CN103633326B - The production method of LiFePO4 - Google Patents
The production method of LiFePO4 Download PDFInfo
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- CN103633326B CN103633326B CN201310697763.1A CN201310697763A CN103633326B CN 103633326 B CN103633326 B CN 103633326B CN 201310697763 A CN201310697763 A CN 201310697763A CN 103633326 B CN103633326 B CN 103633326B
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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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- 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
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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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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses the production method of the LiFePO4 of a kind of product quality and stable performance, it is characterized in that it comprises the following steps: by weight, in ferric phosphate: lithium carbonate: silver nitrate: above-mentioned raw materials is joined ball milling in ball mill by the ratio of deionized water=1.0:0.2 ~ 0.22:0.001 ~ 0.002:0.5 ~ 0.6, filtration drying, reduction calcining, after pulverizing, obtained nanoscale take silver oxide as the LiFePO4 of conductive agent, the inventive method simple possible, the LiFePO4 of synthesis is pure phase, there is good chemical property, steady quality, electricity gram volume is greater than more than 150mAh/g, tap density is 1.65g/cm
3~ 1.70g/cm
3use half-cell to be assembled into button battery, under the multiplying power of 0.5C, charge-discharge test is carried out to this battery, averaged discharge specific discharge capacity is greater than 150mAh/g, circulation coulombic efficiency is greater than 95.0 ﹪, charging constant current ratio is greater than 98 ﹪, electric discharge mean voltage is greater than 3.4V, and after 100 circulations, capability retention is greater 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 satisfied society is 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, due to the toxicity of cobalt acid lithium in anode material for lithium-ion batteries, cycle performance and the high-temperature behavior of LiMn2O4 are poor, lithium nickelate preparation difficulty, make the application of these materials be greatly limited.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 about 3.4V, there is aboundresources, environmental friendliness, long service life, the advantages such as thermal stability is good, cause people to 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 produced can be poor, use half-cell to be assembled into button battery, under the multiplying power of 0.5C, charge-discharge test is carried out to this battery, averaged discharge specific discharge capacity is less than 125mAh/g, seriously constrains its large-scale application.For this reason, researcher has done very large effort in the transmission speed of the conductivity and quickening lithium ion that improve it, and as carbon coated, add conducting polymer, adulterate the metal ion that overprices, and synthesizes the material etc. of more small particle diameter.By first preparing the ferric phosphate of special appearance, be more also the focus studied at present by certain approach synthesizing iron lithium phosphate.
Summary of the invention
The object of this invention is to provide the production method of 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, and a kind of production method of LiFePO4, it comprises the following steps:
(1) by weight, in ferric phosphate: lithium carbonate: silver nitrate: above-mentioned raw materials to be joined in ball mill ball milling 3 hours ~ 4 hours by the ratio of deionized water=1.0:0.2 ~ 0.22:0.001 ~ 0.002:0.5 ~ 0.6, makes material fully mix;
(2) the material after ball milling filters through flame filter press and removes mixing mother liquor, obtains filter residue and sends in drying machine dry;
(3) dried filter residue is sent in calciner and is reduced calcining in an inert atmosphere, first calcine 3 hours ~ 4 hours at 300 DEG C ~ 500 DEG C, then be warming up to 750 DEG C and calcine 8 hours ~ 10 hours again, deionized water is spent again after cooling, until Ph value is 7.0 neutrality, by the washing of excessive lithium hydroxide to the greatest extent;
(4) after the dry materials upper step obtained, send in airslide disintegrating mill and pulverize, until raw meal particle size reaches nanoscale, obtaining take silver oxide as the LiFePO4 of conductive agent.
The present invention step (1) described in ferric phosphate be phosphate dihydrate iron, ferric iron content>=29.70 ﹪, tap density is 1.13g/cm
3~ 1.59g/cm
3, Fe:P=0.99:1, granularity pattern is that class is spherical, particle size distribution is at 0.1 μm ~ 10 μm, 3 μm≤D50≤5 μm, maximum particle size is not more than 10 μm, and the concentration of its sulfate, calcium, magnesium, sodium, potassium, copper, nickel, cadmium, lead, zinc, chromium, chlorine is all less than 10ppm.
The present invention step (1) described in lithium carbonate be battery-level lithium carbonate.
The present invention step (2) in, filter residue and drying to moisture content is 0.5 ﹪ ~ 1.0 ﹪ by baking temperature 105 DEG C ~ 110 DEG C.
The present invention step (3) in, the nitrogen of inert gas to be nitrogen content be 99.99 ﹪, reducing agent is Town Gas or organic carbohydrate.
The present invention step (4) in, dry materials to moisture content is 0.5 ﹪ ~ 1.0 ﹪ by baking temperature 105 DEG C ~ 110 DEG C.
Owing to adopting technique scheme, the present invention achieves goal of the invention preferably, method simple possible, and the LiFePO4 of synthesis is pure phase, has good chemical property, steady quality, and electric gram volume is greater than more than 150mAh/g, and tap density is 1.65g/cm
3~ 1.70g/cm
3use half-cell to be assembled into button battery, under the multiplying power of 0.5C, charge-discharge test is carried out to this battery, averaged discharge specific discharge capacity is greater than 150mAh/g, initial charge specific capacity is greater than 160mAh/g, first discharge specific capacity is greater than 150mAh/g, and circulation coulombic efficiency is greater than 95.0 ﹪, and charging constant current ratio is greater than 98 ﹪, electric discharge mean 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: above-mentioned raw materials to be joined in ball mill ball milling 3 hours ~ 4 hours by the ratio of deionized water=1.0:0.2 ~ 0.22:0.001 ~ 0.002:0.5 ~ 0.6, makes material fully mix;
The present embodiment gets ferric phosphate respectively: lithium carbonate: silver nitrate: deionized water=18 kilogram: 3.6 kilograms: 0.018 kilogram: 9 kilograms to join in ball mill ball milling 4 hours, and material is fully mixed.
Step (1) described in ferric phosphate be phosphate dihydrate iron, ferric iron content>=29.70 ﹪, tap density is 1.13g/cm
3~ 1.59g/cm
3, Fe:P=0.99:1, granularity pattern is that class is spherical, particle size distribution is at 0.1 μm ~ 10 μm, 3 μm≤D50≤5 μm, maximum particle size is not more than 10 μm, 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 through flame filter press and removes mixing mother liquor, obtains filter residue and sends in drying machine dry;
The present invention step (2) in, filter residue and drying to moisture content is 0.5 ﹪ ~ 1.0 ﹪ by baking temperature 105 DEG C ~ 110 DEG C.The present embodiment baking temperature 105 DEG C, filter residue and drying to moisture content is 1.0 ﹪.
(3) dried filter residue is sent in calciner and is reduced calcining in an inert atmosphere, first calcine 3 hours ~ 4 hours at 300 DEG C ~ 500 DEG C, then be warming up to 750 DEG C and calcine 8 hours ~ 10 hours again, deionized water is spent again after cooling, until Ph value is 7.0 neutrality, by the washing of excessive lithium hydroxide to the greatest extent;
The present invention step (3) in, the nitrogen of inert gas to be nitrogen content be 99.99 ﹪, reducing agent is Town Gas or organic carbohydrate.The present embodiment reducing agent is Town Gas, first calcines 3 hours at 450 DEG C, is then warming up to 750 DEG C and calcines 8 hours again, spend deionized water again after cooling, until Ph value is 7.0 neutrality, by the washing of excessive lithium hydroxide to the greatest extent.
(4) after the dry materials upper step obtained, send in airslide disintegrating mill and pulverize, until raw meal particle size reaches nanoscale, obtaining take silver oxide as the LiFePO4 of conductive agent.
The present invention step (4) in, dry materials to moisture content is 0.5 ﹪ ~ 1 ﹪ by baking temperature 105 DEG C ~ 110 DEG C.The present embodiment baking temperature 105 DEG C, filter residue and drying to moisture content is 1.0 ﹪.
The LiFePO4 product of preparation is detected by X-ray diffractometer (XRD, Rigaku Rigaku), can find out that LiFePO4 is pure phase.Above-mentioned LiFePO4 being used half-cell to be assembled into button battery, under the multiplying power of 0.5C, carry out charge-discharge test averaged discharge specific discharge capacity to this battery be 158mAh/g, initial charge specific capacity is 165mAh/g, first discharge specific capacity is 157mAh/g, circulation coulombic efficiency 95.2 ﹪, charging constant current is than 98 ﹪, electric discharge mean voltage 3.42V, 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, and large as conductive agent capacitance per unit volume amount, 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 gets ferric phosphate respectively: lithium carbonate: silver nitrate: deionized water=18 kilogram: 3.6 kilograms: 0.018 kilogram: 9 kilograms and reducing agent sucrose 2 kilograms to join in ball mill ball milling together 4 hours, 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 is detected by X-ray diffractometer (XRD, Rigaku Rigaku), can find out that LiFePO4 is pure phase.Above-mentioned LiFePO4 being used half-cell to be assembled into button battery, under the multiplying power of 0.5C, carry out charge-discharge test averaged discharge specific discharge capacity to this battery be 151mAh/g, initial charge specific capacity is 167mAh/g, first discharge specific capacity is 153mAh/g, circulation coulombic efficiency 91.2 ﹪, charging constant current is than 98.7 ﹪, electric discharge mean voltage 3.4V, capability retention 97.9 ﹪ after 100 circulations.
With the LiFePO4 of said method synthesis, there is good chemical property as can be seen here, can use in wide spectrum.
Claims (3)
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: above-mentioned raw materials to be joined in ball mill ball milling 3 hours ~ 4 hours by the ratio of deionized water=1.0:0.2 ~ 0.22:0.001 ~ 0.002:0.5 ~ 0.6, makes material fully mix;
Step (1) described in ferric phosphate be phosphate dihydrate iron, ferric iron content>=29.70 ﹪, tap density is 1.13g/cm
3~ 1.59g/cm
3, Fe:P=0.99:1, granularity pattern is that class is spherical, particle size distribution is at 0.1 μm ~ 10 μm, 3 μm≤D50≤5 μm, maximum particle size is not more than 10 μm, 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 through flame filter press and removes mixing mother liquor, obtains filter residue and sends in drying machine dry;
(3) dried filter residue is sent in calciner and is reduced calcining in an inert atmosphere, first calcine 3 hours ~ 4 hours at 300 DEG C ~ 500 DEG C, then be warming up to 750 DEG C and calcine 8 hours ~ 10 hours again, deionized water is spent again after cooling, until pH value is 7.0 neutrality, by the washing of excessive lithium hydroxide to the greatest extent;
Step (3) in, the nitrogen of inert gas to be nitrogen content be 99.99 ﹪, reducing agent is Town Gas or organic carbohydrate;
(4) after the dry materials upper step obtained, send in airslide disintegrating mill and pulverize, until raw meal particle size reaches nanoscale, obtaining take silver oxide as the LiFePO4 of conductive agent.
2. the production method of LiFePO4 according to claim 1, it is characterized in that step (2) in, filter residue and drying to moisture content is 0.5 ﹪ ~ 1.0 ﹪ by baking temperature 105 DEG C ~ 110 DEG C.
3. the production method of LiFePO4 according to claim 1, it is characterized in that step (4) in, dry materials to moisture content is 0.5 ﹪ ~ 1.0 ﹪ by baking temperature 105 DEG C ~ 110 DEG C.
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| CN103633326B true CN103633326B (en) | 2016-01-20 |
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| 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 |
| CN116779848A (en) * | 2023-03-08 | 2023-09-19 | 宁德新能源科技有限公司 | Negative electrode material, negative electrode plate, secondary battery and power utilization device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101112979A (en) * | 2007-06-27 | 2008-01-30 | 广州市鹏辉电池有限公司 | Solid-phase method for preparation of high-density spherical-like ferric phosphate lithium |
| 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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| CN100420075C (en) * | 2005-12-22 | 2008-09-17 | 上海交通大学 | Method for preparing lithium ion battery anode material lithium ion phosphate |
| CN101314463B (en) * | 2007-05-28 | 2011-04-06 | 上海比亚迪有限公司 | Method of producing active compound lithium iron phosphate of lithium ion secondary battery anode |
| CN101373831B (en) * | 2007-08-24 | 2012-07-25 | 比克国际(天津)有限公司 | Method for preparing lithium ion battery anode material lithium iron phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101112979A (en) * | 2007-06-27 | 2008-01-30 | 广州市鹏辉电池有限公司 | Solid-phase method for preparation of high-density spherical-like ferric phosphate lithium |
| 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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