0.8-1.2) to obtain a mixture; putting the mixture into aqueous solution containing boric acid, soluble salts and soluble organics, uniformly stirring, putting the solution into a high temperature furnace, performing heating treatment on the solution by one segment or by segments at a temperature rise rate of 1 to 30 DEG C/min in the non-air or non-oxidizing atmosphere, naturally cooling the solution, and synthesizing ferrous phosphate powder containing carbon simple substance and doped ions; and levigating the synthesized ferrous phosphate powder and controlling the grain size to between 1 and 50um. The synthesized lithium iron phosphate with the full substitute structure has good electronic conductivity.

Description

Synthetic method with LiFePO 4 of full substitute structure
Technical field
This patent relates to anode material for lithium-ion batteries, and ferric phosphate lithium cell material especially is specially the synthetic method of the LiFePO 4 with full substitute structure.
Background technology
Application form from the energy, the demand growth of large-scale removable power supply is very fast, this mainly is the result of automobile power power supply development, this has just proposed renewal, higher requirement to battery industry, presses for that volume is little, specific energy is high, the secondary cell of lightweight large-scale high energy, high reliability.Polyanion group PO4 in the material 3-The stable of whole three-dimensional frame structure played an important role, make LiFePO 4Have good stability and fail safe, and theoretical capacity also reaches 170mAh/g, have and suitable specific power and the specific energy of present business-like metal oxide cathode material, can be in the medium-term and long-term stable storage of electrolyte.But the lithium ion chemical diffusion coefficient of material and electronic conductivity are too low, caused the theoretical capacity of material not discharged to greatest extent and heavy-current discharge performance not good.It is at present main that to overcome lithium ion chemical diffusion coefficient and the too low method of electronic conductivity be to coat and doping removes to overcome low chemical diffusion coefficient of lithium ion and electronic conductivity, but, by discovering, the effect of the method raising electronic conductivity of this single substitutional ion LiFePO4 is limited.
Summary of the invention
This patent is to overcome the prior art deficiency, and a kind of synthetic method of full alternative structure LiFePO4 is provided.
Technical scheme of the present invention is
1, get lithium salts, molysite and phosphate, in lithium ion: iron ion: phosphate anion mol ratio (0.8～1.2): (0.8～1.2): the ratio of (0.8～1.2) is evenly mixed and is obtained mixture.Wherein: lithium salts is wherein a kind of of lithium hydroxide, lithium sulfate, lithium oxalate, lithium acetate, lithium carbonate and lithium nitrate.Molysite is wherein a kind of of ferric sulfate, ferrous sulfate, ferrous oxalate, ferric acetate and ferric nitrate.Phosphate is ammonium dihydrogen phosphate.
2, a certain amount of mixture is put into a certain amount of aqueous solution that contains boric acid, solubility salt and the organic class of solubility, after evenly stirring, put into high temperature furnace, in non-air or non-oxidizing atmosphere, one section of heating rate or segmentation heat treated with 1-30 ℃/min, natural cooling synthesizes the ferrous phosphate powder that contains carbon simple substance (representing with C) and dopant ion (representing with A, B, C and D) and (uses Li then 0.8～1.2-xA xFe 0.8～ 1.2-yB yP 0.8～1.2-zC zO 4-wD wExpression), the x in the formula, y, z and w value are decided according to the addition content of respective substance; Wherein:
(1) mass ratio of the aqueous solution and mixture be=(0.1-10): 1;
(2) comprise at least in the solubility salt in the aqueous solution: several in nitrate, acetate, sulfate or the hydrochloride of lithium fluoride and aluminium, titanium, magnesium, zirconium, vanadium, manganese, nickel, cobalt, niobium, rhodium, barium, chromium element, addition content guarantees: when the lithium ion in the lithium salts was 1 mole, the amount of substance sum of the ion in the solubility salt was greater than 0 mole and less than 0.1 mole.
(3) the organic class material of the solubility in the aqueous solution comprises at least: sucrose, glucose and can be decomposed into a kind of in the soluble high-molecular compound with good electric conductivity carbon class material through pyrolysis.Addition content guarantees: the carbon content in the organic class material of solubility and the ratio of ferrous phosphate powder quality are less than 10%.
3, above synthetic ferrous phosphate lithium powder is levigate, particle diameter is controlled between the 1-50um.
The present invention adopts said method, the LiFePO4 of synthetic full alternative structure.
Embodiment
In order to be illustrated more clearly in the present invention, enumerate following examples, but it there is not any restriction to the present invention.
Embodiment one:
(1) at first lithium oxalate, ferrous oxalate and three kinds of materials of ammonium dihydrogen phosphate in lithium ion: iron ion: the phosphate anion mol ratio is that 1: 1: 1 ratio is evenly mixed the acquisition mixture.
(2) getting mixture 1kg puts into the aqueous solution that 1kg contains glucose and magnesium nitrate, zirconium nitrate, boric acid and lithium fluoride and stirs, heating rate with 20 ℃/min under nitrogen atmosphere heats, in 700 ℃ of constant temperature 10 hours, natural cooling then, the synthetic ferrous phosphate lithium powder that contains carbon simple substance and full substitutional ion, wherein:
Contain glucose 10g, iron ion among the aqueous solution B of requirement 1kg: magnesium ion: zirconium ion: boron ion: the fluorine ion mol ratio is 0.99: 0.01: 0.01: 0.01: 0.01.
According to step (1) as can be known 1kg mixture A contain 1.62 moles lithium oxalate (Li 2C 2O 4Molecular weight 102), 3.24 moles of ferrous oxalate (FeC 2O 4143) and 3.24 mole of phosphoric acid ammonium dihydrogen (NH molecular weight: 4H 2PO 4Molecular weight: 115), so the last synthetic lithium iron phosphate cathode material LiMg that contains carbon simple substance and doped metal ion 0.01Fe 0.99Zr 0.01P 0.99B 0.01O 3.99F 0.01Expression;
(3) synthetic ferrous phosphate lithium powder is levigate, particle diameter is controlled between the 1-50um, and the conductance of sample is 2.1*10 -3S cm -1
Embodiment two:
(1) at first with lithium carbonate, ferrous oxalate and three kinds of materials of ammonium dihydrogen phosphate in lithium ion: iron ion: the phosphate anion mol ratio is that 1: 1: 1 ratio is evenly mixed the acquisition mixture;
(2) getting the 1kg mixture puts into the aqueous solution that 2kg contains polyvinyl alcohol and magnesium sulfate, cobalt nitrate, boric acid and lithium fluoride and stirs, heating rate with 10 ℃/min under nitrogen atmosphere heats, in 300 ℃ of constant temperature 5 hours, continue then to heat up, in 700 ℃ of constant temperature 5 hours, natural cooling, the synthetic ferrous phosphate lithium powder that contains carbon simple substance and full substitutional ion, wherein:
Contain polyvinyl alcohol 10g, iron ion in the aqueous solution of requirement 1kg: magnesium ion: cobalt ions: boron ion: the fluorine ion mol ratio is 0.99: 0.01: 0.01: 0.01: 0.01
According to step (1) as can be known the 1kg mixture contain 1.70 moles lithium carbonate (Li 2CO 3Molecular weight 74), 3.48 moles of ferrous oxalate (FeC 2O 4143) and 3.4 mole of phosphoric acid ammonium dihydrogen (NH molecular weight: 4H 2PO 4Molecular weight: 115), so the last synthetic lithium iron phosphate cathode material that contains carbon simple substance and doped metal ion can be used LiMg 0.01Fe 0.99Co 0.01P 0.99B 0.01O 3.99F 0.01Expression;
(3) synthetic ferrous phosphate lithium powder is levigate, particle diameter is controlled between the 1-50um, and the conductance of sample is 2.5*10 -3S cm -1
For the ease of calculating, when three kinds of materials of the lithium salts in the embodiment of the invention, molysite, ammonium dihydrogen phosphate mix all in lithium ion: iron ion: the phosphate anion mol ratio is that 1: 1: 1 ratio is carried out, thereby X, Y, Z value in the last ferrous phosphate lithium powder molecular formula of synthesizing are equated, but this can not be as the restriction to technical solution of the present invention.

Claims (8)

1. have the synthetic method of the LiFePO 4 of full substitute structure, it is characterized in that: described method step is as follows:
(1) get lithium salts, molysite and phosphate, in lithium ion: iron ion: phosphate anion mol ratio (0.8～1.2): (0.8～1.2): the ratio of (0.8～1.2) is evenly mixed and is obtained mixture;
(2) mixture is put into the aqueous solution that contains boric acid, solubility salt and the organic class of solubility, after evenly stirring, put into high temperature furnace, in non-air or non-oxidizing atmosphere, one section of heating rate or segmentation heat treated with 1-30 ℃/min, natural cooling synthesizes the ferrous phosphate powder that contains carbon simple substance and dopant ion then;
(3) synthetic ferrous phosphate lithium powder is levigate, particle diameter is controlled between the 1-50um.
2. the described synthetic method of claim 1 is characterized in that: described lithium salts is wherein a kind of of lithium hydroxide, lithium sulfate, lithium oxalate, lithium acetate, lithium carbonate and lithium nitrate.
3. the described synthetic method of claim 1 is characterized in that: described molysite is wherein a kind of of ferric sulfate, ferrous sulfate, ferrous oxalate, ferric acetate and ferric nitrate.
4. the described synthetic method of claim 1, it is characterized in that: described phosphate is ammonium dihydrogen phosphate.
5. the described synthetic method of claim 1, it is characterized in that: the chemical formula of described ferrous phosphate is: use Li 0.8～1.2-xA xFe 0.8～1.2-yB yP 0.8～1.2-zC zO 4-wD w, A, B, C and D are dopant ion, the x in the formula, y, z and w value are decided according to the addition content of respective substance.
6. the described synthetic method of claim 1 is characterized in that: the mass ratio of the described aqueous solution and described mixture for=(0.1-10): 1.
7. the described synthetic method of claim 1, it is characterized in that: comprise at least in the solubility salt in the described aqueous solution: several in nitrate, acetate, sulfate or the hydrochloride of lithium fluoride and aluminium, titanium, magnesium, zirconium, vanadium, manganese, nickel, cobalt, niobium, rhodium, barium, chromium element, addition content guarantees: when the lithium ion in the lithium salts was 1 mole, the amount of substance sum of the ion in the solubility salt was greater than 0 mole and less than 0.1 mole.
8. the described synthetic method of claim 1, it is characterized in that: the organic class material of the solubility in the described aqueous solution comprises at least: sucrose, glucose and can be decomposed into a kind of in the soluble high-molecular compound with good electric conductivity carbon class material through pyrolysis, addition content guarantees: the carbon content in the organic class material of solubility and the ratio of ferrous phosphate powder quality are less than 10%.
CN201010159642A 2010-04-29 2010-04-29 Method for synthesizing lithium iron phosphate with full substitute structure Pending CN101807697A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102569738A (en) * 2010-12-30 2012-07-11 北京当升材料科技股份有限公司 Preparation method of lithium iron phosphate material
CN102569790A (en) * 2010-12-30 2012-07-11 北京当升材料科技股份有限公司 Lithium iron phosphate material
WO2023207121A1 (en) * 2022-04-25 2023-11-02 湖北万润新能源科技股份有限公司 High-compaction lithium iron phosphate positive electrode material and preparation method therefor, and positive electrode and battery thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1803592A (en) * 2005-12-23 2006-07-19 清华大学 Method for preparing lithium enriched lithium ion phosphate powder
CN1837033A (en) * 2006-03-24 2006-09-27 山东科技大学 Process for synthesizing LiFePO4 as positive electrode materials of lithium ion cell
CN101364643A (en) * 2008-07-18 2009-02-11 杭州赛诺索欧电池有限公司 Boron containing lithium iron phosphate/carbon composite material and preparation thereof
CN101369657A (en) * 2007-08-13 2009-02-18 深圳市比克电池有限公司 Multicomponent doping spherical lithium iron phosphate anode material and method of manufacturing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1803592A (en) * 2005-12-23 2006-07-19 清华大学 Method for preparing lithium enriched lithium ion phosphate powder
CN1837033A (en) * 2006-03-24 2006-09-27 山东科技大学 Process for synthesizing LiFePO4 as positive electrode materials of lithium ion cell
CN101369657A (en) * 2007-08-13 2009-02-18 深圳市比克电池有限公司 Multicomponent doping spherical lithium iron phosphate anode material and method of manufacturing the same
CN101364643A (en) * 2008-07-18 2009-02-11 杭州赛诺索欧电池有限公司 Boron containing lithium iron phosphate/carbon composite material and preparation thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102569738A (en) * 2010-12-30 2012-07-11 北京当升材料科技股份有限公司 Preparation method of lithium iron phosphate material
CN102569790A (en) * 2010-12-30 2012-07-11 北京当升材料科技股份有限公司 Lithium iron phosphate material
WO2023207121A1 (en) * 2022-04-25 2023-11-02 湖北万润新能源科技股份有限公司 High-compaction lithium iron phosphate positive electrode material and preparation method therefor, and positive electrode and battery thereof

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Open date: 20100818