CN103682338B - Preparation method for high-conductivity LiFePO4 cathode material - Google Patents
Preparation method for high-conductivity LiFePO4 cathode material Download PDFInfo
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- CN103682338B CN103682338B CN201310719798.0A CN201310719798A CN103682338B CN 103682338 B CN103682338 B CN 103682338B CN 201310719798 A CN201310719798 A CN 201310719798A CN 103682338 B CN103682338 B CN 103682338B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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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 relates to a preparation method for a high-conductivity LiFePO4 cathode material. The method comprises the following steps: ferric citrate, zinc citrate and citric acid are completely dissolved in deionized water to obtain a solution, wherein the dissolving temperature is controlled to be 50-70 DEG C, meanwhile, ammonium dihydrogen phosphate and lithium hydroxide are completely dissolved in deionized water together so as to obtain an LiH2PO4 solution, the two solutions are mixed uniformly, then mixture is poured into a high-pressure reaction kettle for heating for 6-8 h at a constant temperature between 180 DEG C and 200 DEG C. According to the invention, the LiFePO4 is synthesized through a hydrothermal method, and the synthesized LiFePO4 has the advantages of small particle diameter and good uniformity of grain size. The reaction temperature and the energy consumption are low.
Description
Technical field
The present invention relates to a kind of preparation method of high-conductivity LiFePO4 cathode material, more particularly, to by phosphoric acid
Ferrous lithium（LiFePO4）Doping modification method, belong to technical field of lithium ion.
Background technology
Due to LiFePO 4（LiFePO4）Raw material sources extensively, relative low price the 1/5 of cobalt acid lithium (about), right
Environmental friendliness, security performance projects, and theoretical specific capacity height (about 170mAh/g) is so that it is in various movable power source fields, special
It is not that large-sized power field of power supplies needed for auto industry has great market prospects.But the topmost problem of LiFePO 4
It is that its electron conduction is low, lithium ion diffusion velocity is slow.Document report is had to coat to improve this by carbon or metal ion at present
One problem, such as Croce, F.;D Epifanio,A.;Hassoun,J.;Deptula,A.;Olczac,T.;Scrosati,
B.Electrochemical and solid-state letters.2002,5:It was recently reported that respectively in LiFePO in A474In
Cu and Ag of admixture 1%, result capacity improves about 25mAh/g, however, using the dispersion of the conductive materials such as carbon and metallic or
The method of cladding, mainly changes the electric conductivity between particle and particle, and to LiFePO4Electric conductivity within particle but shadow
Sound is little.Work as LiFePO4When the size of particle is not sufficiently small (>200nm), high current to be obtained, high power capacity charge and discharge electrical
Can be still relatively difficult.Therefore, how to improve LiFePO4Electric conductivity within particle, that is, improve LiFePO4The conduction of crystal
Property is still a key issue of this area.At present, industrial LiFePO 4（LiFePO4）Synthesis more adopt synthesis in solid state
Method, but the LiFePO 4 using solid-phase synthesis synthesis（LiFePO4）The material particle size that there is synthesis is larger, and thing is mutually not
Uniformly the shortcomings of.
Patent CN101315981A discloses a kind of lithium iron phosphate anode material for lithium ion battery, with hydro-thermal method preparation
LiFePO 4 be presoma, then it is uniformly mixed with conductive materials predecessor, metal cation salt, finally in inert atmosphere
Middle roasting, obtains conductive materials cladding, the lithium iron phosphate cathode material of metal ion mixing.Its presoma separate be dried after with
Metal cation salt mixes, and is solid phase and solid phase mixing, the method for employing is ball milling it is difficult to mix.Last reaction needs
Carry out under an inert atmosphere, technique controlling difficulty is big.
Content of the invention
The purpose of the present invention is to overcome above-mentioned deficiency, and provides a kind of preparation of high-conductivity LiFePO4 cathode material
Method, synthesized LiFePO 4（LiFePO4）Have that grain diameter is less and the good advantage of uniform particle diameter concurrently.
The technical solution used in the present invention is：
A kind of preparation method of high-conductivity LiFePO4 cathode material is as follows including step：
（1）Stoichiometrically mol ratio is 1：0.9～0.975：1：0.0083～0.034：2 weigh lithium hydroxide respectively
（LiOH）, ironic citrate（FeC6H5O7）, ammonium dihydrogen phosphate（NH4H2PO4）, zinc citrate（Zn3(C6H5O7)2·2H2O）And lemon
Lemon acid（C6H8O7）；
（2）Ironic citrate, zinc citrate and citric acid are completely dissolved in deionized water, solution temperature controls 50～
70 DEG C, ammonium dihydrogen phosphate is completely dissolved together with lithium hydroxide in deionized water simultaneously and obtains LiH2PO4Solution；
（3）Until completely dissolved two solution are mixed, be stirred making it mix using magnetic stirring apparatus, then
Pour in autoclave, in 180～200 DEG C of heated at constant temperature 6～8h；
（4）After the completion of reaction, question response kettle naturally cools to room temperature, will wherein precipitated product move into centrifuge tube in, spend from
Sub- water is repeated centrifugation and purifies for several times, and products therefrom after purification is put into vacuum drying chamber, after the completion of dried process
To LiFe0.975Zn0.025PO4Compound.
Above-mentioned steps（1）Middle citric acid solution concentration range is 0.01～1mol/L, zinc citrate solution concentration is
0.001-0.0045mol/L and citric acid solution concentration range are 0.01～1mol/L.
LiH2PO4The concentration range of solution is 1～12mol/L.
Above-mentioned steps（4）The condition of middle dried process is dried 4～24 hours at being 60～120 DEG C.
Of the present invention by hydro-thermal method synthesizing lithium ferrous phosphate（LiFePO4）, synthesized LiFePO 4
（LiFePO4）Have that grain diameter is less and the good advantage of uniform particle diameter concurrently.The flow chart that hydro-thermal method synthesizes LiZnxFe1-xPO4
As accompanying drawing 1.In LiFePO 4（LiFePO4）In material system, use zinc（Zn）Ionic compartmentation iron（Fe）Ion position, generates
LiZnxFe1-xPO4, metal-doped after its electron conduction tool improve a lot.
Beneficial effects of the present invention are as follows：
In LiFePO 4（LiFePO4）In material system, use zinc（Zn）Ionic compartmentation iron（Fe）Ion position, generates
LiZnxFe1-xPO4, metal-doped after its electron conduction tool improve a lot.Of the present invention phosphorus is synthesized by hydro-thermal method
Ferrous silicate lithium（LiFePO4）, synthesized LiFePO 4（LiFePO4）Have grain diameter concurrently less good with uniform particle diameter
Advantage.Reaction temperature is low, less energy consumption.Reaction does not need inert atmosphere protection.
Brief description
Fig. 1 is hydro-thermal method synthesis LiZnxFe1-xPO4Flow chart.
Fig. 2 is sample particle diameter distribution map
Specific embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment 1
（1）Stoichiometrically weigh the lithium hydroxide of 1mol respectively（LiOH）, the ironic citrate of 0.975mol
（FeC6H5O7）, the ammonium dihydrogen phosphate of 1mol（NH4H2PO4）, the zinc citrate of 0.0083mol（Zn3(C6H5O7)2·2H2O）And
2mol citric acid（C6H8O7）.
（2）First by the ironic citrate of 0.975mol（FeC6H5O7）, the zinc citrate of 0.0083mol（Zn3(C6H5O7)2·
2H2O）With 2mol citric acid q.s deionized water（About 2L）In be completely dissolved, solution temperature control 60 DEG C.To simultaneously
The ammonium dihydrogen phosphate of 1mol（NH4H2PO4）With 1mol lithium hydroxide（LiOH）Complete in the deionized water (about 4L) of q.s together
CL obtains LiH2PO4Solution.
（3）Until completely dissolved two solution are mixed, be stirred making it mix using magnetic stirring apparatus, will mix
Close solution to pour in autoclave, in 180 DEG C of heated at constant temperature 6h.
（4）After the completion of reaction, question response kettle naturally cools to room temperature, will wherein precipitated product move into centrifuge tube in, spend from
Sub- water is repeated centrifugation and purifies for several times, products therefrom after purification is carried out putting into vacuum drying chamber, dried process completes
After obtain LiFe0.975Zn0.025PO4Compound.Prepared sample particle diameter distribution map such as Fig. 2.
Embodiment 2
（1）Stoichiometrically weigh the lithium hydroxide of 1mol respectively（LiOH）, the ironic citrate of 0.95mol
（FeC6H5O7）, the ammonium dihydrogen phosphate of 1mol（NH4H2PO4）, the zinc citrate of 0.0167mol（Zn3(C6H5O7)2·2H2O）And
2mol citric acid（C6H8O7）.
（2）First by the ironic citrate of 0.95mol（FeC6H5O7）, the zinc citrate of 0.0167mol（Zn3(C6H5O7)2·
2H2O）It is completely dissolved in the deionized water of q.s with 2mol citric acid, solution temperature controls 60 DEG C.Simultaneously by the phosphorus of 1mol
Acid dihydride ammonium（NH4H2PO4）With 1mol lithium hydroxide（LiOH）It is completely dissolved in the deionized water of q.s together and obtain
LiH2PO4Solution.
（3）Until completely dissolved two solution are mixed, be stirred making it mix using magnetic stirring apparatus, will mix
Close solution to pour in autoclave, in 190 DEG C of heated at constant temperature 7h.
（4）After the completion of reaction, question response kettle naturally cools to room temperature, will wherein precipitated product move into centrifuge tube in, spend from
Sub- water is repeated centrifugation and purifies for several times, products therefrom after purification is carried out putting into vacuum drying chamber, dried process completes
After obtain LiFe0.95Zn0.05PO4Compound.
Embodiment 3
（1）Stoichiometrically weigh the lithium hydroxide of 1mol respectively（LiOH）, the ironic citrate of 0.9mol
（FeC6H5O7）, the ammonium dihydrogen phosphate of 1mol（NH4H2PO4）, the zinc citrate of 0.034mol（Zn3(C6H5O7)2·2H2O）And
2mol citric acid（C6H8O7）.
（2）First by the ironic citrate of 0.9mol（FeC6H5O7）, the zinc citrate of 0.034mol（Zn3(C6H5O7)2·2H2O）
It is completely dissolved in the deionized water of q.s with 2mol citric acid, solution temperature controls 70 DEG C.Simultaneously by the di(2-ethylhexyl)phosphate of 1mol
Hydrogen ammonium（NH4H2PO4）With 1mol lithium hydroxide（LiOH）It is completely dissolved in the deionized water of q.s together and obtain LiH2PO4Molten
Liquid.
（3）Until completely dissolved two solution are mixed, be stirred making it mix using magnetic stirring apparatus, will mix
Close solution to pour in autoclave, in 200 DEG C of heated at constant temperature 8h.
（4）After the completion of reaction, question response kettle naturally cools to room temperature, will wherein precipitated product move into centrifuge tube in, spend from
Sub- water is repeated centrifugation and purifies for several times, products therefrom after purification is carried out putting into vacuum drying chamber, dried process completes
After obtain LiFe0.9Zn0.1PO4Compound.
Claims (1)
1. a kind of preparation method of high-conductivity LiFePO4 cathode material, is characterized in that, as follows including step：
（1）Stoichiometrically weigh the lithium hydroxide of 1mol respectively（LiOH）, the ironic citrate of 0.975mol
（FeC6H5O7）, the ammonium dihydrogen phosphate of 1mol（NH4H2PO4）, the zinc citrate of 0.0083mol（Zn3(C6H5O7)2•2H2O）With
And 2mol citric acid（C6H8O7）；
（2）First by the ironic citrate of 0.975mol（FeC6H5O7）, the zinc citrate of 0.0083mol（Zn3(C6H5O7)2•
2H2O）It is completely dissolved in 2L deionized water with 2mol citric acid, solution temperature controls 60 DEG C, simultaneously by the di(2-ethylhexyl)phosphate of 1mol
Hydrogen ammonium（NH4H2PO4）With 1mol lithium hydroxide（LiOH）It is completely dissolved in 4L deionized water together and obtain LiH2PO4Solution；
（3）Until completely dissolved two solution are mixed, be stirred making it mix using magnetic stirring apparatus, will mix molten
Liquid is poured in autoclave, in 180 DEG C of heated at constant temperature 6h；
（4）After the completion of reaction, question response kettle naturally cools to room temperature, will wherein move in centrifuge tube by precipitated product, deionized water
Centrifugation is repeated purify for several times, products therefrom after purification is put into vacuum drying chamber, obtains after the completion of dried process
LiFe0.975Zn0.025PO4Compound.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101630731A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Nanoscale lithium iron phosphate used as cathode material of lithium ion battery and preparation method thereof |
| CN101628714A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Carbon-free nanoscale lithium iron phosphate and preparation method thereof |
| CN101630730A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Nanoscale lithium iron phosphate compound and preparation method thereof |
| CN102013468A (en) * | 2009-09-07 | 2011-04-13 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing high-conductivity lithium iron phosphate anode material |
| CN102530906A (en) * | 2010-12-16 | 2012-07-04 | 中国科学院福建物质结构研究所 | Microwave-hydrothermal method for preparing cathode materials of nano lithium iron phosphate batteries |
-
2013
- 2013-12-23 CN CN201310719798.0A patent/CN103682338B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101630731A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Nanoscale lithium iron phosphate used as cathode material of lithium ion battery and preparation method thereof |
| CN101628714A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Carbon-free nanoscale lithium iron phosphate and preparation method thereof |
| CN101630730A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Nanoscale lithium iron phosphate compound and preparation method thereof |
| CN102013468A (en) * | 2009-09-07 | 2011-04-13 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing high-conductivity lithium iron phosphate anode material |
| CN102530906A (en) * | 2010-12-16 | 2012-07-04 | 中国科学院福建物质结构研究所 | Microwave-hydrothermal method for preparing cathode materials of nano lithium iron phosphate batteries |
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