微波辅助溶剂热法制备LiMn1<italic style="font-style: italic">-x</italic>Mg<italic style="font-style: italic">x</italic>PO4/C正极材料

朱计划; 陈姚; 丘秀莲; 黄宇明; 郑成; 杨伟

doi:10.11949/0438-1157.20190027

您当前的位置：

首页 >

文章列表页 >

微波辅助溶剂热法制备LiMn₁_-xMg_xPO₄/C正极材料

材料化学工程与纳米技术 | 更新时间：2026-07-24

- 微波辅助溶剂热法制备LiMn₁_-xMg_xPO₄/C正极材料
- Preparation of LiMn₁_-xMg_xPO₄/C cathode materials by microwave-assisted solvothermal method
- 化工学报 2019年70卷第7期页码：2775-2785
- 作者机构：
  
  广州大学化学化工学院，广东广州 510006
- 作者简介：
  
  朱计划（1992—），男，硕士研究生，497691268@qq.com
  杨伟（1982—），男，博士，副教授，wyang@gzhu.edu.cn
- 基金信息：
  
  国家自然科学基金项目(21878058);广东省自然科学基金项目(2018A030313423)
- DOI：10.11949/0438-1157.20190027
  中图分类号： TM 912
- 收稿：2019-01-09，
  
  修回：2019-04-16，
  
  网络首发：2026-07-24，
  
  纸质出版：2019-07-05
- 稿件说明：
移动端阅览
朱计划, 陈姚, 丘秀莲, 黄宇明, 郑成, 杨伟. 微波辅助溶剂热法制备LiMn_1-_xMg_xPO₄/C正极材料[J]. 化工学报, 2019, 70(7): 2775-2785 DOI: 10.11949/0438-1157.20190027.

ZHU Jihua, CHEN Yao, QIU Xiulian, HUANG Yuming, ZHENG Cheng, YANG Wei. Preparation of LiMn_1-_xMg_xPO₄/C cathode materials by microwave-assisted solvothermal method[J]. CIESC Journal, 2019, 70(7): 2775-2785 DOI: 10.11949/0438-1157.20190027.
朱计划, 陈姚, 丘秀莲, 黄宇明, 郑成, 杨伟. 微波辅助溶剂热法制备LiMn_1-_xMg_xPO₄/C正极材料[J]. 化工学报, 2019, 70(7): 2775-2785 DOI: 10.11949/0438-1157.20190027. DOI：

ZHU Jihua, CHEN Yao, QIU Xiulian, HUANG Yuming, ZHENG Cheng, YANG Wei. Preparation of LiMn_1-_xMg_xPO₄/C cathode materials by microwave-assisted solvothermal method[J]. CIESC Journal, 2019, 70(7): 2775-2785 DOI: 10.11949/0438-1157.20190027. DOI：

摘要

采用微波辅助溶剂热法的合成途径，成功制备出镁掺杂的磷酸锰镁锂(LiMn

/C)电极材料。采用X-射线衍射、扫描电镜、恒电流充放电等测试方法对晶体结构，微观形态和电化学性能进行表征。结果表明微波辅助溶剂热样品LiMn

-x

/C为具备较大比表面积和介孔结构的片层状形貌材料。该片层状纳米结构有利于锂离子脱嵌/镶嵌反应，Mg

掺杂在片层状纳米晶体合成过程中发挥着重要作用，可以提高材料的电化学活性和电化学表现。其中LiMn

0.95

0.05

/C材料在0.1 C和5 C倍率下最高可逆放电容量分别为141.2和95.3 (mA·h)/g，具备较高的放电容量和倍率性能表现。与传统溶剂热法相比，微波辅助溶剂热法的反应时间显著降低且制备得到的材料具备优异的电化学性能表现，对于制备其他锂离子电池材料具有指导意义。

Abstract

Magnesium-doped lithium manganese phosphate(LiMn

-x

/C) electrode materials were successfully prepared by microwave-

assisted solvothermal synthesis. X-Ray diffraction

scanning electron microscope

thermogravimetry and Brunaur-Emmett-Teller method were employed to characterize crystal structures and morphology

and the electrochemical characteristics of the as-prepared materials were evaluated by galvanostatic charge/discharge

cyclic voltammetry and AC impedance method. The results showed that the plate-like LiMn

-x

/C samples

which were synthesized from the microwave-assisted solvothermal method

possessed large specific surface area and well-defined mesoporous structure. In particular

doping exerts a significant effect on synthesizing flake-like nanocrystal which favors lithium-ion extraction/insertion reactions

improving the electrochemical activity and electrochemical performance of LiMnPO

/C material. As a result

the LiMn

0.95

0.05

/C nanoparticle exhibited a high reversible capacity of 141.2 and 95.3 (mA·h)/g at 0.1 C and 5 C

respectively

exhibited outstanding charge/discharge performance and rate capability. Compared to conventional solvothermal synthetic route

microwave-assisted solvothermal approach led to a significant decrease in the reaction time and the as-prepared material possessed excellent electrochemical performance. It is extraordinary and remarkable for the preparation of high-performance LiMnPO

cathode material

providing a new method for the preparation of electrode materials for Li-ion batteries.

关键词

Keywords

references

Armand M , Tarascon J M . Building better batteries [J ] . Nature , 2008 , 451 ( 7179 ): 652 - 657 .

Dunn B , Kamath H , Tarascon J M . Electrical energy storage for the grid: a battery of choices [J ] . Science , 2011 , 334 ( 6058 ): 928 - 935 .

Nitta N , Wu F , Lee J T , et al . Li-ion battery materials: present and future [J ] . Materials Today , 2015 , 18 ( 5 ): 252 - 264 .

Padhi A K , Najundaswamy K S , Goodenough J B . Phospho-olivines as positive-electrode materials for rechargeable lithium batteries [J ] . Journal of the Electrochemical Society , 1997 , 144 ( 4 ): 1188 - 1194 .

Masquelier C , Croguennec L . Polyanionic (phosphates, silicates, sulfates) frameworks as electrode materials for rechargeable Li (or Na) batteries [J ] . Chemical Reviews , 2013 , 113 ( 8 ): 6552 - 6591 .

Aravindan V , Gnanaraj J , Lee Y S , et al . LiMnPO 4 —a next generation cathode material for lithium-ion batteries [J ] . Journal of Materials Chemistry A , 2013 , 1 ( 11 ): 3518 - 3539 .

Deng Y F , Yang C X , Zou K X , et al . Recent advances of Mn-rich LiFe 1 -y Mn y PO 4 (0.5 ≤ y < 1.0) cathode materials for high energy density lithium ion batteries [J ] . Advanced Energy Materials , 2017 , 7 ( 13 ): 1614 - 6840 .

Devaraju M K , Honma I . Hydrothermal and solvothermal process towards development of LiMPO 4 (M=Fe, Mn) nanomaterials for lithium-ion batteries [J ] . Advanced Energy Materials , 2012 , 2 ( 3 ): 284 - 297 .

Morgan D , van der Ven A , Ceder G . Li conductivity in Li x MPO 4 (M = Mn, Fe, Co, Ni) olivine materials [J ] . Electrochemical and Solid State Letters , 2004 , 7 ( 2 ): A30 -A 32 .

Yamada A , Hosoya M , Chung S C , et al . Olivine-type cathodes: achievements and problems [J ] . Journal of Power Sources , 2003 , 119-121 ( 6 ): 232 - 238 .

Zhao M , Fu Y , Xu N , et al . High performance LiMnPO 4 /C prepared by a crystallite size control method [J ] . Journal of Materials Chemistry A , 2014 , 2 ( 36 ): 15070 - 15077 .

Dinh H C , Mho S I , Yeo I H , et al . Superior high rate capability of size-controlled LiMnPO 4 /C nanosheets with preferential orientation [J ] . RSC Advances , 2015 , 5 ( 122 ): 100709-100714 .

Lei Z H , Naveed A , Lei J Y , et al . High performance nano-sized LiMn 1- x Fe x PO 4 cathode materials for advanced lithium-ion batteries [J ] . RSC Advances , 2017 , 7 ( 69 ): 43708 - 43715 .

Yan S Y , Wang C Y , Gu R M , et al . Enhanced kinetic behaviors of LiMn 0.5 Fe 0.5 PO 4 /C cathode material by Fe substitution and carbon coating [J ] . Journal of Solid State Electrochemistry , 2015 , 19 ( 10 ): 2943 - 2950 .

Oh S M , Oh S W , Yoon C S , et al . High-performance carbon-LiMnPO 4 nanocomposite cathode for lithium batteries [J ] . Advanced Functional Materials , 2010 , 20 ( 19 ): 3260 - 3265 .

Wang F X , WangX W , Chang Z , et al . Electrode materials with tailored facets for electrochemical energy storage [J ] . Nanoscale Horizons , 2016 , 1 ( 4 ): 272 - 289 .

Jung Y H , Park W B , Pyo M , et al . A multi-element doping design for a high-performance LiMnPO 4 cathode via metaheuristics computation [J ] . Journal of Materials Chemistry A , 2017 , 5 ( 19 ): 8939 - 8945

Lu Q , Hutchings G S , Zhou Y , et al . Nanostructured flexible Mg-modified LiMnPO 4 matrix as high-rate cathode materials for Li-ion batteries [J ] . Journal of Materials Chemistry A , 2014 , 2 ( 18 ): 6368 - 6373 .

Wang Y , Yang H , Wu C Y , et al . Facile and controllable one-pot synthesis of nickel-doped LiMn 0.8 Fe 0.2 PO 4 nanosheets as high performance cathode materials for lithium-ion batteries [J ] . Journal of Materials Chemistry A , 2017 , 5 ( 35 ): 18674 - 18683 .

Duan J G , Hu G R , Cao Y B , et al . Synthesis of high-performance Fe-Mg-co-doped LiMnPO 4 /C via a mechano-chemical liquid-phase activation technique [J ] . Ionics , 2016 , 22 ( 5 ): 609 - 619

Zhang J , Luo S , Wang Q , et al . Yttrium substituting in Mn site to improve electrochemical kinetics activity of sol-gel synthesized LiMnPO 4 /C as cathode for lithium ion battery [J ] . Journal of Solid State Electrochemistry , 2017 , 21 ( 11 ): 3189 - 3194 .

Wang C , Li S , Han Y , et al . Assembly of LiMnPO 4 nanoplates into microclusters as a high-performance cathode in lithium-ion batteries [J ] . ACS Applied Materials & Interfaces , 2017 , 9 ( 33 ): 27618 - 27624

Pan X , Gao Z . Hydrothermal synthesis and electrochemical properties of dispersed LiMnPO 4 wedges [J ] . Crystengcomm , 2013 , 15 ( 38 ): 7808 - 7814 .

Guo H , Wu C , Xie J , et al . Controllable synthesis of high-performance LiMnPO 4 nanocrystals by a facile one-spot solvothermal process [J ] . Journal of Materials Chemistry A , 2014 , 2 ( 27 ): 10581 - 10588 .

Assat G , Manthiram A . Rapid microwave-assisted solvothermal synthesis of non-olivine cecum polymorphs of LiMPO 4 (M = Mn, Fe, Co, and Ni) at low temperature and pressure [J ] . Inorganic Chemistry , 2015 , 54 ( 20 ): 10015 - 10022 .

Zhu J N , Li W C , Cheng F , et al . Synthesis of LiMnPO 4 /C with superior performance as Li-ion battery cathodes by a two-stage microwave solvothermal process [J ] . Journal of Materials Chemistry A , 2015 , 3 ( 26 ): 13920 - 13925 .

Ahmet Ö . Positive effects of a particular type of microwave-assisted methodology on the electrochemical properties of olivine LiMPO 4 (M=Fe, Co and Ni) cathode materials [J ] . Chemical Engineering Journal , 2018 , 331 : 501 - 509 .

Cui Y T , Xu N , Kou L Q , et al . Enhanced electrochemical performance of different morphological LiMnPO 4 /C nanoparticles from hollow-sphere Li 3 PO 4 precursor via a delicate polyol-assisted hydrothermal method [J ] . Journal of Power Sources , 2014 , 249 ( 3 ): 42 - 47 .

Guo H , Wu C , Liao L , et al . Performance improvement of lithium manganese phosphate by controllable morphology tailoring with acid-engaged nano engineering [J ] . Inorganic Chemistry , 2015 , 54 ( 2 ): 667 - 674 .

Wang L , Zhang H , Liu Q , et al . Modifying high-voltage olivine-type LiMnPO 4 cathode via Mg substitution in high-orientation crystal [J ] . ACS Applied Energy Materials , 2018 , 1 ( 11 ): 5928 - 5935 .

Hu C , Yi H , Fang H , et al . Improving the electrochemical activity of LiMnPO 4 via Mn-site co -substitution with Fe and Mg [J ] . Electrochemistry Communications , 2010 , 12 ( 12 ): 1784 - 1787 .

Kumar P R , Venkateswarlu M , Misra M , et al . Enhanced conductivity and electrical relaxation studies of carbon-coated LiMnPO 4 nanorods [J ] . Ionics , 2012 , 19 ( 3 ): 461 - 469 .

Zhao Y , Peng L L , Liu B R , et al . Single-crystalline LiFePO 4 nanosheets for high-rate Li-ion batteries [J ] . Nano Letters , 2014 , 14 ( 5 ): 2849 - 2853 .

Bakenov Z , Taniguchi I . LiMn 1 -x Mg x PO 4 /C cathodes for lithium batteries prepared by a combination of spray pyrolysis with wet ball milling [J ] . Journal of the Electrochemical Society , 2010 , 157 ( 4 ): A430 -A 436 .

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

不同碳导电剂对铁-空气电池性能的影响

垂直多孔碳包覆的FeF3正极的构筑及储锂性能研究

Co-Mn比例调控对LiNi0.8Co0.10-yMn0.05+yAl0.05O2材料性能影响探究

利用表面改性制备磷酸锰锂/石墨烯锂离子电池复合材料

温和条件下太阳能光热催化氨合成与分解的研究进展

微波辅助溶剂热法制备LiMn1-xMgxPO4/C正极材料

Preparation of LiMn1-xMgxPO4/C cathode materials by microwave-assisted solvothermal method

DOI：10.11949/0438-1157.20190027

摘要

Abstract

关键词

Keywords

references

微波辅助溶剂热法制备LiMn₁_-xMg_xPO₄/C正极材料

Preparation of LiMn₁_-xMg_xPO₄/C cathode materials by microwave-assisted solvothermal method