氟化石墨材料的改性及其电化学性能研究
收稿日期: 2018-01-31
修回日期: 2018-03-28
网络出版日期: 2018-04-16
基金资助
无基金项目资助
Modifications and Electrochemical Properties of Graphite Fluoride
Received date: 2018-01-31
Revised date: 2018-03-28
Online published: 2018-04-16
本文以商用氟化石墨为原料，通过水合肼还原的方法对氟化石墨（CFx）进行改性处理，系统研究了不同水合肼用量对材料电化学性能的影响. 采用XRD、SEM、EDS、XPS、交流阻抗（EIS）和恒流放电测试技术，对改性氟化石墨材料的物相及电化学性能进行了分析研究. 结果表明，采用改性氟化石墨材料制备的锂/氟化碳（Li/CFx）电池的电压滞后现象得到明显改善，且不同水合肼用量对材料的电化学性能有重要影响. H-CFx-2（CFx：C2H6O：N2H4·H2O 的比例为1：2：1）材料的综合性能最佳，在0.1C 倍率下，材料的克比容量达到794.5 mAh·g-1，平台电压为2.53V，电压滞后现象的低波电压为2.37 V.
张亮 , 张红梅 , 万伟华 , 魏俊华 . 氟化石墨材料的改性及其电化学性能研究[J]. 电化学, 2018 , 24(4) : 385 -391 . DOI: 10.13208/j.electrochem.180131
The commercial fluorinated graphite (CFx) was used as the raw material, which was modified by the reduction of hydrazine hydrate (N2H4·H2O). The effects of hydrazine hydrate contents on the electrochemical properties of fluorinated graphite were systematically studied. The crystal phases and electrochemical properties of the modified fluorinated graphite were analyzed by XRD, SEM, EDS, XPS, EIS techniques and constant current discharge measurement. The results showed that the voltage hysteresis response of Lithium-fluorocarbon battery prepared by the modified fluorinated graphite was obviously improved, while the amount of hydrazine hydrate had an important influence on the electrochemical performance of the materials. The H-CFx-2 material had the best overall performance (CFx:C2H6O: N2H4·H2O was 1:2:1). At 0.1C, the specific capacity of the material reached 794.5 mAh·g-1, the platform voltage was 2.53 V, and the low-wave voltage of the voltage hysteresis was 2.37 V.
[1] Reddy T B, Handbook of Batteries(fourth Ed.)[M]. McGraw-Hill, 2011:284-285.
[2] Zhang S S, Foster D, Wolfenstine J, et al. Electrochemical characteristic and discharge mechanism of a primary Li/CFx cell[J]. Journal of Power Sources, 2009, 187: 233-237.
[3] Nagata M, Yi J, Tomicsi M. Performance of lithium primary cell using a hybrid positive electrode of LiV3O8 and CFx[C]//Battery/energy technology (general)-218th ECS Meeting,
10-15 October 2010, Las Vegas, Nevada, USA, ECS Transactions, 2011, 33(39): 223-237.
[4] Sideris P J, Yew R, Nieves I, et al. Charge transfer in Li/CFx–silver vanadium oxide hybrid cathode batteries revealed by solid state 7Li and 19F nuclear magnetic resonance spectroscopy[J]. Journal of Power Sources, 2014, 254: 293-297.
[5] Chen D(陈笛), Wang X H(王兴贺), Meng X L(孟宪玲), et al. Process for preparing cathode MnO2 with additive CFx[J]. Chinese Journal of Power Sources(电源技术), 2013, 37(6): 973-975.
[6]Yang K(杨凯), Liu X S(刘雪省), Zhang J(张晶), et al. Investigation of a primary Li cell whose cathode was made of the mixture of fluorinated carbon and electrolytic manganese dioxide[J]. Journal of Functional Materials(功能材料), 2014, 45(22): 22075-22078.
[7] Yazami R, Hamwi A, Guérin K, et al. Fluorinated carbon nanofibres for high energy and high power densities primary lithium batteries[J]. Electrochemistry Communications, 2007, 9(7): 1850-1855.
[8] Li Y, Feng Y, Feng W. Deeply fluorinated multi-wall carbon nanotubes for high energy and power densities lithium/carbon fluorides battery[J]. Electrochimica Acta, 2013, 107: 343-349.
[9] Sun C, Feng Y, Li Y, et al. Solvothermally exfoliated fluorographene for high-performance lithium primary batteries[J]. Nanoscale, 2014, 6(5): 2634-2641.
[10] Xu Y(许耀), Lu L(詹亮), Wang Y(王赟), et al. Fluorinated grapheme as a cathode material for high performance primary lithium ion batteries [J]. New Carbon Materials(新型碳材料), 2015, 30(1): 79-85.
[11] Zhang S S, Foster D, Read J. Enhancement of discharge performance of Li/CFx cell by thermal treatment of CFx cathode material[J]. Journal of Power Sources, 2009, 188:601-605.
[12] Zhang S S, Foster D, Read J. Carbothermal treatment for the improved discharge performance of primary Li/CFx battery[J]. Journal of Power Sources, 2009, 191: 648-652.
[13] Zhu L, Pan Y, Li L, et al. Preparation of CFx@C Microcapsules as a high-rate capability cathode oflithium primary battery. Journal of the Electrochemical Society.2016, 11:14-22.
[14] Dong Q F（董全峰）, Zheng M S（郑明森）, Huang Z C（黄镇财）, et al. The synthesis, characteristics and performance of CNT composites as anodic materials in litiumion battery（电化学）, 2005, 11(2): 152-156.
[15] Li Y, Chen Y, Feng W, et al. The improved discharge performance of Li/CFx batteries by using multi-walled carbon nanotubes as conductive additive[J]. Journal of Power Sources, 2011, 196(4): 2246-2250.
[16] Hightower A, Darolles I, Yazami R. Surface species on Ag modified carbon fluoride (CFx) rechargeable battery electrodes measured by XPS[C]//The 15th International Meeting on Lithium Batteries-IMLB, 2010 June 28, Montreal, Canada, 2010: 518.
[17] Wu C L, Wang H B, Liao C B, et al. Enhanced performance of Li-O2 battery based on CFx/C composites as cathode materials[J]. Electrochimica Acta, 2015, 186:631-641.
[18] Okotrub A V, Babin K S, Guselnikov A V, et al. Interaction of NH3 with the reduced surface of graphite fluoride C2F[J]. Phys. Status Solidi B, 2010, 247, 2010, 247(11/12): 3039-3042.．
[19] Ma Y C. Preparation of fluorinated fluorine and the preparation of fluorinated fluorine by chemical reduction[D]. NanJing, Nanjing University of Science and Technology(南京理工大学), 2012.
[20] Touhara H, Okino F. Property control of carbon materials by fluorination[J]. Carbon, 2000, 38(2): 241-267.
[21] Fulvio P F, Brown S S, Adcock J, et al. Low-temperature fluorination of soft-templated mesoporous carbons for a high-power lithium/carbon fluoride battery[J]. Chemistry of Materials, 2011, 23(20): 4420-4427.
[22] Groult H, Durand-Vidal S, Devilliers D, et al. Kinetics of fluorine evolution reaction on carbon anodes: influence of the surface C-F films [J]. Journal of Fluorine Chemistry, 2001, 107(2): 247-254.
[23] Li G Y, Li Y H, Zhang H, et al. Time-dependent density functional theory study on a fluorescent chemosensor based on C−H···F hydrogen-bond interaction[J]. Communications in Computational Chemistry, 2013, 1(1): 88-98.
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