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CN104852045A - Method for preparing spherical lithium iron phosphate with high polymer lattice dispersion technology - Google Patents

Method for preparing spherical lithium iron phosphate with high polymer lattice dispersion technology Download PDF

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Publication number
CN104852045A
CN104852045A CN201410056887.6A CN201410056887A CN104852045A CN 104852045 A CN104852045 A CN 104852045A CN 201410056887 A CN201410056887 A CN 201410056887A CN 104852045 A CN104852045 A CN 104852045A
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China
Prior art keywords
lithium
source
compound
dispersion technology
macromolecule network
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CN201410056887.6A
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Chinese (zh)
Inventor
常敬杭
程迪
徐云军
尹正中
王宗衡
李涛
韩红芳
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HENAN LONGKE NEW ENERGY CO Ltd
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HENAN LONGKE NEW ENERGY CO Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The invention discloses a method for preparing spherical lithium iron phosphate with a high polymer lattice dispersion technology. The method comprises the following steps: grinding a lithium source compound, an iron source compound and a phosphorus source compound in a ball mill, and performing heating treatment in a protective atmosphere to obtain a precursor; and grinding the precursor, a carbon source, a high polymer lattice reagent, an anion additive and a cationic additive in a mixed way in the ball mill, performing secondary calcination treatment in the protective atmosphere, and performing ball-milling crushing treatment to obtain a spherical lithium iron phosphate product. The spherical lithium iron phosphate prepared with the method disclosed by the invention has the advantages of high compaction density, excellent processing performance, high capacity, excellent cycle performance and the like. Moreover, the method is simple and easily-controllable in process, and suitable for large-scale industrial production.

Description

A kind of macromolecule network dispersion technology prepares the method for spherical LiFePO 4
Technical field
The present invention relates to a kind of preparation method of ball shape ferric phosphate lithium compound, particularly a kind of macromolecule network dispersion technology prepares the method for spherical LiFePO 4.
Background technology
The advantages such as lithium ion battery is high with its voltage, energy density large, long service life, memory-less effect and operating temperature range are wide, be rapidly spread since appearance, be widely used in the portable equipments such as mobile phone, MP3, UPS, camera, notebook computer.And along with growth in the living standard in recent years, and warm for global environment in countries in the world, the thinking of environmental protection and energy saving, electric bicycle replaces traditional vehicles just gradually, the research and development of electric automobile have been put on the schedule of future work by each big country especially, and this proposes larger challenge to high power capacity, high-power lithium ion battery.
Positive electrode is an important component part of lithium ion battery, in lithium ion battery charge and discharge process, not only to be provided in positive and negative lithium intercalation compound back and forth embedding/de-required lithium, but also the lithium will undertaken required for negative material surface formation SEI film, therefore, the key point that a kind of high performance positive electrode has become restriction lithium battery industry development now how is researched and developed.
Numerous as LiCoO 2, LiNiO 2, LiMn 2o 4, LiFePO 4in positive electrode Deng lithium battery, there is the LiFePO4 of olivine structural, due to its abundant raw material source, the advantage such as cost is low, environmental friendliness, security performance are high, specific capacity is high, discharge platform is steady, thermal stability and cycle performance are excellent, become the emphasis of current countries in the world research.In LiFePO4 preparation technology in the past, how to improve its conductivity is a difficult problem always, constrains its development.
Summary of the invention
The present invention is directed to the problems referred to above, provide a kind of method of macromolecule network dispersion technology synthesizing spherical LiFePO4.The anion of the metal cation and improvement capacity that improve circulation is incorporated into LiFePO 4inside lattice, thus obtain the spherical LiFePO 4 of function admirable.Technical characterstic of the present invention is the peptizaiton utilizing macromolecule network agent, processes under the condition of high temperature to the surface of lithium iron phosphate particles, the spheric granules of formation rule.
Principle of the present invention adds Doped anions additive, cationic additive and macromolecule network agent in the precursor obtained in pre-burning, utilize the peptizaiton of macromolecule network agent under the high temperature conditions, process is continued to lithium iron phosphate particles, make the carbon source added can be distributed to homogenizing the surface of LiFePO4, the spheric granules of formation rule.
A kind of macromolecule network dispersion technology of the present invention prepares the method for spherical LiFePO 4, comprises the following steps:
1), by Li source compound, Fe source compound and P source compound in grinding in ball grinder 0.1 ~ 10 hour, obtain mixture, in protective atmosphere, mixture is obtained precursor in 4 ~ 30 hours in 300 ~ 600 DEG C of heat treated;
2), by precursor, carbon source, macromolecule network agent, anionic additive, cationic additive mixed grinding 0.2 ~ 10 hour in ball mill; in protective atmosphere, carry out secondary clacining process 4 ~ 30 hours in 400 ~ 900 DEG C again, finally carry out ball mill crushing process and obtain spherical LiFePO4 product.
Described macromolecule network agent is one or more in polyvinyl alcohol, carboxymethyl cellulose, polyethylene glycol and polyacrylamide.
Described lithium source is one or more of lithium compound, described source of iron is one or more of iron compound, described phosphorus source is one or more of phosphate cpd, described carbon source is one or more in glucose, vitamin c, cyclodextrin, acetylene black, described cationic additive is one or more in Zn, Mg, Al, Cr, Nd, Nb element, and described anionic additive is one or both in S, F element.
Described lithium compound is lithium carbonate, lithium dihydrogen phosphate; Described iron compound is ferrous oxalate, ferric orthophosphate, iron oxide; Described phosphate cpd is ammonium dihydrogen phosphate, lithium dihydrogen phosphate, phosphoric acid.
The protective atmosphere of described heating treatment step and secondary clacining treatment process is one or more in nitrogen, argon gas and hydrogen.
The spherical LiFePO 4 utilizing method of the present invention to prepare, have the advantages such as compacted density is high, processing characteristics is excellent, capacity is high, cycle performance is excellent, and technique is simple and easy to control, is applicable to large-scale industrial production.
Embodiment
Embodiment 1:
Be that 1:1:1 prepares burden by lithium carbonate, ferrous oxalate and ammonium dihydrogen phosphate according to Li:Fe:P mol ratio, in grinding in ball grinder mixing in 2 hours, in nitrogen atmosphere, mixture obtained precursor in 25 hours in 500 DEG C of heat treated.By precursor, macromolecule network agent PVAC polyvinylalcohol, zinc oxide ZnO and lithium fluoride LiF according to the weight ratio of 1:0.03:0.01:0.01 mixed grinding 2 hours in ball mill; in protective atmosphere, carry out secondary clacining process 25 hours in 800 DEG C again, finally carry out ball mill crushing process and obtain spherical LiFePO4 product.
Embodiment 2:
Be that 1:1:1 prepares burden by lithium carbonate, iron oxide and lithium dihydrogen phosphate according to Li:Fe:P mol ratio, in grinding in ball grinder mixing in 2 hours, in nitrogen atmosphere, mixture obtained precursor in 15 hours in 500 DEG C of heat treated.By precursor, macromolecule network agent polyethylene glycol PEG, aluminium oxide Al 2o 3with lithium fluoride LiF according to the weight ratio of 1:0.03:0.01:0.02 mixed grinding 2.5 hours in ball mill, then carry out secondary clacining process 25 hours in 800 DEG C in protective atmosphere, finally carry out ball mill crushing process and obtain spherical LiFePO4 product.
Embodiment 3:
Be that 1:1:1 prepares burden by lithium carbonate, ferric orthophosphate and ammonium dihydrogen phosphate according to Li:Fe:P mol ratio, in grinding in ball grinder mixing in 2 hours, in nitrogen atmosphere, mixture obtained precursor in 20 hours in 500 DEG C of heat treated.By precursor, macromolecule network agent carboxymethyl sodium cellulosate CMC, magnesium oxide MgO and lithium fluoride LiF according to the weight ratio of 1:0.03:0.02:0.01 mixed grinding 3 hours in ball mill; in protective atmosphere, carry out secondary clacining process 25 hours in 800 DEG C again, finally carry out ball mill crushing process and obtain spherical LiFePO4 product.
Embodiment 4:
Be that 1:1:1 prepares burden by lithium carbonate, ferrous oxalate and phosphoric acid according to Li:Fe:P mol ratio, in grinding in ball grinder mixing in 3 hours, in nitrogen atmosphere, mixture obtained precursor in 15 hours in 500 DEG C of heat treated.By precursor, macromolecule network agent polypropylene amine PAM, chromium oxide Cr 2o 3with lithium fluoride LiF according to the weight ratio of 1:0.03:0.02:0.02 mixed grinding 4 hours in ball mill, then carry out secondary clacining process 20 hours in 800 DEG C in protective atmosphere, finally carry out ball mill crushing process and obtain spherical LiFePO4 product.
Experimental example:
The spherical LiFePO 4 that embodiment 1 ~ embodiment 4 is prepared and lithium ion battery negative material Delanium, take vinylidene as pole plate binding agent, make positive plate and the negative plate of lithium ion battery respectively, take microporous polypropylene membrane as electrode diaphragm, with volume ratio dimethyl carbonate: diethyl carbonate: the lithium hexafluoro phosphate of the 1mol/L of ethylene carbonate=1:1:1 is that electrolyte is assembled into lithium ion battery.
Lithium ion anode material performance table prepared by table 1 embodiment
Note: capability retention refers to the ratio of the capacity after being recycled to 1000 times and initial capacity.
Because this method utilizes the peptizaiton of macromolecule network agent, under the condition of high temperature, the surface of lithium iron phosphate particles is processed, the spheric granules of formation rule.More regular than the lithium iron phosphate particles of conventional method synthesis, good sphericity, thus there is outstanding chemical property.

Claims (5)

1. macromolecule network dispersion technology prepares a method for spherical LiFePO 4, it is characterized in that comprising the following steps:
1), by Li source compound, Fe source compound and P source compound in grinding in ball grinder 0.1 ~ 10 hour, obtain mixture, in protective atmosphere, mixture is obtained precursor in 4 ~ 30 hours in 300 ~ 600 DEG C of heat treated;
2), by precursor, carbon source, macromolecule network agent, anionic additive, cationic additive mixed grinding 0.2 ~ 10 hour in ball mill; in protective atmosphere, carry out secondary clacining process 4 ~ 30 hours in 400 ~ 900 DEG C again, finally carry out ball mill crushing process and obtain spherical LiFePO4 product.
2. a kind of macromolecule network dispersion technology according to claim 1 prepares the method for spherical LiFePO 4, it is characterized in that: described macromolecule network agent is one or more in polyvinyl alcohol, carboxymethyl cellulose, polyethylene glycol and polyacrylamide.
3. a kind of macromolecule network dispersion technology according to claim 1 prepares the method for spherical LiFePO 4, it is characterized in that: described lithium source is one or more of lithium compound, described source of iron is one or more of iron compound, described phosphorus source is one or more of phosphate cpd, described carbon source is one or more in glucose, vitamin c, cyclodextrin, acetylene black, described cationic additive is one or more in Zn, Mg, Al, Cr, Nd, Nb element, and described anionic additive is one or both in S, F element.
4. a kind of macromolecule network dispersion technology according to claim 3 prepares the method for spherical LiFePO 4, it is characterized in that: described lithium compound is lithium carbonate, lithium dihydrogen phosphate; Described iron compound is ferrous oxalate, ferric orthophosphate, iron oxide; Described phosphate cpd is ferric orthophosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, phosphoric acid.
5. a kind of macromolecule network dispersion technology according to claim 1 prepares the method for spherical LiFePO 4, it is characterized in that: the protective atmosphere of described heating treatment step and secondary clacining treatment process is one or more in nitrogen, argon gas and hydrogen.
CN201410056887.6A 2014-02-19 2014-02-19 Method for preparing spherical lithium iron phosphate with high polymer lattice dispersion technology Pending CN104852045A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106099103A (en) * 2016-08-24 2016-11-09 合肥国轩电池材料有限公司 A kind of preparation method of low-cost and high-performance LiFePO 4 material
CN113745521A (en) * 2021-09-05 2021-12-03 浙江大学 A kind of preparation method and application of zinc electrode material capable of suppressing self-discharge

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101369659A (en) * 2007-08-17 2009-02-18 深圳市比克电池有限公司 Novel lithium iron phosphate positive electrode material for lithium ion battery and preparation method thereof
CN101399343A (en) * 2007-09-25 2009-04-01 比亚迪股份有限公司 Preparing method of anode active material lithium iron phosphate for lithium ionic secondary cell
CN102126715A (en) * 2011-02-12 2011-07-20 新乡市中科科技有限公司 Preparation method of spherical lithium iron phosphate
US20130157133A1 (en) * 2011-11-17 2013-06-20 Brookhaven Science Associates, Llc Process for Producing Defect-Free Lithium Metal Phosphate Electrode Materials
CN103441271A (en) * 2013-08-16 2013-12-11 上海微纳科技有限公司 Anion-cation double-doped lithium iron phosphate anode material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101369659A (en) * 2007-08-17 2009-02-18 深圳市比克电池有限公司 Novel lithium iron phosphate positive electrode material for lithium ion battery and preparation method thereof
CN101399343A (en) * 2007-09-25 2009-04-01 比亚迪股份有限公司 Preparing method of anode active material lithium iron phosphate for lithium ionic secondary cell
CN102126715A (en) * 2011-02-12 2011-07-20 新乡市中科科技有限公司 Preparation method of spherical lithium iron phosphate
US20130157133A1 (en) * 2011-11-17 2013-06-20 Brookhaven Science Associates, Llc Process for Producing Defect-Free Lithium Metal Phosphate Electrode Materials
CN103441271A (en) * 2013-08-16 2013-12-11 上海微纳科技有限公司 Anion-cation double-doped lithium iron phosphate anode material and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106099103A (en) * 2016-08-24 2016-11-09 合肥国轩电池材料有限公司 A kind of preparation method of low-cost and high-performance LiFePO 4 material
CN113745521A (en) * 2021-09-05 2021-12-03 浙江大学 A kind of preparation method and application of zinc electrode material capable of suppressing self-discharge
CN113745521B (en) * 2021-09-05 2023-02-17 浙江大学 Preparation method and application of a zinc electrode material capable of inhibiting self-discharge

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