CN103496741A - Li3VO4 negative electrode material prepared by solid-phase reaction method - Google Patents
Li3VO4 negative electrode material prepared by solid-phase reaction method Download PDFInfo
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- CN103496741A CN103496741A CN201310440371.7A CN201310440371A CN103496741A CN 103496741 A CN103496741 A CN 103496741A CN 201310440371 A CN201310440371 A CN 201310440371A CN 103496741 A CN103496741 A CN 103496741A
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Abstract
The invention provides a novel negative electrode material Li3VO4 of a lithium ion battery, which is prepared by using vanadium pentoxide and lithium carbonate as precursors. According to the principle, high-temperature heating is utilized to supply reaction energy to reacting raw materials, so that the reacting raw materials gradually undergo a solid-phase reaction, and Li3VO4 with excellent crystallization performance can be obtained. According to the Li3VO4 material, the first charging and discharging capacities are respectively 1002 and 739mAh/g, the charging and discharging capacities after 50 times of circulation are respectively 639 and 643mAh/g, the average granularity of particles of the material is 5 mu m, and the particles are formed by massive small particles with sizes of about 300nm.
Description
Technical field
The present invention relates to a class Novel cathode material for lithium ion battery, particularly a kind of Li
3vO
4preparation method and storage lithium characteristic thereof, belong to field of electrochemical power source.
Background technology
Lithium ion battery is the third generation small battery after nickel-cadmium cell, nickel metal hydride battery, there is the advantages such as operating voltage is high, specific energy large, the discharge potential curve is steady, self-discharge is little, have extended cycle life, low-temperature performance is good, memoryless, pollution-free, can meet portable type electronic product miniaturization, lightweight, free of contamination requirement.Lithium ion battery has been widely used in the electronic products such as mobile communication, notebook computer at present, but, as the power supply as mobile equipments such as electric vehicle, man-made satellite, field operations communications, also needs further to improve specific energy and the power of battery.The key of research and development high-energy-density, high power lithium ion cell is to design and prepare the electrode materials of heavy body, high rate capability.At present, positive electrode material is generally containing lithium transition group metallic oxide (LiCoO
2, LiFePO
4, LiN
1-y-zmn
yco
zo
zdeng), the possibility that increases substantially the positive electrode material specific storage on existing positive electrode material architecture basics is little, further improves the significantly raising that capacity of lithium ion battery can only rely on the negative material capacity.Traditional graphite cathode material density is lower, and volume capacity is lower, and therefore, the research and development Novel cathode material for lithium ion battery becomes a key factor that affects the lithium ion battery development.Ternary lithium, vanadium compound system have shown good chemical property as lithium ion battery electrode material, thereby have been subject to studying comparatively widely and paying close attention to.Wherein, Li
3vO
4be ternary lithium, the barium oxide that a kind of relative molecular weight is less, as lithium ion battery electrode material, be expected to show higher theoretical capacity, at present, about the research of its chemical property, there is not yet report.Based on above research background, this patent relates to a kind of simple method of invention and prepares novel tertiary compound L i
3vO
4material, using that it has shown excellent stable circulation performance as lithium ion battery negative.
Summary of the invention
Purpose of the present invention be take Vanadium Pentoxide in FLAKES and Quilonum Retard and is prepared Novel cathode material for lithium ion battery Li as precursor
3vO
4.Its principle has utilized heat to provide reaction energy for reaction raw materials, makes reaction raw materials that solid state reaction occur gradually, finally obtains the Li that crystal property is good
3vO
4.
Li involved in the present invention
3vO
4synthesis material is Vanadium Pentoxide in FLAKES and Quilonum Retard, and the reaction occurred in the solid state reaction process is:
V
2O
5 + 3Li
2CO
3 → 2Li
3VO
4 + 3CO
2↑ (1)
In the material preparation process, first by Vanadium Pentoxide in FLAKES and Quilonum Retard in molar ratio 1:2-5 take mixing, ball milling was placed in heating container after 1 hour, was heated to 400 ~ 700 ℃ of reactions 1 ~ 10 hour under air conditions, naturally cooling can obtain Li
3vO
4sample.
Li involved in the present invention
3vO
4negative material and preparation method have following outstanding feature:
(1) Li
3vO
4first the charge and discharge capacity be respectively 1002,739mAh/g, after 50 circulations, the charge and discharge capacity is respectively 639,643 mAh/g;
(2) synthesis technique is simple, easy handling, and the material preparation cost is low;
(3) the gained sample purity is high, and crystal property is good;
(4) prepared material capacity is high, the cycle performance excellence;
(5) Li
3vO
4the particle median size is 5 um, and particle consists of the small-particle that is about 300nm of taking measurements greatly.
the accompanying drawing explanation:
The prepared Li of Fig. 1 embodiment 1
3vO
4xRD figure spectrum;
The SEM figure of Fig. 2 embodiment 1;
The discharge curve first (a) of Fig. 3 embodiment 1 and cycle performance figure (b), wherein current density 0.1 mA cm
-2.
embodiment:
Embodiment 1
Vanadium Pentoxide in FLAKES and Quilonum Retard be take to mol ratio and take and mix as 1:3, ball milling 1 hour, be transferred in crucible or quartz boat, and crucible or quartz boat are moved in high temperature process furnances, and under 500 ℃ of conditions, in air, calcining is 5 hours, and naturally cooling can obtain Li
3vO
4sample.Result shows, prepared sample is Li through the XRD figure spectrum analysis
3vO
4, as shown in Figure 1, all diffraction peak and the Li of rhombic system in figure
3vO
4correspondence, lattice parameter is
a=0.6319 nm, b=0.5448 nm,
c=0.4940 nm, corresponding to XRD card JCPDS, No. 38-1247; Strong and sharp-pointed diffraction peak shows, prepared Li
3vO
4crystal property is good.Diffraction peak without other materials is detected, and shows that prepared sample purity is very high.Prepared Li
3vO
4through SEM scanning, as seen from Figure 2, prepared Li
3vO
4the particle median size is 5 um.Particle consists of the small-particle that is about 300nm of taking measurements greatly.With prepared Li
3vO
4particle shows that as lithium ion battery negative material the charge and discharge capacity is 739,1002 mAh/g first, and after 50 circulations, the charge and discharge capacity is respectively 639,643 mAh/g, has shown fabulous stable circulation performance (as shown in Figure 3).
Embodiment 2
Vanadium Pentoxide in FLAKES and Quilonum Retard be take to mol ratio and take and mix as 1:2, ball milling 1 hour, be transferred in crucible or quartz boat, and crucible or quartz boat are moved in high temperature process furnances, and under 400 ℃ of conditions, in air, calcining is 7 hours, and naturally cooling can obtain Li
3vO
4sample.
Embodiment 3
Vanadium Pentoxide in FLAKES and Quilonum Retard be take to mol ratio and take and mix as 1:5, ball milling 1 hour, be transferred in crucible or quartz boat, and crucible or quartz boat are moved in high temperature process furnances, and under 700 ℃ of conditions, in air, calcining is 6 hours, and naturally cooling can obtain Li
3vO
4sample.
Embodiment 4
Vanadium Pentoxide in FLAKES and Quilonum Retard be take to mol ratio and take and mix as 1:3, ball milling 1 hour, be transferred in crucible or quartz boat, and crucible or quartz boat are moved in high temperature process furnances, and under 600 ℃ of conditions, in air, calcining is 9 hours, and naturally cooling can obtain Li
3vO
4sample.
Claims (4)
1. a solid phase reaction method prepares Li
3vO
4negative material is characterized in that: take Vanadium Pentoxide in FLAKES and Quilonum Retard as raw material, ball milling prepares Li by high temperature sintering
3vO
4.
2. solid phase reaction method according to claim 1 prepares Li
3vO
4negative material is characterized in that: Vanadium Pentoxide in FLAKES and Quilonum Retard are mixed to ball milling 1 ~ 3 hour with mol ratio 1:2-5.
3. solid phase reaction method according to claim 1 prepares Li
3vO
4negative material is characterized in that: under air conditions, and 400 ~ 700 ℃ of lower sintering 1 ~ 10 hour.
4. solid phase reaction method according to claim 1 prepares Li
3vO
4negative material is characterized in that: described Li
3vO
4be particulate state, mean sizes is less than 5 um.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104124446A (en) * | 2014-07-01 | 2014-10-29 | 三峡大学 | Graphite/Li3VO4 lithium ion battery composite negative electrode material and preparation method thereof |
| CN104393241A (en) * | 2014-11-14 | 2015-03-04 | 三峡大学 | Preparation method of lithium-ion battery negative electrode material |
| CN104409713A (en) * | 2014-11-14 | 2015-03-11 | 三峡大学 | Novel lithium ion battery anode material and preparation method thereof |
| CN105133016A (en) * | 2015-10-09 | 2015-12-09 | 新疆大学 | Preparation method and application of lithium vanadate nonlinear optical crystal |
| CN105810928A (en) * | 2014-12-30 | 2016-07-27 | 微宏动力***（湖州）有限公司 | Biphase negative electrode material for lithium ion secondary battery and preparation method thereof |
| CN106299301A (en) * | 2016-09-27 | 2017-01-04 | 华北理工大学 | A kind of Li with excellent storage lithium performance3vO4the pattern of nano wire regulates and controls method mutually with thing |
| CN106299356A (en) * | 2016-09-27 | 2017-01-04 | 华北理工大学 | A kind of lithium ion battery lithium vanadate Li3vO4the efficient microwave radiation synthesis process of nano flower |
| CN110294494A (en) * | 2019-07-25 | 2019-10-01 | 哈尔滨工业大学 | Lithium vanadate anode mends lithium additive and its application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101853939A (en) * | 2009-03-31 | 2010-10-06 | 比亚迪股份有限公司 | Cathodic active material as well as preparation method and battery thereof |
| CN103145419A (en) * | 2013-04-01 | 2013-06-12 | 桂林理工大学 | Microwave dielectric ceramic Li3VO4 capable of being sintered at low temperature and preparation method thereof |
-
2013
- 2013-09-25 CN CN201310440371.7A patent/CN103496741B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101853939A (en) * | 2009-03-31 | 2010-10-06 | 比亚迪股份有限公司 | Cathodic active material as well as preparation method and battery thereof |
| CN103145419A (en) * | 2013-04-01 | 2013-06-12 | 桂林理工大学 | Microwave dielectric ceramic Li3VO4 capable of being sintered at low temperature and preparation method thereof |
Non-Patent Citations (7)
| Title |
|---|
| DONG JIN KIM ET AL.: ""Growth and characterization of Li3VO4 single crystals by the Czochralski method"", 《JOURNAL OF CRYSTAL GROWTH》, vol. 217, 31 December 2000 (2000-12-31), pages 383 - 387 * |
| HUIQIAO LI ET AL.: ""Li3VO4：A Promising Insertion Anode Material for Lithium-Ion Batteries"", 《ADV.ENGRGY MATER.》, vol. 3, 6 December 2012 (2012-12-06), XP022935038, DOI: 10.1016/S1001-0521(07)60049-7 * |
| SHIN’ICHI SAKATA ET AL.: ""Preparation of low-temperature Li3VO4 single crystal by floating zone technique"", 《JOURNAL OF CRYSTAL GROWTH》, vol. 135, 31 December 1994 (1994-12-31), pages 555 - 560, XP000484440, DOI: 10.1016/0022-0248(94)90147-3 * |
| WON-TAE KIM ET AL.: ""Synthesis and lithium intercalation properties of Li3VO4 as a new anode material for secondary lithium batteries"", 《JOURNAL OF POWER SOURCES》, vol. 244, 6 February 2013 (2013-02-06), XP028692057, DOI: 10.1016/j.jpowsour.2013.01.163 * |
| 刘进等: ""固相配位法制备低结晶度钒酸锂电极材料"", 《电源技术 研究与设计》, vol. 30, no. 7, 31 July 2006 (2006-07-31), pages 552 - 554 * |
| 宋秀芹等: ""Li3VO4离子导体材料的合成及其离子导电性"", 《中国有色金属学报》, vol. 10, no. 4, 31 August 2000 (2000-08-31), pages 591 - 595 * |
| 张泽志等: ""低结晶度钒酸锂电极材料的固相配位合成研究"", 《河南教育学院学报(自然科学版)》, vol. 18, no. 4, 31 December 2009 (2009-12-31), pages 22 - 24 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104124446A (en) * | 2014-07-01 | 2014-10-29 | 三峡大学 | Graphite/Li3VO4 lithium ion battery composite negative electrode material and preparation method thereof |
| CN104393241A (en) * | 2014-11-14 | 2015-03-04 | 三峡大学 | Preparation method of lithium-ion battery negative electrode material |
| CN104409713A (en) * | 2014-11-14 | 2015-03-11 | 三峡大学 | Novel lithium ion battery anode material and preparation method thereof |
| CN105810928A (en) * | 2014-12-30 | 2016-07-27 | 微宏动力***（湖州）有限公司 | Biphase negative electrode material for lithium ion secondary battery and preparation method thereof |
| CN105810928B (en) * | 2014-12-30 | 2019-02-22 | 微宏动力***（湖州）有限公司 | A kind of lithium ion secondary battery two-phase negative electrode material and preparation method thereof |
| CN105133016A (en) * | 2015-10-09 | 2015-12-09 | 新疆大学 | Preparation method and application of lithium vanadate nonlinear optical crystal |
| CN106299301A (en) * | 2016-09-27 | 2017-01-04 | 华北理工大学 | A kind of Li with excellent storage lithium performance3vO4the pattern of nano wire regulates and controls method mutually with thing |
| CN106299356A (en) * | 2016-09-27 | 2017-01-04 | 华北理工大学 | A kind of lithium ion battery lithium vanadate Li3vO4the efficient microwave radiation synthesis process of nano flower |
| CN106299301B (en) * | 2016-09-27 | 2019-06-18 | 苏州科技大学 | A kind of Li with excellent storage lithium performance3VO4The pattern of nano wire mutually regulates and controls method with object |
| CN106299356B (en) * | 2016-09-27 | 2019-06-21 | 苏州科技大学 | A kind of lithium ion battery lithium vanadate Li3VO4The efficient microwave radiation synthesis process of nano flower |
| CN110294494A (en) * | 2019-07-25 | 2019-10-01 | 哈尔滨工业大学 | Lithium vanadate anode mends lithium additive and its application |
| CN110294494B (en) * | 2019-07-25 | 2022-04-01 | 哈尔滨工业大学 | Lithium vanadate anode lithium supplement additive and application thereof |
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Effective date of registration: 20221118 Address after: 405400 Chongqing Kai Zhou Industrial Park, Zhao Jia light industrial food industry park No. 5 standard workshop. Patentee after: CHONGQING JIABAOCHENG ENERGY TECHNOLOGY Co.,Ltd. Address before: 443002 No. 8, University Road, Yichang, Hubei Patentee before: CHINA THREE GORGES University |
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