本文由氧化石墨烯通过水热法制备直接获得石墨烯。采用热重-差热分析方法检测了石墨烯受热过程中的质量变化和氧化温度。利用热分析-质谱联用技术在400-650°C温度区间得到了水和二氧化碳正离子质谱峰,这说明石墨烯氧化过程中的质...本文由氧化石墨烯通过水热法制备直接获得石墨烯。采用热重-差热分析方法检测了石墨烯受热过程中的质量变化和氧化温度。利用热分析-质谱联用技术在400-650°C温度区间得到了水和二氧化碳正离子质谱峰,这说明石墨烯氧化过程中的质量损失是由羟基水和二氧化碳脱除造成的。同时,还采用非等温热分析动力学方法,利用5、10、15°C?min^(-1)三种不同升温速率获得了石墨烯材料在空气气氛下的热分析动力学参数。通过Kissinger方法计算出石墨烯氧化过程中的活化能(Ea)和指前因子的对数(lg(A/s-1))分别为155.11 k J?mol^(-1)和6.90。利用Ozawa-Flynn-Wall(FWO)方法还建立了活化能和指前因子与反应转化率之间的关系。基于以上研究结果,本工作将对石墨烯在热界面、导热和先进复合材料等领域的应用提供参考价值。展开更多
Zinc-air batteries(ZnABs) with high theoretical capacity and environmental benignity are the most promising candidates for next-generation electronics. However, their large-scale applications are greatly hindered due ...Zinc-air batteries(ZnABs) with high theoretical capacity and environmental benignity are the most promising candidates for next-generation electronics. However, their large-scale applications are greatly hindered due to the lack of high-efficient and cost-effective electrocatalysts. Transition metal phosphides(TMPs) have been reported as promising electrocatalysts. Notably,(Ni_(1-x)Cr_(x))_(2) P(0≤x≤0.15) is an unstable electrocatalyst, which undergoes in-situ electrochemical oxidation during the initial oxygen evolution reaction(OER) and even in the activation cycles, and is eventually converted to Cr-NiOOH serving as the actual OER active sites with high efficiency. Density functional theory(DFT) simulations and experimental results elucidate that the OER performance could be significantly promoted by the synergistic effect of surface engineering and electronic modulations by Cr doping and in-situ phase transformation. The constructed rechargeable ZnABs could stably cycle for more than 208 h at 5 m A cm^(-2), while the voltage degradation is negligible. Furthermore, the developed catalytic materials could be assembled into flexible and all-solid-state Zn ABs to power wearable electronics with high performance.展开更多
Solid-state lithium-metal-batteries(SSLMBs)using garnet Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)as the solid electrolyte are expected to conquer the safety concerns of high energy Li batteries with organic liquid e...Solid-state lithium-metal-batteries(SSLMBs)using garnet Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)as the solid electrolyte are expected to conquer the safety concerns of high energy Li batteries with organic liquid electrolytes owing to its nonflammable nature and good mechanical strength.However,the poor interfacial contact between the Li anode and LLZTO greatly restrains the practical applications of the electrolyte,because large polarization,dendritic Li formation and penetration can occur at the interfaces.Here,an effective method is proposed to improve the wettability of the LLZTO toward lithium and reduce the interfacial resistance by engineering universal lithiophilic interfacial layers.Thanks to the in-situ formed lithiophilic and ionic conductive Co/Li_(2)O interlayers,the symmetric Li/CoO-LLZTO/Li batteries present much smaller overpotential,ultra-low areal specific resistance(ASR,12.3 X cm^(2)),high critical current density(CCD,1.1 mA cm^(-2)),and outstanding cycling performance(1696 h at a current density of 0.3 mA cm^(-2))at 25℃.Besides,the solid-state Li/CoO-LLZTO/LFP cells deliver an excellent electrochemical performance with a high coulombic efficiency of~100%and a long cycling time over 185 times.Surprisingly,the high-voltage(4.6 V)solid state Li/CoO-LLZTO/Li_(1.4)Mn_(0.6)Ni_(0.2)Co_(0.2)O_(2.4)(LMNC622)batteries can also realize an ultra-high specific capacity(232.5 mAh g-1)under 0.1 C at 25℃.This work paves an effective way for practical applications of the dendrite-free SSLMBs.展开更多
基金supported by the National Natural Science Foundation of China(51325203,51472263)Shanghai Materials Genome Project,China(14DZ2261200)+2 种基金Shanghai Technical Platform for Testing and Characterization on Inorganic Materials,China(14DZ2292900)Shanghai Sailing Program,China(16YF1413100)Program of the Innovative Fund of Shanghai Institute of Ceramics,Chinese Academy of Science(Y37ZC4143G)~~
文摘本文由氧化石墨烯通过水热法制备直接获得石墨烯。采用热重-差热分析方法检测了石墨烯受热过程中的质量变化和氧化温度。利用热分析-质谱联用技术在400-650°C温度区间得到了水和二氧化碳正离子质谱峰,这说明石墨烯氧化过程中的质量损失是由羟基水和二氧化碳脱除造成的。同时,还采用非等温热分析动力学方法,利用5、10、15°C?min^(-1)三种不同升温速率获得了石墨烯材料在空气气氛下的热分析动力学参数。通过Kissinger方法计算出石墨烯氧化过程中的活化能(Ea)和指前因子的对数(lg(A/s-1))分别为155.11 k J?mol^(-1)和6.90。利用Ozawa-Flynn-Wall(FWO)方法还建立了活化能和指前因子与反应转化率之间的关系。基于以上研究结果,本工作将对石墨烯在热界面、导热和先进复合材料等领域的应用提供参考价值。
基金supported by the National Natural Science Foundation of China (21603019 and 201503025)the National Key Research and Development Program of China (2016YFE0125900)the program for the Hundred Talents Program of Chongqing University。
文摘Zinc-air batteries(ZnABs) with high theoretical capacity and environmental benignity are the most promising candidates for next-generation electronics. However, their large-scale applications are greatly hindered due to the lack of high-efficient and cost-effective electrocatalysts. Transition metal phosphides(TMPs) have been reported as promising electrocatalysts. Notably,(Ni_(1-x)Cr_(x))_(2) P(0≤x≤0.15) is an unstable electrocatalyst, which undergoes in-situ electrochemical oxidation during the initial oxygen evolution reaction(OER) and even in the activation cycles, and is eventually converted to Cr-NiOOH serving as the actual OER active sites with high efficiency. Density functional theory(DFT) simulations and experimental results elucidate that the OER performance could be significantly promoted by the synergistic effect of surface engineering and electronic modulations by Cr doping and in-situ phase transformation. The constructed rechargeable ZnABs could stably cycle for more than 208 h at 5 m A cm^(-2), while the voltage degradation is negligible. Furthermore, the developed catalytic materials could be assembled into flexible and all-solid-state Zn ABs to power wearable electronics with high performance.
基金supported by the National Natural Science Foundation of China (21603019 and 201503025)Program for the Hundred Talents Program of Chongqing University。
文摘Solid-state lithium-metal-batteries(SSLMBs)using garnet Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)as the solid electrolyte are expected to conquer the safety concerns of high energy Li batteries with organic liquid electrolytes owing to its nonflammable nature and good mechanical strength.However,the poor interfacial contact between the Li anode and LLZTO greatly restrains the practical applications of the electrolyte,because large polarization,dendritic Li formation and penetration can occur at the interfaces.Here,an effective method is proposed to improve the wettability of the LLZTO toward lithium and reduce the interfacial resistance by engineering universal lithiophilic interfacial layers.Thanks to the in-situ formed lithiophilic and ionic conductive Co/Li_(2)O interlayers,the symmetric Li/CoO-LLZTO/Li batteries present much smaller overpotential,ultra-low areal specific resistance(ASR,12.3 X cm^(2)),high critical current density(CCD,1.1 mA cm^(-2)),and outstanding cycling performance(1696 h at a current density of 0.3 mA cm^(-2))at 25℃.Besides,the solid-state Li/CoO-LLZTO/LFP cells deliver an excellent electrochemical performance with a high coulombic efficiency of~100%and a long cycling time over 185 times.Surprisingly,the high-voltage(4.6 V)solid state Li/CoO-LLZTO/Li_(1.4)Mn_(0.6)Ni_(0.2)Co_(0.2)O_(2.4)(LMNC622)batteries can also realize an ultra-high specific capacity(232.5 mAh g-1)under 0.1 C at 25℃.This work paves an effective way for practical applications of the dendrite-free SSLMBs.
