石墨烯引导LiFePO_4纳米片的一步溶剂热反应制备及其电化学性能
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摘要
针对本征低的电子导电率和锂离子迁移速率导致LiFePO_4较差的电化学性能,以石墨烯作为模板,采用一步溶剂热法制备梭形结构的LiFePO_4/石墨烯(LFP/G)复合正极材料;采用XRD和SEM等表征复合正极材料的物相结构和微观形貌,微米级梭型LiFePO_4颗粒是由平均厚度约为55 nm的纳米薄片堆叠而成。电化学性能研究结果表明:在0.1C倍率下,LFP/G复合正极材料的初始可逆比容量可达153.2 mA·h/g,高于相同条件下LiFePO_4的;在10C倍率下充放电时,LFP/G表现出高达85.9m A·h/g的可逆比容量,远高于LiFePO_4的可逆比容量(56.3m A·h/g),展现出明显增强的电化学倍率性能。
Aiming at the intrinsic shortcomings of LiFePO_4, a spindle-like LiFePO_4/graphene(LFP/G) composite cathode material was conveniently prepared by a one-step solvothermal method using graphene as a template. The as-obtained material was characterized by XRD, SEM and other methods. The results show that the micron-sized spindle-like LiFePO_4 particles are stacked by nano-sheets with average thickness of about 55 nm. Electrochemical performance study results show that the LFP/G composite cathode material exhibits an initial reversible specific capacity of 153.2 mA·h/g at0.1 C rate, which is higher than that of LiFePO_4 under the same conditions; when charged and discharged at 10 C rate,LFP/G exhibits a reversible specific capacity of up to 85.9 m A·h/g, which is much higher than that of LiFePO_4(56.3 mA·h/g), exhibiting significantly enhanced electrochemical rate performance.
Aiming at the intrinsic shortcomings of LiFePO_4, a spindle-like LiFePO_4/graphene(LFP/G) composite cathode material was conveniently prepared by a one-step solvothermal method using graphene as a template. The as-obtained material was characterized by XRD, SEM and other methods. The results show that the micron-sized spindle-like LiFePO_4 particles are stacked by nano-sheets with average thickness of about 55 nm. Electrochemical performance study results show that the LFP/G composite cathode material exhibits an initial reversible specific capacity of 153.2 mA·h/g at0.1 C rate, which is higher than that of LiFePO_4 under the same conditions; when charged and discharged at 10 C rate,LFP/G exhibits a reversible specific capacity of up to 85.9 m A·h/g, which is much higher than that of LiFePO_4(56.3 mA·h/g), exhibiting significantly enhanced electrochemical rate performance.
引文
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[23]YI Xu,ZHANG Fu-qin,ZHANG Bao,YU Wan-jing,DAIQiong-yu,HU Sheng-yong,HE Wen-jie,TONG Hui,ZHENGJun-chao,LIAO Ji-qiao.(010)facets dominated LiFePO4nano-flakes confined in 3D porous graphene network as a high-performance Li-ion battery cathode[J].Ceram Int,2018,44:18181-18188.
[24]WANG Qi,PENG Da-chun,CHEN Yu-xi,XIA Xiao-hong,LIUHong-bo,HE Yue-de,M,Qian.A facile surfactant-assisted self-assembly of LiFePO4/graphene composites with improved rate performance for lithium ion batteries[J].J Electroanal Chem,2018,818:68-75.
[25]LIU Tao,LESKES M,YU Wan-jing,MOORE A J,ZHOU Li-na,BAYLEY P M,KIM G,GREY C P.Cycling Li-O2 batteries via Li OH formation and decomposition[J].Science,2015,350(6260):530-533.
[2]JIN En-mei,JIN Bo,JUN D,PARK K,GU Hai-bon,KIM K.Astudy on the electrochemical characteristics of LiFePO4 cathode for lithium polymer batteries by hydrothermal method[J].JPower Sources,2008,178(2):801-806.
[3]GONG Chun-li,XUE Zhi-gang,WEN Sheng,YE Yun-sheng,XIE Xiao-lin.Advanced carbon materials/olivine LiFePO4composites cathode for lithium ion batteries[J].J Power Sources,2016,318(30):93-112.
[4]PADHI A K,NANJUNDASWAMY K S,GOODENOUGH J B.Phospho-olivines as positive-electrode materials for rechargeable lithium batteries[J].J Electrochem Soc,1997,144(4):1188-1194.
[5]KIM W,RYU W,HAN D,LIM S,EOM J,KWON H.Fabrication of graphene embedded LiFePO4 using a catalyst assisted self-assembly method as a cathode material for high power lithium-ion batteries[J].ACS Appl Mater Interfaces,2014,6(7):4731-4736.
[6]WANG Li,WANG Hai-bo,LIU Zhi-hong,XIAO Chen,DONGShan-mu,HAN Peng-xian,ZHANG Zhong-yi,ZHANGXiao-ying,BI Cai-feng,GUI Guang-lei.A facile method of preparing mixed conducting LiFePO4/graphene composites for lithium-ion batteries[J].Solid State Ionics,2010,181(37):1685-1689.
[7]ZHAO Yu,PENG Le-le,LIU Bo-rui,YU Gui-hua.Single-crystalline LiFePO4 nanosheets for high-rate Li-ion batteries[J].Nano Lett.,2014,14(5):2849-2853.
[8]TIAN Gui-ying,SCHEIBA F,PFAFFMANN L,FEDLER A,CHAKRAVADHANULA V S K,BALACHANDRAN G,ZHANZi-jian,EHRENBERG H.Electrostatic self-assembly of Li Fe PO4 cathodes on a three-dimensional substrate for lithium ion batteries[J].Electrochim Acta,2018,283:1375-1383.
[9]POSAIAH P,ZHU Jing-hui,HUSSAIN O M,LIU Zhong-gui,QIU Ye-jun.Well-dispersed rod-like LiFePO4 nanoparticles on reduced graphene oxide with excellent electrochemical performance for Li-ion batteries[J].J Electroanal Chem,2018,811:1-7.
[10]XU Huan,CHANG Jie,SUN Jing,GAO Lian.Grapheneencapsulated LiFePO4 nanoparticles with high electrochemical performance for lithium ion batteries[J].Mater Lett,2012,83:27-30.
[11]ZHOU Xu-feng,WANG Feng,ZHU Yi-mei,LIU Zhao-ping.Graphene modified LiFePO4 cathode materials for high power lithium ion batteries[J].J Mater Chem,2011,21:3353-3358.
[12]WEI Wei,LüWei,WU Ming-bo,SU Fang-yuan,HE Yan-bing,LI Bao-hua,KANG Fei-yu,YANG Quan-hong.The effect of graphene wrapping on the performance of LiFePO4 for a lithium ion battery[J].Carbon,2013,57:530-533.
[13]SHI Yi,CHOU Shu-lei,WANG Jia-zhao,WEXLER D,LIHui-jun,LIU Hua-kun,WU Yu-ping.Graphene wrapped Li Fe PO4/C composites as cathode materials for Li-ion batteries with enhanced rate capability[J].J Mater Chem,2012,22:16465-16470.
[14]LIU Wan-min,LIU Qi-long,QIN Mu-lan,XU Lü,DENGJi-yong.Inexpensive and green synthesis of multi-doped Li Fe PO4/C composites for lithium-ion batteries[J].Electrochim Acta,2017,257:82-88.
[15]YAN Ying-lin,LI Qiao-le,REN Bing,YANG Rong,XUYun-hua,ZHONG Li-sheng,WU Hong.An efficient process to fabricate spherical hierarchical LiFePO4/C cathode composites with controllable coating thickness[J].Ionics,2018,24:671-679.
[16]RAJ H,SIL A.Effect of carbon coating on electrochemical performance of LiFePO4 cathode material for Li-ion battery[J].Ionics,2018,24:2543-2553.
[17]NAGARAJU D,KUEZMA M,SURESH G.Li Fe PO4 wrapped reduced graphene oxide for high performance Li-ion battery electrode[J].J Mater Sci,2015,50(12):4244-4249.
[18]OH S W,HUANG Zhen-dong,ZHANG Biao,YU Yang,HEYan-bing,KIM Jang-kyo.Low temperature synthesis of graphene-wrapped LiFePO4 nanorod cathodes by the polyol method[J].J Mater Chem,2012,22:17215-17221.
[19]LUO Wen-bin,CHOU Shu-lei,ZHAI Yu-chun,LIU Hua-kun.Self-assembled graphene and LiFePO4 composites with superior high rate capability for lithium ion batteries[J].J Mater Chem A,2014,2:4927-4931.
[20]LONGONI G,PANDA J K,GAGLIANI L,BRESCIA R,MANNA L,BONACCORSO F,PELLEGRINI V.In situ Li Fe PO4 nano-particles grown on few-layer graphene flakes as high-power cathode nanohybrids for lithium-ion batteries[J].Nano Energy,2018,51:656-667.
[21]WANG Hong-bin,LIU Li-jia,WANG Run-wei,YAN Xiao,WANG Zi-qi,HU Jiang-tao,CHEN Hai-biao,JIANG Shang,NILing,QIU Hai-long,TANG Hai-tong,WEI Ying-jin,ZHANGZong-tao,QIU Shi-lun,PAN Feng.Self-assembly of antisite defectless nano-LiFePO4@C/reduced graphene oxide microspheres for high-performance lithium-ion batteries[J].Chem Sus Chem,2018,11:2255-2261.
[22]RAJOBA S J,JADHAV L D,KALUBARME R S,PATIL P S,VARMA S,WANI B N.Electrochemical performance of Li Fe PO4/GO composite for Li-ion batteries[J].Ceram Int,2018,44:6886-6893.
[23]YI Xu,ZHANG Fu-qin,ZHANG Bao,YU Wan-jing,DAIQiong-yu,HU Sheng-yong,HE Wen-jie,TONG Hui,ZHENGJun-chao,LIAO Ji-qiao.(010)facets dominated LiFePO4nano-flakes confined in 3D porous graphene network as a high-performance Li-ion battery cathode[J].Ceram Int,2018,44:18181-18188.
[24]WANG Qi,PENG Da-chun,CHEN Yu-xi,XIA Xiao-hong,LIUHong-bo,HE Yue-de,M,Qian.A facile surfactant-assisted self-assembly of LiFePO4/graphene composites with improved rate performance for lithium ion batteries[J].J Electroanal Chem,2018,818:68-75.
[25]LIU Tao,LESKES M,YU Wan-jing,MOORE A J,ZHOU Li-na,BAYLEY P M,KIM G,GREY C P.Cycling Li-O2 batteries via Li OH formation and decomposition[J].Science,2015,350(6260):530-533.