Fluorinated carbons CF_xhold the highest theoretical energy density(e.g.,2180 W h kg^(-1)when x=1)among all cathode materials of lithium primary batteries.However,the low conductivity and severe polarization limit it ...Fluorinated carbons CF_xhold the highest theoretical energy density(e.g.,2180 W h kg^(-1)when x=1)among all cathode materials of lithium primary batteries.However,the low conductivity and severe polarization limit it to achieve its theory.In this study,we design a new electrolyte,namely 1 M LiBF_(4)DMSO:DOL(1:9 vol.),achieving a high energy density in Li/CF_xprimary cells.The DMSO with a small molecular size and high donor number successfully solvates Li^(+)into a defined Li^(+)-solvation structure.Such solvated Li^(+)can intercalate into the large-spacing carbon layers and achieve an improved capacity.Consequently,when discharged to 1.0 V,the CF_(1.12)cathode demonstrates a specific capacity of 1944 m A h g^(-1)with a specific energy density of 3793 W h kg^(-1).This strategy demonstrates that designing the electrolyte is powerful in improving the electrochemical performance of CF_(x) cathode.展开更多
Forming an ultrathin conducting layer on a fluorinated carbon(CFx)surface for reducing severe electrochemical polarization in lithium/fluorinated carbon primary batteries(Li/CF_(x))remains a considerable challenge for...Forming an ultrathin conducting layer on a fluorinated carbon(CFx)surface for reducing severe electrochemical polarization in lithium/fluorinated carbon primary batteries(Li/CF_(x))remains a considerable challenge for achieving batteries with excellent rate capability.Herein,CFxwas modified by using acetylene/argon mixture plasma combined with MnO_(2)particles.The CF_(x)/C/MnO_(2)composite effectively reduced the voltage hysteresis and improved the electrochemical performance of Li/CF_(x).The excellent rate performance of CF_(x)/C/MnO_(2)was due to the high electrochemical activity provided by the atomicscale conductive carbon layer and ultrafine MnO_(2)particles.Compared with pristine CF_(x),the charge transfer resistance of the optimized CF_(x)/C/MnO_(2)decreased from 218.5 to 48.2Ω,the discharge rate increased from 2C to 10C,and the power density increased from 3.11 to 13.44 kW·g^(-1),The intrinsic reason for the enhanced rate performance was attributed to the fact that the ultrathin carbon layer acted as a conductive bridge to reduce the voltage hysteresis at the initial stage of the Li/CF_(x)discharge,and the high electrochemical activity of the ultrafine MnO_(2)particles provided a faster lithium-ion diffusion rate.展开更多
The enhancement of the fluorination degree of carbon fluorides(CF_(x))compounds is the most effective method to improve the energy densities of Li/CF_(x)batteries because the specific capacity of CF_(x)is proportional...The enhancement of the fluorination degree of carbon fluorides(CF_(x))compounds is the most effective method to improve the energy densities of Li/CF_(x)batteries because the specific capacity of CF_(x)is proportional to the molar ratio of F to C atoms(F/C).In this study,B-doped graphene(BG)is prepared by using boric acid as the doping source and then the prepared BG is utilized as the starting material for the preparation of CF_(x).The B-doping enhances the F/C ratio of CF_(x)without hindering the electrochemical activity of the C–F bond.During the fluorination process,B-containing functional groups are removed from the graphene lattice.This facilitates the formation of a defect-rich graphene matrix,which not only enhances the F/C ratio due to abundant perfluorinated groups at the defective edges but also serves as the active site for extra Li+storage.The prepared CF_(x)exhibits the maximum specific capacity of 1204 mAh g^(−1),which is 39.2%higher than that of CF_(x)obtained directly from graphene oxide(without B-doping).An unprecedented energy density of 2974 Wh kg^(−1)is achieved for the asprepared CF_(x)samples,which is significantly higher than the theoretically calculated energy density of commercially available fluorinated graphite(2180 Wh kg^(−1)).Therefore,this study demonstrates a great potential of B-doping to realize the ultrahigh energy density of CF_(x)cathodes for practical applications.展开更多
研究了相同氟碳比的氟化石墨(F-graphtie)和氟化多壁碳纳米管(F-MWCNTs)的电化学性能。高纯石墨化多壁碳纳米管经氟化处理后,获得一种核壳结构的F-WMCNTs(氟碳原子比C/F=1∶1)。经TEM、XRD、XPS表征表明,F-WMCNTs外层被氟化,形成氟化碳...研究了相同氟碳比的氟化石墨(F-graphtie)和氟化多壁碳纳米管(F-MWCNTs)的电化学性能。高纯石墨化多壁碳纳米管经氟化处理后,获得一种核壳结构的F-WMCNTs(氟碳原子比C/F=1∶1)。经TEM、XRD、XPS表征表明,F-WMCNTs外层被氟化,形成氟化碳结构,而内层依然保持原有的石墨结构。以此F-WMCNTs作正极活性材料组装成锂氟(Li/CF_x)一次电池。经电化学测试表明,在相同的放电倍率下,对比F-graphite电极(C/F=1∶1),F-WMCNTs电极能够有效提高Li/CF_x一次电池的放电容量和电压平台。大倍率(≥1 C)放电时,尤其明显。当放电倍率为0.05 C时,F-WMCNTs极和F-graphite电极比容量分别为822 m Ah/g和786.1 m Ah/g,F-WMCNTs电极放电容量比F-graphite电极提高4.5%。当放电倍率为2 C时,F-WMCNTs电极和F-graphite电极分别达到375.4 m Ah/g和283.7 m Ah/g,F-WMCNTs电极的放电比容量比F-graphite电极提高了32.2%。F-WMCNTs电极显示出优异的倍率性能。展开更多
基金supported by the National Natural Science Foundation of China(Nos.52072061,22322903,12174162)the Natural Science Foundation of Sichuan,China(No.2023NSFSC1914)21C Innovation Laboratory,Contemporary Amperex Technology Ltd.by project No.21C-OP-202103。
文摘Fluorinated carbons CF_xhold the highest theoretical energy density(e.g.,2180 W h kg^(-1)when x=1)among all cathode materials of lithium primary batteries.However,the low conductivity and severe polarization limit it to achieve its theory.In this study,we design a new electrolyte,namely 1 M LiBF_(4)DMSO:DOL(1:9 vol.),achieving a high energy density in Li/CF_xprimary cells.The DMSO with a small molecular size and high donor number successfully solvates Li^(+)into a defined Li^(+)-solvation structure.Such solvated Li^(+)can intercalate into the large-spacing carbon layers and achieve an improved capacity.Consequently,when discharged to 1.0 V,the CF_(1.12)cathode demonstrates a specific capacity of 1944 m A h g^(-1)with a specific energy density of 3793 W h kg^(-1).This strategy demonstrates that designing the electrolyte is powerful in improving the electrochemical performance of CF_(x) cathode.
基金financially supported by the National Natural Science Foundation of China(No.51972045)the Fundamental Research Funds for the Chinese Central Universities,China(No.ZYGX2019J025)。
文摘Forming an ultrathin conducting layer on a fluorinated carbon(CFx)surface for reducing severe electrochemical polarization in lithium/fluorinated carbon primary batteries(Li/CF_(x))remains a considerable challenge for achieving batteries with excellent rate capability.Herein,CFxwas modified by using acetylene/argon mixture plasma combined with MnO_(2)particles.The CF_(x)/C/MnO_(2)composite effectively reduced the voltage hysteresis and improved the electrochemical performance of Li/CF_(x).The excellent rate performance of CF_(x)/C/MnO_(2)was due to the high electrochemical activity provided by the atomicscale conductive carbon layer and ultrafine MnO_(2)particles.Compared with pristine CF_(x),the charge transfer resistance of the optimized CF_(x)/C/MnO_(2)decreased from 218.5 to 48.2Ω,the discharge rate increased from 2C to 10C,and the power density increased from 3.11 to 13.44 kW·g^(-1),The intrinsic reason for the enhanced rate performance was attributed to the fact that the ultrathin carbon layer acted as a conductive bridge to reduce the voltage hysteresis at the initial stage of the Li/CF_(x)discharge,and the high electrochemical activity of the ultrafine MnO_(2)particles provided a faster lithium-ion diffusion rate.
基金financialy supported by the State Key Program of National Natural Science Foundation of China(no.52130303)the National Natural Science Foundation of China(no.51773147 and 51973151)
文摘The enhancement of the fluorination degree of carbon fluorides(CF_(x))compounds is the most effective method to improve the energy densities of Li/CF_(x)batteries because the specific capacity of CF_(x)is proportional to the molar ratio of F to C atoms(F/C).In this study,B-doped graphene(BG)is prepared by using boric acid as the doping source and then the prepared BG is utilized as the starting material for the preparation of CF_(x).The B-doping enhances the F/C ratio of CF_(x)without hindering the electrochemical activity of the C–F bond.During the fluorination process,B-containing functional groups are removed from the graphene lattice.This facilitates the formation of a defect-rich graphene matrix,which not only enhances the F/C ratio due to abundant perfluorinated groups at the defective edges but also serves as the active site for extra Li+storage.The prepared CF_(x)exhibits the maximum specific capacity of 1204 mAh g^(−1),which is 39.2%higher than that of CF_(x)obtained directly from graphene oxide(without B-doping).An unprecedented energy density of 2974 Wh kg^(−1)is achieved for the asprepared CF_(x)samples,which is significantly higher than the theoretically calculated energy density of commercially available fluorinated graphite(2180 Wh kg^(−1)).Therefore,this study demonstrates a great potential of B-doping to realize the ultrahigh energy density of CF_(x)cathodes for practical applications.
文摘研究了相同氟碳比的氟化石墨(F-graphtie)和氟化多壁碳纳米管(F-MWCNTs)的电化学性能。高纯石墨化多壁碳纳米管经氟化处理后,获得一种核壳结构的F-WMCNTs(氟碳原子比C/F=1∶1)。经TEM、XRD、XPS表征表明,F-WMCNTs外层被氟化,形成氟化碳结构,而内层依然保持原有的石墨结构。以此F-WMCNTs作正极活性材料组装成锂氟(Li/CF_x)一次电池。经电化学测试表明,在相同的放电倍率下,对比F-graphite电极(C/F=1∶1),F-WMCNTs电极能够有效提高Li/CF_x一次电池的放电容量和电压平台。大倍率(≥1 C)放电时,尤其明显。当放电倍率为0.05 C时,F-WMCNTs极和F-graphite电极比容量分别为822 m Ah/g和786.1 m Ah/g,F-WMCNTs电极放电容量比F-graphite电极提高4.5%。当放电倍率为2 C时,F-WMCNTs电极和F-graphite电极分别达到375.4 m Ah/g和283.7 m Ah/g,F-WMCNTs电极的放电比容量比F-graphite电极提高了32.2%。F-WMCNTs电极显示出优异的倍率性能。
