Molten salts play multiple important roles in the electrolysis of solid metal compounds,particularly oxides and sulfides,for the extraction of metals or alloys.Some of these roles are positive in assisting the extract...Molten salts play multiple important roles in the electrolysis of solid metal compounds,particularly oxides and sulfides,for the extraction of metals or alloys.Some of these roles are positive in assisting the extraction of metals,such as dissolving the oxide or sulfide anions,and transporting them to the anode for discharging,and offering the high temperature to lower the kinetic barrier to break the metal-oxygen or metal-sulfur bond.However,molten salts also have unfavorable effects,including electronic conductivity and significant capability of dissolving oxygen and carbon dioxide gases.In addition,although molten salts are relatively simple in terms of composition,physical properties,and decomposition reactions at inert electrodes,in comparison with aqueous electrolytes,the high temperatures of molten salts may promote unwanted electrode-electrolyte interactions.This article reviews briefly and selectively the research and development of the F ray-F arthing-Chen(FFC)Cambridge Process in the past two decades,focusing on observations,understanding,and solutions of various interactions between molten salts and cathodes at different reduction states,including perovskitization,non-wetting of molten salts on pure metals,carbon contamination of products,formation of oxychlorides and calcium intermetallic compounds,and oxygen transfer from the air to the cathode product mediated by oxide anions in the molten salt.展开更多
Silicon has a large impact on the energy supply and economy in the modern world. In industry, high purity silicon is firstly prepared by carbothermic reduction of silica with the produced raw silicon being further ref...Silicon has a large impact on the energy supply and economy in the modern world. In industry, high purity silicon is firstly prepared by carbothermic reduction of silica with the produced raw silicon being further refined by a modified Siemens method. This process suffers from the disadvantages of high cost and contaminant release and emission. As an alternative, the molten salt electrolysis approach, particularly the FFC Cambridge Process(FFC: Fray-Farthing-Chen), could realize high purity silicon products with morphology-controllable nanostructures at low or mild temperatures(generally 650–900 ℃). In this article, we review the development, reaction mechanisms, and electrolysis conditions of silicon production by the FFC Cambridge Process. Applications of the silicon products from electrolysis in molten salts are also discussed in terms of energy applications, including using them as the photovoltaic element in solar cells and as the charge storage phase in the negative electrode(negatrode) of lithium ion batteries.展开更多
Fabrication of stable,reproducible and reusable reference electrodes for low energy and high-temperature steam splitting is of great interest for hydrogen fuel production without anthropogenic carbon dioxide(CO2)emiss...Fabrication of stable,reproducible and reusable reference electrodes for low energy and high-temperature steam splitting is of great interest for hydrogen fuel production without anthropogenic carbon dioxide(CO2)emission.This study has been conducted for the detection of suitable material for the fabrication of novel reference electrode.In the present scenario,this research is designed to fabricate a novel nickel reference electrode by using operating conditions of eutectic molten hydroxide(NaOH-KOH,49-51 mol%)at temperature 300℃in an ion-conducting membrane of alumina and mullite tube.Afterwards,the designed nickel reference electrode has been examined for its reusability and stability by using electrochemical technique and cyclic voltammetry.Five scans of cyclic voltammetry are performed for both membrane fabricated reference electrode.A slight positive shift in oxidation peaks is observed for mullite membrane electrode(64 mV from scan 1 to 5).The stability measurements are noted by changing the scan rate between 50 and 150 mV s−1.Furthermore,the results show that the Ni/Ni(OH)2 reference electrode covered with a mullite membrane is stable and reusable at 300℃temperature without any deterioration.The stability and reusability of prepared nickel reference electrode covered by mullite tube in the eutectic molten hydroxide were up to 9 days to carry out an electrochemical investigation,while for alumina tube reference electrode the stability and reliability were up to 3 days.The internal electrolytic material and ionic conductance can play an important role for future studies with this reference electrode along with optimisation of temperature and scan rate parameters.展开更多
Device level performance of aqueous halide supercapatteries fabricated with equal electrode mass of activated carbon or graphene nanoplatelets has been characterized.It was revealed that the surface oxygen groups in t...Device level performance of aqueous halide supercapatteries fabricated with equal electrode mass of activated carbon or graphene nanoplatelets has been characterized.It was revealed that the surface oxygen groups in the graphitic structures of the nanoplatelets contributed toward a more enhanced charge storage capacity in bromide containing redox electrolytes.Moreover,the rate performance of the devices could be linked to the effect of the pore size of the carbons on the dynamics of the inactive alkali metal counterion of the redox halide salt.Additionally,the charge storage performance of aqueous halide supercapatteries with graphene nanoplatelets as the electrode material may be attributed to the combined effect of the porous structure on the dynamics of the non-active cations and a possible interaction of the Br^(-)/(Br_(2)+Br^(-)_(3))redox triple with the surface oxygen groups within the graphitic layer of the nanoplatelets.Generally,it has been shown that the surface groups and microstructure of electrode materials must be critically correlated with the redox electrolytes in the ongoing efforts to commercialize these devices.展开更多
嵌入型过渡金属氧化物因具有安全的工作电压、高比容量和快速的嵌锂能力而受到广泛关注.但低本征电导率特性严重影响其作为锂电负极材料的寿命和性能.本文通过简便易行、可规模化放大的二氧化碳热处理方法构筑了具有新型嵌覆型碳结构的N...嵌入型过渡金属氧化物因具有安全的工作电压、高比容量和快速的嵌锂能力而受到广泛关注.但低本征电导率特性严重影响其作为锂电负极材料的寿命和性能.本文通过简便易行、可规模化放大的二氧化碳热处理方法构筑了具有新型嵌覆型碳结构的Nb_(2)O_(5)/C纳米杂化材料.在控制碳含量的前提下,实现了颗粒聚集体内部表面可控碳包覆.以嵌覆型碳结构的Nb_(2)O_(5)/C纳米杂化材料为负极组装的锂离子电池在40 mA g(-1)电流密度下容量可达387 mA hg(-1),而在200 mA g(-1)电流密度下循环500次后,容量保持率在92%以上.采用电化学滴定、差分电化学质谱(DEMS)等方法对嵌覆型五氧化二铌/碳纳米杂化材料脱嵌锂动力学过程以及产气行为进行了研究.本文提出的嵌覆型碳结构有望为高性能嵌入型过渡金属氧化物的结构设计提供参考.展开更多
文摘Molten salts play multiple important roles in the electrolysis of solid metal compounds,particularly oxides and sulfides,for the extraction of metals or alloys.Some of these roles are positive in assisting the extraction of metals,such as dissolving the oxide or sulfide anions,and transporting them to the anode for discharging,and offering the high temperature to lower the kinetic barrier to break the metal-oxygen or metal-sulfur bond.However,molten salts also have unfavorable effects,including electronic conductivity and significant capability of dissolving oxygen and carbon dioxide gases.In addition,although molten salts are relatively simple in terms of composition,physical properties,and decomposition reactions at inert electrodes,in comparison with aqueous electrolytes,the high temperatures of molten salts may promote unwanted electrode-electrolyte interactions.This article reviews briefly and selectively the research and development of the F ray-F arthing-Chen(FFC)Cambridge Process in the past two decades,focusing on observations,understanding,and solutions of various interactions between molten salts and cathodes at different reduction states,including perovskitization,non-wetting of molten salts on pure metals,carbon contamination of products,formation of oxychlorides and calcium intermetallic compounds,and oxygen transfer from the air to the cathode product mediated by oxide anions in the molten salt.
基金supported by the National Natural Science Foundation of China (No.51602234)Ningbo Municipal Government (3315 Plan and 2014A35001-1)UK Engineering and Physical Science Research Council (EP/J000582/1, GR/R68078)。
文摘Silicon has a large impact on the energy supply and economy in the modern world. In industry, high purity silicon is firstly prepared by carbothermic reduction of silica with the produced raw silicon being further refined by a modified Siemens method. This process suffers from the disadvantages of high cost and contaminant release and emission. As an alternative, the molten salt electrolysis approach, particularly the FFC Cambridge Process(FFC: Fray-Farthing-Chen), could realize high purity silicon products with morphology-controllable nanostructures at low or mild temperatures(generally 650–900 ℃). In this article, we review the development, reaction mechanisms, and electrolysis conditions of silicon production by the FFC Cambridge Process. Applications of the silicon products from electrolysis in molten salts are also discussed in terms of energy applications, including using them as the photovoltaic element in solar cells and as the charge storage phase in the negative electrode(negatrode) of lithium ion batteries.
文摘Fabrication of stable,reproducible and reusable reference electrodes for low energy and high-temperature steam splitting is of great interest for hydrogen fuel production without anthropogenic carbon dioxide(CO2)emission.This study has been conducted for the detection of suitable material for the fabrication of novel reference electrode.In the present scenario,this research is designed to fabricate a novel nickel reference electrode by using operating conditions of eutectic molten hydroxide(NaOH-KOH,49-51 mol%)at temperature 300℃in an ion-conducting membrane of alumina and mullite tube.Afterwards,the designed nickel reference electrode has been examined for its reusability and stability by using electrochemical technique and cyclic voltammetry.Five scans of cyclic voltammetry are performed for both membrane fabricated reference electrode.A slight positive shift in oxidation peaks is observed for mullite membrane electrode(64 mV from scan 1 to 5).The stability measurements are noted by changing the scan rate between 50 and 150 mV s−1.Furthermore,the results show that the Ni/Ni(OH)2 reference electrode covered with a mullite membrane is stable and reusable at 300℃temperature without any deterioration.The stability and reusability of prepared nickel reference electrode covered by mullite tube in the eutectic molten hydroxide were up to 9 days to carry out an electrochemical investigation,while for alumina tube reference electrode the stability and reliability were up to 3 days.The internal electrolytic material and ionic conductance can play an important role for future studies with this reference electrode along with optimisation of temperature and scan rate parameters.
基金funding from the International Doctoral Innovation CentreNingbo Education Bureau+2 种基金Ningbo Science and Technology Bureauthe University of NottinghamNingbo Municipal Government(3315 Plan and 2014A35001-1)
文摘Device level performance of aqueous halide supercapatteries fabricated with equal electrode mass of activated carbon or graphene nanoplatelets has been characterized.It was revealed that the surface oxygen groups in the graphitic structures of the nanoplatelets contributed toward a more enhanced charge storage capacity in bromide containing redox electrolytes.Moreover,the rate performance of the devices could be linked to the effect of the pore size of the carbons on the dynamics of the inactive alkali metal counterion of the redox halide salt.Additionally,the charge storage performance of aqueous halide supercapatteries with graphene nanoplatelets as the electrode material may be attributed to the combined effect of the porous structure on the dynamics of the non-active cations and a possible interaction of the Br^(-)/(Br_(2)+Br^(-)_(3))redox triple with the surface oxygen groups within the graphitic layer of the nanoplatelets.Generally,it has been shown that the surface groups and microstructure of electrode materials must be critically correlated with the redox electrolytes in the ongoing efforts to commercialize these devices.
基金supported by the National Key R&D Program of China(2016YFB0100100)the National Natural Science Foundation of China(51702335 and 21773279)+8 种基金Zhejiang Non-profit Technology Applied Research Program(LGG19B010001)Ningbo Municipal Natural Science Foundation(2018A610084)the CAS-EU S&T Cooperation Partner Program(174433KYSB20150013)the Key Laboratory of Bio-based Polymeric Materials of Zhejiang Provincethe funding from Marie Sklodowska-Curie Fellowship in EUthe Engineering and Physical Sciences Research Council(EPSRC),including the SUPERGEN Energy Storage Hub(EP/L019469/1)Enabling Next Generation Lithium Batteries(EP/M009521/1)Henry Royce Institute for Advanced Materials(EP/R00661X/1,EP/S019367/1,EP/R010145/1)the Faraday Institution All-Solid-State Batteries with Li and Na Anodes(FIRG007,FIRG008)for financial support。
文摘嵌入型过渡金属氧化物因具有安全的工作电压、高比容量和快速的嵌锂能力而受到广泛关注.但低本征电导率特性严重影响其作为锂电负极材料的寿命和性能.本文通过简便易行、可规模化放大的二氧化碳热处理方法构筑了具有新型嵌覆型碳结构的Nb_(2)O_(5)/C纳米杂化材料.在控制碳含量的前提下,实现了颗粒聚集体内部表面可控碳包覆.以嵌覆型碳结构的Nb_(2)O_(5)/C纳米杂化材料为负极组装的锂离子电池在40 mA g(-1)电流密度下容量可达387 mA hg(-1),而在200 mA g(-1)电流密度下循环500次后,容量保持率在92%以上.采用电化学滴定、差分电化学质谱(DEMS)等方法对嵌覆型五氧化二铌/碳纳米杂化材料脱嵌锂动力学过程以及产气行为进行了研究.本文提出的嵌覆型碳结构有望为高性能嵌入型过渡金属氧化物的结构设计提供参考.