工程科学学报，第39卷，第3期：407416,2017年3月 Chinese Journal of Engineering,Vol.39,No.3:407-416,March 2017 D0:10.13374/j.issn2095-9389.2017.03.013;htp:/journals..ustb.edu.cm 高性能锂离子电池负极材料一氧化锰/石墨烯复合材 料的合成 苗小飞”，刘永川”，张祥昕”，陈素晶”，陈远强”，张易宁2)区 1)中国科学院光电材料化学与物理重点实验室，中国科学院福建物质结构研究所，福州3500022)中国科学院大学，北京100049 ☒通信作者，E-mail:ynzhang(@ism.ac.cn 摘要通过冻干一煅烧合成了一氧化锰/石墨烯(MO/rG0)复合材料，并将其用作锂离子电池负极材料.在500mA·g的 电流密度下，M0/rG0复合材料表现出高达830mAh·g的可逆容量，且在充放电循环160圈后，其可逆容量依然高达805 mAh~g.倍率测试结果显示，循环225圈后，在2.0Ag的电流密度下，其可逆容量高达412mAh~g.复合材料中的石墨 烯在提高材料导电性的同时有效地缓解了一氧化锰充放电过程中的体积膨胀.通过对比容量一电压的微分分析，发现复合材 料超出一氧化锰理论容量的部分是由形成了更高价态的锰引起的.MnO/rC0复合材料比纯一氧化锰(p-MnO)更容易出现 高价态的锰，可能是因为G0上残留的氧为电极反应提供了额外所需的氧源.该一氧化锰/石墨烯复合材料因其简单绿色的 合成过程及优异的电化学性质，有望在未来的锂电负极中得到广泛的实际应用. 关键词一氧化锰：石墨烯：锂离子电池；负极材料 分类号TM912.9 Synthesis of MnO/reduced graphene oxide composites as high performance anode materials for Li-ion batteries MIAO Xiao-fei,LIU Yong-chuan,ZHNAG Xiang-in,CHEN Su-jing,CHEN Yuan-qiang),ZHANG Yi-ning) 1)Key Laboratory of Optoelectronic Materials Chemistry and Physics,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sci- ences,Fuzhou 350002,China 2)University of Chinese Academy of Sciences,Beijing 100049,China Corresponding author,E-mail:ynzhang@fjirsm.ac.cn ABSTRACT MnO/reduced graphene oxide (MnO/rGO)composites synthesized through freeze-drying following annealing were used as anode materials for lithium ion batteries.At 500 mAg,the MnO/rGO composite exhibits a reversible capacity as high as 830 mAhgand the specific capacitance remains at 805 mAh'gafter 160 discharge/charge cycles,demonstrating excellent cycling sta- bility.It also shows good rate capacities and delivers a specific capacity of 412 mAh'gat 2.0Agafter 225 cycles at different rates.The rGO increases the electrical conductivity and provides space to accommodate the volume expansion of MnO during charge/ discharge.The extra capacity,over the theoretical value of MnO,is attributed to the formation of higher oxidation state manganese ac- cording to the charge-voltage derivative analysis of the galvanostatic charge-discharge curves.A higher tendency to further oxidize Mn(II)in the MnO/rGO composite maybe result in the extra oxygen source provided by rGO during the electrode reaction.The sim- ple and green synthetic protocol and the excellent electrochemical performance demonstrate the great potential of the MnO/rGO com- posite anode in large scale production and applications. KEY WORDS manganese monoxide:graphene;lithium ion batteries:anode materials 收稿日期：201605-17 基金项目：国家自然科学基金青年基金项目(51602310)：福建省科学技术资助项目(2014H2008):福建省重点引导性资助项目(2015H0052, 2016H0047)工程科学学报，第 39 卷，第 3 期: 407--416，2017 年 3 月 Chinese Journal of Engineering，Vol． 39，No． 3: 407--416，March 2017 DOI: 10． 13374 /j． issn2095--9389． 2017． 03． 013; http: / /journals． ustb． edu． cn 高性能锂离子电池负极材料一氧化锰 /石墨烯复合材 料的合成 苗小飞1) ，刘永川1) ，张祥昕1) ，陈素晶1) ，陈远强1) ，张易宁1，2)  1) 中国科学院光电材料化学与物理重点实验室，中国科学院福建物质结构研究所，福州 350002 2) 中国科学院大学，北京 100049 通信作者，E-mail: ynzhang@ fjirsm． ac． cn 收稿日期: 2016--05--17 基金项目: 国家自然科学基金青年基金项目( 51602310) ; 福建省科学技术资助项目( 2014H2008) ; 福建省重点引导性资助项目( 2015H0052， 2016H0047) 摘 要 通过冻干--煅烧合成了一氧化锰/石墨烯( MnO/ rGO) 复合材料，并将其用作锂离子电池负极材料． 在 500 mA·g － 1的 电流密度下，MnO/ rGO 复合材料表现出高达 830 mAh·g － 1的可逆容量，且在充放电循环 160 圈后，其可逆容量依然高达 805 mAh·g － 1 ． 倍率测试结果显示，循环 225 圈后，在 2. 0 A·g － 1的电流密度下，其可逆容量高达 412 mAh·g － 1 ． 复合材料中的石墨 烯在提高材料导电性的同时有效地缓解了一氧化锰充放电过程中的体积膨胀． 通过对比容量--电压的微分分析，发现复合材 料超出一氧化锰理论容量的部分是由形成了更高价态的锰引起的． MnO/ rGO 复合材料比纯一氧化锰( p--MnO) 更容易出现 高价态的锰，可能是因为 rGO 上残留的氧为电极反应提供了额外所需的氧源． 该一氧化锰/石墨烯复合材料因其简单绿色的 合成过程及优异的电化学性质，有望在未来的锂电负极中得到广泛的实际应用． 关键词 一氧化锰; 石墨烯; 锂离子电池; 负极材料 分类号 TM912. 9 Synthesis of MnO / reduced graphene oxide composites as high performance anode materials for Li-ion batteries MIAO Xiao-fei1) ，LIU Yong-chuan1) ，ZHNAG Xiang-xin1) ，CHEN Su-jing1) ，CHEN Yuan-qiang1) ，ZHANG Yi-ning1，2)  1) Key Laboratory of Optoelectronic Materials Chemistry and Physics，Fujian Institute of Ｒesearch on the Structure of Matter，Chinese Academy of Sci￾ences，Fuzhou 350002，China 2) University of Chinese Academy of Sciences，Beijing 100049，China Corresponding author，E-mail: ynzhang@ fjirsm． ac． cn ABSTＲACT MnO/ reduced graphene oxide ( MnO/ rGO) composites synthesized through freeze-drying following annealing were used as anode materials for lithium ion batteries． At 500 mA·g － 1，the MnO/ rGO composite exhibits a reversible capacity as high as 830 mAh·g － 1 and the specific capacitance remains at 805 mAh·g － 1 after 160 discharge /charge cycles，demonstrating excellent cycling sta￾bility． It also shows good rate capacities and delivers a specific capacity of 412 mAh·g － 1 at 2. 0 A·g － 1 after 225 cycles at different rates． The rGO increases the electrical conductivity and provides space to accommodate the volume expansion of MnO during charge / discharge． The extra capacity，over the theoretical value of MnO，is attributed to the formation of higher oxidation state manganese ac￾cording to the charge-voltage derivative analysis of the galvanostatic charge--discharge curves． A higher tendency to further oxidize Mn( Ⅱ) in the MnO/ rGO composite maybe result in the extra oxygen source provided by rGO during the electrode reaction． The sim￾ple and green synthetic protocol and the excellent electrochemical performance demonstrate the great potential of the MnO/ rGO com￾posite anode in large scale production and applications． KEY WOＲDS manganese monoxide; graphene; lithium ion batteries; anode materials