CN102903915A - Sol-gel method for preparing positive electrode material lithium iron phosphate - Google Patents
Sol-gel method for preparing positive electrode material lithium iron phosphate Download PDFInfo
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- CN102903915A CN102903915A CN2012103093403A CN201210309340A CN102903915A CN 102903915 A CN102903915 A CN 102903915A CN 2012103093403 A CN2012103093403 A CN 2012103093403A CN 201210309340 A CN201210309340 A CN 201210309340A CN 102903915 A CN102903915 A CN 102903915A
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- 238000003980 solgel method Methods 0.000 title claims abstract description 11
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title abstract 3
- 239000007774 positive electrode material Substances 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 5
- 239000002738 chelating agent Substances 0.000 claims abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 12
- 239000010405 anode material Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000008118 PEG 6000 Substances 0.000 claims description 4
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- -1 Polyethylene Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 150000002696 manganese Chemical class 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 229910010710 LiFePO Inorganic materials 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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Classifications
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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
Abstract
The invention relates to a sol-gel method for preparing a positive electrode material lithium iron phosphate. According to the invention, manganese salt, lithium salt, a chelating agent, and phosphate with a molar ratio of 1.9-2.1:1.9-2.1:0.95-1.1:1.9-2.1 are dissolved in water and are well mixed; the pH value of the mixture is regulated to 8-10 by using ammonia water; the mixture is stirred until the mixture is viscous; the mixture is dried and is sintered for 12-24h under a non-oxidative atmosphere and a temperature of 600-700 DEG C, such that lithium iron phosphate is obtained. According to the invention, a synthesizing process is simplified. In the sol step, the raw materials are mixed to a molecular grade, and sintering temperature is reduced. Organics are decomposed during a pretreatment step, and carbon is produced and is uniformly dispersed in a precursor, such that crystal grain excessive growth can be effectively inhibited. The particle size of a synthesized material is uniformly distributed and is small, and the conductivity of the material is improved. Charge-discharge performances and cycling performance of a sample are improved. The method is simple and convenient, and is easy to control. The preparation cost is reduced.
Description
Technical field
The present invention relates to the method that a kind of sol-gel process prepares LiFePO 4 of anode material.
Background technology
Lithium ion battery is considered to best at present environmental protection ideal source, is subject to science and technology and industrial quarters and pays much attention to, and be used widely.LiFePO
4Anode material for lithium-ion batteries as having potentiality has high potential.This material energy density is high, and abundant raw material, cost are low, environmentally friendly.
LiFePO
4Main preparation methods has solid phase method, carbothermic method and hydro thermal method etc., is difficult to the synthetic good LiFePO of chemical property by traditional preparation method
4How to control granule size, improve conductivity and ion diffusion rate and become LiFePO
4The main direction of research.
Summary of the invention
The technical problem to be solved in the present invention provides the method that a kind of sol-gel process prepares LiFePO 4 of anode material, the particle diameter of product is evenly distributed, tiny, conductivity and chemical property improve.
The present invention solves the problems of the technologies described above with following technical scheme:
Technique concrete steps of the present invention are:
Mol ratio is respectively 1.9-2.1:1.9-2.1:0.95-1.1:1.9-2.1 molysite, lithium salts, chelating agent and phosphate to be mixed after water-soluble, the ammoniacal liquor of employing 15% is regulated pH at 8-10, be stirred to thickness, after the drying with its under non-oxidizing atmosphere in 600 ℃ of-700 ℃ of sintering 12-24h, cooling obtains LiFePO4.
Described molysite is ironic citrate or ferric nitrate.
Described lithium salts is lithium hydroxide, lithium nitrate or lithium acetate.
Described chelating agent is PEG-6000, Polyethylene glycol-2000, PEG-4000 or PEG-6000 0.
Described phosphate is ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate.
Described non-oxidizing atmosphere is argon gas, nitrogen or hydrogen.
The present invention has simplified synthesis technique, in the colloidal sol step raw material is mixed into molecular level, reduce sintering temperature, organic substance decomposes Formed and is scattered in equably in the presoma at pretreatment stage, but too growing up of establishment sample crystal grain makes that institute's synthetic material particle diameter is evenly distributed, tiny, conductivity improves; Synthesis temperature and sintering time are adjustable, can obtain varigrained material; The charge-discharge performance of sample and cycle performance improve; Method of the present invention is simple and convenient, be easy to control, and preparation cost reduces.
Description of drawings
Fig. 1 is No. 2 sample LiFePO of the embodiment of the invention 1
4XRD figure.
Fig. 2 is No. 2 sample LiFePO of the embodiment of the invention 1
4SEM figure.
Fig. 3 is No. 2 sample LiFePO of the embodiment of the invention 1
4The first charge-discharge curve.
Fig. 4 is No. 2 sample LiFePO of the embodiment of the invention 1
4The cycle performance curve.
Embodiment
Embodiment 1:
Mix after 0.19mol ferric nitrate and 0.21mol lithium hydroxide, 0.105mol PEG-4000 and 0.21mol ammonium di-hydrogen phosphate is water-soluble, add with 15% ammoniacal liquor and regulate pH to 9, be stirred to thickness, after dry under argon gas atmosphere respectively at 600 ℃, 650 ℃, 700 ℃ sintering 18h, be LiFePO after the cooling
4Resulting product shows to be LiFePO through X-ray diffraction analysis
4, do not have any dephasign, can obtain the particle diameter of product by SEM about 0.1 μ m.With resulting product be assembled into the experiment button cell survey its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, its first discharge capacity and the circulation 30 times after discharge capacity see Table 1.
The experiment condition of table 1 embodiment 1 and result
Embodiment 2:
Mix after 0.20mol ironic citrate and 0.20mol lithium acetate, 0.10mol PEG-10000 and 0.20mol DAP is water-soluble, adopt 15% ammoniacal liquor adjusting pH to 10, be stirred to thickness, after dry under nitrogen atmosphere in 600 ℃ of sintering 12,18 and 24h, be LiFePO after the cooling
4Resulting product shows to be LiFePO through X-ray diffraction analysis
4, do not have any dephasign, can obtain the particle diameter of product by SEM about 0.1 μ m.With resulting product be assembled into the experiment button cell survey its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, its first discharge capacity and the circulation 30 times after discharge capacity see Table 2.
The experiment condition of table 2 embodiment 2 and result
Claims (6)
1. a sol-gel process prepares the method for LiFePO 4 of anode material, it is characterized in that processing step is:
Mol ratio is respectively molysite, lithium salts, chelating agent and the phosphate of 1.9-2.1:1.9-2.1:0.95-1.1:1.9-2.1 to be mixed after water-soluble, ammoniacal liquor with 15% is regulated pH at 8-10, be stirred to thickness, after the drying with its under non-oxidizing atmosphere in 600 ℃ of-700 ℃ of sintering 12-24h, cooling obtains LiFePO4.
2. sol-gel process as claimed in claim 1 prepares the method for LiFePO 4 of anode material, it is characterized in that molysite is ironic citrate or ferric nitrate.
3. sol-gel process as claimed in claim 1 prepares the method for LiFePO 4 of anode material, it is characterized in that lithium salts is lithium hydroxide, lithium nitrate or lithium acetate.
4. sol-gel process as claimed in claim 1 prepares the method for LiFePO 4 of anode material, it is characterized in that chelating agent is PEG-6000, Polyethylene glycol-2000, PEG-4000 or PEG-6000 0.
5. sol-gel process as claimed in claim 1 prepares the method for LiFePO 4 of anode material, it is characterized in that phosphate is ammonium dihydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate.
6. sol-gel process as claimed in claim 1 prepares the method for LiFePO 4 of anode material, it is characterized in that non-oxidizing atmosphere is argon gas, nitrogen or hydrogen.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103093403A CN102903915A (en) | 2012-08-28 | 2012-08-28 | Sol-gel method for preparing positive electrode material lithium iron phosphate |
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|---|---|---|---|
| CN2012103093403A CN102903915A (en) | 2012-08-28 | 2012-08-28 | Sol-gel method for preparing positive electrode material lithium iron phosphate |
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| CN102903915A true CN102903915A (en) | 2013-01-30 |
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| CN2012103093403A Pending CN102903915A (en) | 2012-08-28 | 2012-08-28 | Sol-gel method for preparing positive electrode material lithium iron phosphate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104733728A (en) * | 2013-12-24 | 2015-06-24 | 中国电子科技集团公司第十八研究所 | Preparation method of high-power lithium iron phosphate material |
| CN105764846A (en) * | 2013-11-26 | 2016-07-13 | Sk新技术株式会社 | Lithium composite phosphate-based compound and preparation method therefor |
| CN112864384A (en) * | 2021-03-31 | 2021-05-28 | 神华准能资源综合开发有限公司 | Preparation method and application of positive electrode material lithium iron phosphate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941687A (en) * | 2010-09-27 | 2011-01-12 | 彩虹集团公司 | Method for synthetizing lithium ion battery anode material LiFePO4 |
| CN102324494A (en) * | 2010-07-20 | 2012-01-18 | 上海大象能源科技有限公司 | Lithium iron phosphate / nano-powder tube oxide composite cathode material and preparation method thereof |
| CN102530907A (en) * | 2011-12-10 | 2012-07-04 | 桂林理工大学 | Method for preparing lithium ion battery anode material manganese lithium phosphate by using sol-gel method |
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2012
- 2012-08-28 CN CN2012103093403A patent/CN102903915A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324494A (en) * | 2010-07-20 | 2012-01-18 | 上海大象能源科技有限公司 | Lithium iron phosphate / nano-powder tube oxide composite cathode material and preparation method thereof |
| CN101941687A (en) * | 2010-09-27 | 2011-01-12 | 彩虹集团公司 | Method for synthetizing lithium ion battery anode material LiFePO4 |
| CN102530907A (en) * | 2011-12-10 | 2012-07-04 | 桂林理工大学 | Method for preparing lithium ion battery anode material manganese lithium phosphate by using sol-gel method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105764846A (en) * | 2013-11-26 | 2016-07-13 | Sk新技术株式会社 | Lithium composite phosphate-based compound and preparation method therefor |
| CN105764846B (en) * | 2013-11-26 | 2019-01-15 | Sk新技术株式会社 | Lithium compound phosphoric acid salt compound and preparation method thereof |
| US10421664B2 (en) | 2013-11-26 | 2019-09-24 | Sk Innovation Co., Ltd. | Lithium composite phosphate-based compound and preparation method therefor |
| CN104733728A (en) * | 2013-12-24 | 2015-06-24 | 中国电子科技集团公司第十八研究所 | Preparation method of high-power lithium iron phosphate material |
| CN112864384A (en) * | 2021-03-31 | 2021-05-28 | 神华准能资源综合开发有限公司 | Preparation method and application of positive electrode material lithium iron phosphate |
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Application publication date: 20130130 |