CN103633326A - Production method of lithium iron phosphate - Google Patents
Production method of lithium iron phosphate Download PDFInfo
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- CN103633326A CN103633326A CN201310697763.1A CN201310697763A CN103633326A CN 103633326 A CN103633326 A CN 103633326A CN 201310697763 A CN201310697763 A CN 201310697763A CN 103633326 A CN103633326 A CN 103633326A
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- production method
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- lifepo4
- iron phosphate
- lithium iron
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Classifications
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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
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
Abstract
The invention discloses a production method of lithium iron phosphate with stable product quality and performances. The production method is characterized by comprising the following steps: adding raw materials into a ball mill for ball milling according to the proportion of iron phosphate to lithium carbonate to silver nitrate to deionized water of 1.0: (0.2-0.22): (0.001-0.002): (0.5-0.6), filtering, drying, reducing, calcining and crushing to prepare the nano-scale lithium iron phosphate taking silver oxide as a conductive agent. The method disclosed by the invention is simple and feasible, the synthesized lithium iron phosphate is pure phase and has good electrochemical performances and stable quality, the electrical gram capacity is above 150mAh/g and the tap density is 1.65g/cm<3>-1.70g/cm<3>. The lithium iron phosphate is assembled into a button cell by using a half-cell, charge-discharge testing is performed on the cell at the rate of 0.5C, the average discharge mass specific capacity is more than 150mAh/g, the cyclic coulombic efficiency is more than 95.0%, the charge constant current ratio is more than 98%, the discharge mean voltage is more than 3.4V, and the capacity retention rate after 100 cycles is more than 97.0%.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, specifically a kind of production method of LiFePO4.
Background technology
In order to meet society to electrokinetic cell, electric automobile and various portable electronics, and the requirement to mechanism of new electrochemical power sources, the demand of lithium ion battery increases day by day.The reasons such as at present, in anode material for lithium-ion batteries,, due to the toxicity of cobalt acid lithium, cycle performance and the high-temperature behavior of LiMn2O4 are poor, lithium nickelate preparation difficulty, are greatly limited the application of these materials.And the LiFePO4 with olivine structural is the Olivine-type Cathode Material in Li-ion Batteries that a class is very excellent.Its theoretical specific capacity reaches 170mAh/g, the charging/discharging voltage platform of 3.4V left and right, there is aboundresources, environmental friendliness, long service life, the advantage such as thermal stability is good, causes that people pay close attention to widely, LiFePO4 is considered to the preferred material of substituting cobalt acid lithium, is also one of study hotspot of current anode material for lithium-ion batteries.But, the conductivity of lithium iron phosphate positive material is very poor, electricity gram volume is less than 125mAh/g, the stability test of producing can be poor, use half-cell to be assembled into button battery, under the multiplying power of 0.5C, this battery is carried out to charge-discharge test, average electric discharge specific discharge capacity is less than 125mAh/g, has seriously restricted its large-scale application.For this reason, researcher, having done very large effort aspect the transmission speed of its conductivity of raising and quickening lithium ion, as carbon coated, adds conducting polymer, the metal ion that overprices that adulterates, the material of synthetic more small particle diameter etc.By first preparing the ferric phosphate of special appearance, then it by certain approach synthesizing iron lithium phosphate, is also a focus of studying at present.
Summary of the invention
The production method that the object of this invention is to provide the LiFePO4 of a kind of product quality and stable performance.
The present invention adopts following technical scheme to realize its goal of the invention, a kind of production method of LiFePO4, and it comprises the following steps:
(1) by weight, in ferric phosphate: lithium carbonate: silver nitrate: the ratio of deionized water=1.0:0.2～0.22:0.001～0.002:0.5～0.6 joins in ball mill ball milling 3 hours～4 hours by above-mentioned raw materials, and material is fully mixed;
(2) the material after ball milling filters to remove through flame filter press and mixes mother liquor, obtains filter residue and sends in drying machine dry;
(3) dried filter residue is sent into reduction calcining under inert atmosphere in calciner, first at 300 ℃～500 ℃, calcine 3 hours～4 hours, then being warming up to 750 ℃ calcines 8 hours～10 hours again, after cooling, with deionized water, wash again, until Ph value is 7.0 neutrality, by excessive lithium hydroxide washing to the greatest extent;
(4), after the dry materials upper step being obtained, send in airslide disintegrating mill and pulverize, until raw meal particle size reaches nanoscale, the LiFePO4 that to obtain take silver oxide be conductive agent.
In step, the ferric phosphate described in is (1) phosphate dihydrate iron in the present invention, ferric iron content>=29.70 ﹪, and tap density is 1.13 g/cm
3～1.59g/cm
3, Fe:P=0.99:1, it is spherical that granularity pattern is class, particle size distribution is at 0.1 μ m～10 μ m, 3 μ m≤D50≤5 μ m, maximum particle size is not more than 10 μ m, and the concentration of its sulfate, calcium, magnesium, sodium, potassium, copper, nickel, cadmium, lead, zinc, chromium, chlorine is all less than 10ppm.
In step, the lithium carbonate described in is (1) battery-level lithium carbonate in the present invention.
The present invention step (2) in, 105 ℃～110 ℃ of baking temperatures, are 0.5 ﹪～1.0 ﹪ by filter residue and drying to moisture content.
The present invention step (3) in, inert gas is that nitrogen content is the nitrogen of 99.99 ﹪, reducing agent is Town Gas or organic carbohydrate.
The present invention step (4) in, 105 ℃～110 ℃ of baking temperatures, are 0.5 ﹪～1.0 ﹪ by dry materials to moisture content.
Owing to adopting technique scheme, the present invention has realized goal of the invention preferably, method simple possible, and synthetic LiFePO4 is pure phase, has good chemical property, steady quality, more than electric gram volume is greater than 150mAh/g, tap density is 1.65 g/cm
3～1.70 g/cm
3use half-cell to be assembled into button battery, under the multiplying power of 0.5C, this battery is carried out to charge-discharge test, average electric discharge specific discharge capacity is greater than 150mAh/g, initial charge specific capacity is greater than 160 mAh/g, first discharge specific capacity is greater than 150 mAh/g, and circulation coulomb efficiency is greater than 95.0 ﹪, and charging constant current ratio is greater than 98 ﹪, in electric discharge, threshold voltage is greater than 3.4V, and after 100 circulations, capability retention is greater than 97.0 ﹪.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
(1) by weight, in ferric phosphate: lithium carbonate: silver nitrate: the ratio of deionized water=1.0:0.2～0.22:0.001～0.002:0.5～0.6 joins in ball mill ball milling 3 hours～4 hours by above-mentioned raw materials, and material is fully mixed;
The present embodiment is got respectively ferric phosphate: lithium carbonate: silver nitrate: deionized water=18 kilogram: 3.6 kilograms: 0.018 kilogram: 9 kilograms join in ball mill ball milling 4 hours, material is fully mixed.
The ferric phosphate of step described in is (1) phosphate dihydrate iron, ferric iron content>=29.70 ﹪, and tap density is 1.13 g/cm
3～1.59g/cm
3, Fe:P=0.99:1, it is spherical that granularity pattern is class, particle size distribution is at 0.1 μ m～10 μ m, 3 μ m≤D50≤5 μ m, maximum particle size is not more than 10 μ m, and the concentration of its sulfate, calcium, magnesium, sodium, potassium, copper, nickel, cadmium, lead, zinc, chromium, chlorine is all less than 10ppm.Described lithium carbonate is battery-level lithium carbonate.
(2) the material after ball milling filters to remove through flame filter press and mixes mother liquor, obtains filter residue and sends in drying machine dry;
The present invention step (2) in, 105 ℃～110 ℃ of baking temperatures, are 0.5 ﹪～1.0 ﹪ by filter residue and drying to moisture content.105 ℃ of the present embodiment baking temperatures, filter residue and drying to moisture content is 1.0 ﹪.
(3) dried filter residue is sent into reduction calcining under inert atmosphere in calciner, first at 300 ℃～500 ℃, calcine 3 hours～4 hours, then being warming up to 750 ℃ calcines 8 hours～10 hours again, after cooling, with deionized water, wash again, until Ph value is 7.0 neutrality, by excessive lithium hydroxide washing to the greatest extent;
The present invention step (3) in, inert gas is that nitrogen content is the nitrogen of 99.99 ﹪, reducing agent is Town Gas or organic carbohydrate.The present embodiment reducing agent is Town Gas, first at 450 ℃, calcines 3 hours, is then warming up to 750 ℃ and calcines 8 hours again, cooling after again with deionized water washing, until Ph value is 7.0 neutrality, excessive lithium hydroxide washing is use up.
(4), after the dry materials upper step being obtained, send in airslide disintegrating mill and pulverize, until raw meal particle size reaches nanoscale, the LiFePO4 that to obtain take silver oxide be conductive agent.
The present invention step (4) in, 105 ℃～110 ℃ of baking temperatures, are 0.5 ﹪～1 ﹪ by dry materials to moisture content.105 ℃ of the present embodiment baking temperatures, filter residue and drying to moisture content is 1.0 ﹪.
The LiFePO4 product of preparation detects by X-ray diffractometer (XRD, Rigaku Rigaku), can find out that LiFePO4 is pure phase.Use half-cell to be assembled into button battery above-mentioned LiFePO4 carries out charge-discharge test to this battery and on average discharges specific discharge capacity for 158mAh/g under the multiplying power of 0.5C, initial charge specific capacity is 165 mAh/g, first discharge specific capacity is 157 mAh/g, circulation coulomb efficiency 95.2 ﹪, charging constant current is than 98 ﹪, threshold voltage 3.42V in electric discharge, capability retention 97.6 ﹪ after 100 circulations.
The present invention adopts silver oxide as the conductive agent of LiFePO4 product, and silver oxide undergoes no deterioration, large as conductive agent capacitance per unit volume amount, and the tap density of the LiFePO4 product of preparation is greater than 1.6g/cm3, can keep superperformance in the normal state.
Embodiment 2:
The present embodiment is got respectively ferric phosphate: lithium carbonate: silver nitrate: deionized water=18 kilogram: 3.6 kilograms: 0.018 kilogram: 2 kilograms of 9 kilograms and reducing agent sucrose join in ball mill ball milling 4 hours together, and material is fully mixed.Step (3) in, the present embodiment reducing agent is the sucrose in organic carbohydrate.Remaining with embodiment 1.
The LiFePO4 product of preparation detects by X-ray diffractometer (XRD, Rigaku Rigaku), can find out that LiFePO4 is pure phase.Use half-cell to be assembled into button battery above-mentioned LiFePO4 carries out charge-discharge test to this battery and on average discharges specific discharge capacity for 151mAh/g under the multiplying power of 0.5C, initial charge specific capacity is 167 mAh/g, first discharge specific capacity is 153 mAh/g, circulation coulomb efficiency 91.2 ﹪, charging constant current is than 98.7 ﹪, threshold voltage 3.4V in electric discharge, capability retention 97.9 ﹪ after 100 circulations.
With the synthetic LiFePO4 of said method, there is good chemical property as can be seen here, can in wide spectrum, use.
Claims (6)
1. a production method for LiFePO4, is characterized in that it comprises the following steps:
(1) by weight, in ferric phosphate: lithium carbonate: silver nitrate: the ratio of deionized water=1.0:0.2～0.22:0.001～0.002:0.5～0.6 joins in ball mill ball milling 3 hours～4 hours by above-mentioned raw materials, and material is fully mixed;
(2) the material after ball milling filters to remove through flame filter press and mixes mother liquor, obtains filter residue and sends in drying machine dry;
(3) dried filter residue is sent into reduction calcining under inert atmosphere in calciner, first at 300 ℃～500 ℃, calcine 3 hours～4 hours, then being warming up to 750 ℃ calcines 8 hours～10 hours again, after cooling, with deionized water, wash again, until Ph value is 7.0 neutrality, by excessive lithium hydroxide washing to the greatest extent;
(4), after the dry materials upper step being obtained, send in airslide disintegrating mill and pulverize, until raw meal particle size reaches nanoscale, the LiFePO4 that to obtain take silver oxide be conductive agent.
2. the production method of LiFePO4 according to claim 1, is characterized in that the ferric phosphate described in is (1) phosphate dihydrate iron in step, ferric iron content>=29.70 ﹪, and tap density is 1.13 g/cm
3～1.59g/cm
3, Fe:P=0.99:1, it is spherical that granularity pattern is class, particle size distribution is at 0.1 μ m～10 μ m, 3 μ m≤D50≤5 μ m, maximum particle size is not more than 10 μ m, and the concentration of its sulfate, calcium, magnesium, sodium, potassium, copper, nickel, cadmium, lead, zinc, chromium, chlorine is all less than 10ppm.
3. the production method of LiFePO4 according to claim 1, is characterized in that the lithium carbonate described in is (1) battery-level lithium carbonate in step.
4. the production method of LiFePO4 according to claim 1, it is characterized in that step (2) in, 105 ℃～110 ℃ of baking temperatures, are 0.5 ﹪～1.0 ﹪ by filter residue and drying to moisture content.
5. the production method of LiFePO4 according to claim 1, it is characterized in that step (3) in, inert gas is that nitrogen content is the nitrogen of 99.99 ﹪, reducing agent is Town Gas or organic carbohydrate.
6. the production method of LiFePO4 according to claim 1, it is characterized in that step (4) in, 105 ℃～110 ℃ of baking temperatures, are 0.5 ﹪～1.0 ﹪ by dry materials to moisture content.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107814372A (en) * | 2017-11-02 | 2018-03-20 | 沈阳国科金能新材料有限公司 | A kind of preparation method and application of lithium iron phosphate positive material |
| CN110970608A (en) * | 2019-12-19 | 2020-04-07 | 湖南裕能新能源电池材料有限公司 | Lithium iron battery material and preparation method thereof |
| CN116053471A (en) * | 2023-03-08 | 2023-05-02 | 宁德新能源科技有限公司 | Negative electrode material, negative electrode plate, secondary battery and power utilization device |
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| CN101314463A (en) * | 2007-05-28 | 2008-12-03 | 上海比亚迪有限公司 | Method of producing active compound lithium iron phosphate of lithium ion secondary battery anode |
| CN101332985A (en) * | 2008-07-31 | 2008-12-31 | 福建师范大学 | Method for preparing conducting phosphide-doped positive electrode material of LiFePO4 |
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2013
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Patent Citations (5)
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| CN1803591A (en) * | 2005-12-22 | 2006-07-19 | 上海交通大学 | Method for preparing lithium ion battery anode material lithium ion phosphate |
| CN101314463A (en) * | 2007-05-28 | 2008-12-03 | 上海比亚迪有限公司 | Method of producing active compound lithium iron phosphate of lithium ion secondary battery anode |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107814372A (en) * | 2017-11-02 | 2018-03-20 | 沈阳国科金能新材料有限公司 | A kind of preparation method and application of lithium iron phosphate positive material |
| CN110970608A (en) * | 2019-12-19 | 2020-04-07 | 湖南裕能新能源电池材料有限公司 | Lithium iron battery material and preparation method thereof |
| CN116053471A (en) * | 2023-03-08 | 2023-05-02 | 宁德新能源科技有限公司 | Negative electrode material, negative electrode plate, secondary battery and power utilization device |
| CN116053471B (en) * | 2023-03-08 | 2023-08-18 | 宁德新能源科技有限公司 | Negative electrode material, negative electrode plate, secondary battery and power utilization device |
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