CN101456550B - Method for preparing lithium ionic cell anode material lithium vanadium fluorophosphate by hydro-thermal synthesis reaction - Google Patents
Method for preparing lithium ionic cell anode material lithium vanadium fluorophosphate by hydro-thermal synthesis reaction Download PDFInfo
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- CN101456550B CN101456550B CN2009101138022A CN200910113802A CN101456550B CN 101456550 B CN101456550 B CN 101456550B CN 2009101138022 A CN2009101138022 A CN 2009101138022A CN 200910113802 A CN200910113802 A CN 200910113802A CN 101456550 B CN101456550 B CN 101456550B
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- lithium
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- anode material
- fluoride
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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 discloses a method for preparing a lithium ion battery anode material, namely vanadium lithium fluophosphate, through hydrothermal synthesis reaction, which comprises: dissolving ammonium metavanadate, phosphate, organic acid, lithium salt and villaumite into water according to the mol ratio of 1.9-2.1:1.9:2.1:0.95-1.1:1.9-2.1:1.9-2.1, making the mixture react for 1 to 4 days in a hydrothermal synthesis reaction kettle at a temperature of between 200 and 350 DEG C, and drying the mixture to obtain a finished product, namely LiVPO4F. The method is simple and convenient, is easy to control, has low cost, simplifies the synthesis technology, and improves the charge and discharge performance and the cycle performance of samples.
Description
Technical field
The present invention relates to the method that a kind of hydrothermal synthesis reaction prepares lithium ion battery anode material vanadium lithium phosphate.
Background technology
Lithium-ion secondary cell has a lot of good characteristics, has been widely used on portable type electronic product, communication tool, electromobile, the energy storage device.The performance of lithium ion battery depends on positive electrode material to a great extent.Wherein vanadium is the fluorophosphoric acid vanadium lithium (LiVPO in the positive electrode material
4F) because to have a reversibility good, the starting material source is abundant, specific storage higher (theoretical capacity is 156mAh/g), platform be than higher (4.2V vs Li
+/ Li) etc. advantage has caused the attention of height.But following shortcoming has hindered its practical application: V during (1) is synthetic
3+Easily be oxidized to V
5+, be difficult to obtain monophasic LiVPO
4F; 2) lithium ion is at LiVPO
4The diffusion difficulty causes the utilization ratio of active material low among the F; (3) LiVPO
4The specific conductivity of F itself is also very low, causes its heavy-current discharge performance poor.Existing research improves LiVPO by following several respects
4The performance of F: (1) adopts inert atmosphere to protect V
3+(2) LiVPO of synthetic small particle size
4F is to improve the diffusibility of lithium ion; (3) add conductive agent and improve specific conductivity.Bibliographical information synthesizes LiVPO at present
4The F material mainly adopts hydrogen reduction method and two step carbothermic methods.Hydrogen reduction method is owing to adopt pure H
2As reductive agent, when experimental implementation because H
2Inflammable and explosive character and very dangerous, be unfavorable for suitability for industrialized production.And shortcoming such as the skewness of institute's synthetic materials particle diameter and conductivity be low.Two go on foot carbothermic methods owing to take two-step reaction to synthesize, complex process, and synthesis condition harshness, and cause prepared material particle size skewness, conductivity and cycle performance bad.
Summary of the invention
The object of the present invention is to provide a kind of hydrothermal synthesis reaction to prepare anode material for lithium-ion batteries LiVPO
4The method of F.The synthetic sample temperature reduces, and the size distribution of sample is even, tiny, specific conductivity improves, reduces cost, thereby has improved the chemical property of sample, has simplified the purpose of synthesis 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: mix after the ammonium meta-vanadate of 1.9-2.1, phosphoric acid salt, organic acid, lithium salts and villiaumite are water-soluble, 200 ℃-350 ℃ reaction 1-4d are finished product LiVPO after the drying in the hydrothermal synthesis reaction still
4F.
Described lithium salts is a kind of in Lithium Acetate, lithium chloride, lithium nitrate and the lithium fluoride;
Described organic acid is a kind of in oxysuccinic acid, hexanodioic acid, propanedioic acid and the citric acid;
Described villiaumite is a kind of in Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride and the lithium fluoride;
Described phosphoric acid salt is a kind of in primary ammonium phosphate, Secondary ammonium phosphate, potassiumphosphate and the sodium phosphate;
The present invention directly uses the pentavalent vanadium to make raw material, has solved the easy problem of oxidation of vanadium ion; Simplified synthesis technique, can suppress too growing up of sample crystal grain effectively, made that institute's synthetic materials size distribution is even, tiny, specific conductivity improves; Adjustable between 200 ℃-350 ℃ of the synthesis temperatures, can obtain varigrained material; Generated time 1-4d can obtain varigrained material; Method is simple and convenient, be easy to control; The charge-discharge performance of sample and cycle performance improve, and have reduced cost.
Description of drawings
Fig. 1 is No. 4 sample LiVPO of the embodiment of the invention 1
4The XRD figure of F.
Fig. 2 is No. 4 sample LiVPO of the embodiment of the invention 1
4The SEM figure of F.
Fig. 3 is No. 4 sample LiVPO of the embodiment of the invention 1
4The first charge-discharge curve of F.
Fig. 4 is No. 4 sample LiVPO of the embodiment of the invention 1
4The cycle performance curve of F.
Embodiment
Embodiment 1:
0.19mol ammonium meta-vanadate and 0.21mol Lithium Acetate, 0.105mol oxysuccinic acid, 0.20mol Neutral ammonium fluoride and 0.21mol Secondary ammonium phosphate are mixed after water-soluble, react 1d respectively in 200 ℃, 250 ℃, 300 ℃, 350 ℃, be finished product LiVPO after the drying
4F.Resulting product shows to be LiVPO through X-ray diffraction analysis
4F does not have any dephasign, and the particle diameter that can obtain product by SEM is 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 1C, discharge and recharge, its first loading capacity and the circulation 30 times after loading capacity see Table 1.
The experiment condition of table 1 embodiment 1 and result
Embodiment 2:
0.20mol ammonium meta-vanadate and 0.20mol lithium fluoride, 0.10mol hexanodioic acid, 0.21mol Sodium Fluoride and 0.20mol primary ammonium phosphate are mixed after water-soluble, react 1,2,3 and 4d respectively in 350 ℃, be finished product LiVPO after the drying
4F.Resulting product shows to be LiVPO through X-ray diffraction analysis
4F does not have any dephasign, and the particle diameter that can obtain product by SEM is 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 1C, discharge and recharge, its first loading capacity and the circulation 30 times after loading capacity see Table 2.
The experiment condition of table 2 embodiment 2 and result
Embodiment 3:
0.205mol ammonium meta-vanadate and 0.19mol lithium chloride, 0.095mol citric acid, 0.19mol Potassium monofluoride and 0.19mol potassiumphosphate are mixed after water-soluble, react 4d respectively in 230 ℃, 280 ℃, 310 ℃, 330 ℃, be finished product LiVPO after the drying
4F.Resulting product shows to be LiVPO through X-ray diffraction analysis
4F does not have any dephasign, and the particle diameter that can obtain product by SEM is 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 1C, discharge and recharge, its first loading capacity and the circulation 30 times after loading capacity see Table 3.
The experiment condition of table 3 embodiment 3 and result
Embodiment 4:
0.21mol ammonium meta-vanadate and 0.195mol lithium nitrate, 0.11mol propanedioic acid, 0.195mol lithium fluoride and 0.205mol sodium phosphate are mixed after water-soluble, in 330 ℃ react 1.5,2.5,3.5 respectively, 3.8d, be finished product LiVPO after the drying
4F.Resulting product shows to be LiVPO through X-ray diffraction analysis
4F does not have any dephasign, and the particle diameter that can obtain product by SEM is 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 1C, discharge and recharge, its first loading capacity and the circulation 30 times after loading capacity see Table 4.
The experiment condition of table 4 embodiment 4 and result
Claims (1)
1. a hydrothermal synthesis reaction prepares the method for lithium ion battery anode material vanadium lithium phosphate, it is characterized in that concrete steps are: mol ratio is respectively 1.9-2.1: 1.9-2.1: 0.95-1.1: 1.9-2.1: mix after the ammonium meta-vanadate of 1.9-2.1, phosphoric acid salt, organic acid, lithium salts and villiaumite are water-soluble, 200 ℃-350 ℃ reaction 1-4d are finished product LiVPO after the drying in the hydrothermal synthesis reaction still
4F;
Described lithium salts is a kind of in Lithium Acetate, lithium chloride, lithium nitrate and the lithium fluoride; Described villiaumite is a kind of in Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride and the lithium fluoride; Described phosphoric acid salt is a kind of in primary ammonium phosphate, Secondary ammonium phosphate, potassiumphosphate and the sodium phosphate; Described organic acid is a kind of in oxysuccinic acid, propanedioic acid and the citric acid.
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| CN2009101138022A CN101456550B (en) | 2009-01-06 | 2009-01-06 | Method for preparing lithium ionic cell anode material lithium vanadium fluorophosphate by hydro-thermal synthesis reaction |
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| CN2009101138022A CN101456550B (en) | 2009-01-06 | 2009-01-06 | Method for preparing lithium ionic cell anode material lithium vanadium fluorophosphate by hydro-thermal synthesis reaction |
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| CN101456550B true CN101456550B (en) | 2011-03-30 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103840157B (en) * | 2014-03-19 | 2016-01-20 | 中南大学 | A kind of preparation method of nano-sheet lithium ion battery anode material vanadium lithium phosphate |
| CN103872289B (en) * | 2014-03-28 | 2017-04-05 | 中南大学 | A kind of ball-shaped lithium-ion battery anode material LiVPO4The preparation method of F |
| CN104401957B (en) * | 2014-10-13 | 2016-08-24 | 济南大学 | A kind of hydrothermal preparing process of positive electrode material of lithium secondary cell fluorophosphoric acid cobalt lithium |
| CN106495124A (en) * | 2015-09-08 | 2017-03-15 | 中国科学院过程工程研究所 | A kind of fluorophosphoric acid vanadium sodium salt, low temperature environment-friendly preparation method thereof and application thereof |
| CN105133012B (en) * | 2015-10-09 | 2018-06-29 | 新疆大学 | It is hydrated the preparation method and purposes of lithium borate nonlinear optical crystal |
| CN107799754A (en) * | 2017-10-31 | 2018-03-13 | 湖南国盛石墨科技有限公司 | A kind of preparation method of fluorophosphoric acid vanadium lithium/fluorinated graphene composite positive pole |
| CN109360980A (en) * | 2018-11-14 | 2019-02-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of positive electrode boric acid vanadium lithium and products thereof and application |
| CN111293307B (en) * | 2018-12-06 | 2021-06-29 | 中国科学院大连化学物理研究所 | Carbon-supported sodium vanadium fluorophosphate and preparation and application thereof |
| CN112850684B (en) * | 2019-11-27 | 2022-07-08 | 中国科学院大连化学物理研究所 | Preparation method and application of lithium vanadium fluorophosphate |
| CN112186163B (en) * | 2020-10-09 | 2021-12-28 | 西安交通大学 | Lithium vanadium fluorophosphate lithium-ion battery positive electrode material and synthesis method thereof |
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