The present work uses PEO solution to well disperse carbon fiber and identifies percolation thresholds of carbon fiber and carbon black which are used as conductive fillers.The resultant cathode plates have an average...The present work uses PEO solution to well disperse carbon fiber and identifies percolation thresholds of carbon fiber and carbon black which are used as conductive fillers.The resultant cathode plates have an average compressive strength of 27.3 MPa and flexural strength of 29.09 MPa,which demonstrate excellent mechanical properties.The Cu^(2+)removal efficiency was measured at different current densities in EC process with cement-based cathode plate,while the voltage changes were recorded.The results showed that the cement-based cathode plate operated stably and achieved 99.7%removal of 1 L of simulated wastewater with a Cu^(2+)concentration of 200 ppm at a current density of 8 m A/cm^(2)for 1 h.Characterization of floc and tested cathode plates,SEM and EDS analyses,and repeatability testing of the tested plates demonstrate the reusability of the plates,proving that cement-based plates can effectively replace metal cathode plates,reduce the cost of EC and improve the applicability of EC devices.展开更多
A green and effective electrolytic process was developed to produce high-purity Mg metal using primary and secondary resources containing Mg O as a feedstock. The electrolysis of various Mg O resources was conducted u...A green and effective electrolytic process was developed to produce high-purity Mg metal using primary and secondary resources containing Mg O as a feedstock. The electrolysis of various Mg O resources was conducted using a Cu cathode in MgF2– LiF – KCl molten salt at 1043 K by applying an average current of 1.44 A for 12.5 h. The electrolysis of calcined North Korean magnesite and seawater Mg O clinker yielded Mg alloys of MgCu2and(Cu) phases with current efficiencies of 89.6–92.4%. The electrolysis of oxidized Mg O-C refractory brick, aged ferronickel slag, and ferronickel slag yielded Mg alloys of MgCu2and(Cu) phases with current efficiencies of 59.3–92.3%. The vacuum distillation of Mg alloys obtained was conducted at 1300 K for 10 h to produce high-purity Mg metal. After vacuum distillation, Mg metal with a purity of above 99.994% was obtained. Therefore, this study demonstrates the feasibility of the production of high-purity Mg metal from various Mg O resources using a novel electrolytic process with a Cu cathode, followed by vacuum distillation.展开更多
Layered oxides of P2-type Nao.68Cuo.34Mno.6602, P2-type Nao.68Cuo.34Mno.50Tio.1602, and O＇3-type NaCuo.67Sbo.3302 were synthesized and evaluated as cathode materials for room-temperature sodium-ion batteries. The fir...Layered oxides of P2-type Nao.68Cuo.34Mno.6602, P2-type Nao.68Cuo.34Mno.50Tio.1602, and O＇3-type NaCuo.67Sbo.3302 were synthesized and evaluated as cathode materials for room-temperature sodium-ion batteries. The first two materials can deliver a capacity of around 70 mAh/g. The Cu2＋ is oxidized to Cu3＋ during charging, and the Cu3＋ goes back to Cu2＋ upon discharging. This is the first demonstration of the highly reversible change of the redox couple of Cu2＋/Cu3＋ with high storage potential in secondary batteries.展开更多
In this study,a novel Mg production process for producing high-purity Mg metal from dolomite was developed.When the electrolysis of calcined dolomite was conducted using Cu cathode and C anode in MgF_(2)–LiF molten s...In this study,a novel Mg production process for producing high-purity Mg metal from dolomite was developed.When the electrolysis of calcined dolomite was conducted using Cu cathode and C anode in MgF_(2)–LiF molten salt at 1083–1173 K by applying an average current of 1.42–1.46 A for 9.50–21.0 h,the current efficiency of 66.4–88.6%was obtained.The produced Mg alloys consisted of MgCu_(2)and Cu(Mg)or MgCu_(2)and CuMg_(2)phases,depending on the Mg concentration in the Mg alloy.When the electrolysis of calcined dolomite was conducted in MgF_(2)–LiF–CaF_(2)molten salt at 1083 K,the current efficiency was 40.9–71.4%,owing to undesired reactions such as electroreduction of Ca^(2+)or/and CO_(3)^(2−)ions.Meanwhile,the current efficiency increased from 40.9%to 63.2%by utilizing a Pt anode,because the occurrence of CO_(3)^(2−)ions in the molten salt was prevented.After vacuum distillation of the obtained Mg alloys at 1300 K for 10 h,Mg metal with a purity of 99.9996–99.9998%was produced.Therefore,the feasibility of this novel process for the production of high-purity Mg metal from dolomite was demonstrated.展开更多
Rechargeable Mg batteries potentially display lower cost and competitive energy density compared with their Li-ion counterparts.However,the practical implementation of high area-capacity cathodes still remains a formi...Rechargeable Mg batteries potentially display lower cost and competitive energy density compared with their Li-ion counterparts.However,the practical implementation of high area-capacity cathodes still remains a formidably challenging task.This work presents the sulfur/copper integrated cathodes fabricated by the conventional blade-coating process and slurry-dipping method.The sulfur/copper foil integrated cathodes deliver a high area-capacity of 2.6 mAh cm^(-2)after 40 cycles,while the sulfur/copperfoam integrated cathode exhibits an ultrahigh area-capacity of 35.4 mAh cm^(-2),corresponding to 743.1 Wh L^(-1)at the electrode level(1.5 times higher than the LiCoO_(2)-graphite system).The in-situ formed copper sulfide intermediates with sufficient cation defects can act as functional intermediates to regulate the sulfur electrochemistry during the first discharge process.The subsequent cycles are operated by the reversible displacement reaction between Mg-ions and copper sulfide active substances.In particular,the copper ions prefer to extrude along the[001]direction in copper sulfides lattice and simultaneously the rock-salt MgS crystals are generated.Besides,the nonuniform surface topography of the cycled Mgmetal anode,caused by the spatial inhomogeneity in current distribution,is demonstrated to lead to the battery performance degradation for high area-capacity Mg batteries.展开更多
The cyclic voltammetry was used to study the electrochemical reaction of Sm(III) in NaCl-KCl equimolar mixture on the Co and Cu cathodes. It is reasonable to presume that the reduction of Sm(III) to Sm(II) was realize...The cyclic voltammetry was used to study the electrochemical reaction of Sm(III) in NaCl-KCl equimolar mixture on the Co and Cu cathodes. It is reasonable to presume that the reduction of Sm(III) to Sm(II) was realized on Co and Cu electrodes respectively at first step. Sm(II) was subject to the reduction and formed alloys with Co and Cu on the electrode surface.展开更多
Na-ion batteries(NIBs)are regarding as the optimum complement for Li-ion batteries along with the rapid development of stationary energy storage systems.In order to meet the commercial demands of cathodes for NIBs,O3-...Na-ion batteries(NIBs)are regarding as the optimum complement for Li-ion batteries along with the rapid development of stationary energy storage systems.In order to meet the commercial demands of cathodes for NIBs,O3-type Cu containing layered oxide Na_(0.9)0Cu_(0.22)Fe_(0.30)Mn_(0.48O_(2))with good comprehensive performance and low-cost element components is very promising for the practical use.However,only part of the Cu^(3+)/Cu^(2+)redox couple participated in the redox reaction,thus impairing the specific capacity of the cathode materials.Herein,Mg2+-doped O3-Na0.90Mg0.08Cu0.22Fe0.30Mn0.40O_(2)layered oxide without Mn3+was synthesized successfully,which exhibited improved reversible specific capacity of 118 mAh/g in the voltage range of 2.4-4.0 V at 0.2 C,corresponding to the intercalation/deintercalation of 0.47 Na+(0.1 more than that of Na_(0.9)0Cu_(0.22)Fe_(0.30)Mn_(0.48O_(2))).This work demonstrates an important strategy to obtain advanced layered oxide cathodes for NIBs.展开更多
Recently, the hydrometallurgy for metal refining is getting more and more popularin China. During a traditional hydrometallurgical process sulphuric acid is often used. In many cases, the working conditions in the sol...Recently, the hydrometallurgy for metal refining is getting more and more popularin China. During a traditional hydrometallurgical process sulphuric acid is often used. In many cases, the working conditions in the solvent extraction and electro winning processes could be very tough for the commonly used material of different equipment and components, such as, austenitic stainless steels of 304/304L and 316L. In a copper refinery, a permanent cathode plate made of 316L was taken out of production due to heavy corrosion. The samples from the corroded plate were investigated thoroughly, possible reasons were pointed out and new material was suggested in this work. It is expected this research could help the copper refineries and Sanmen Sanyou to select the proper cathode plates in complicated working conditions.展开更多
Metal–metal battery bears great potential for next-generation large-scale energy storage system because of its simple manufacture process and low production cost.However,the cross-over of metal cations from the catho...Metal–metal battery bears great potential for next-generation large-scale energy storage system because of its simple manufacture process and low production cost.However,the cross-over of metal cations from the cathode to the anode causes a loss in capacity and influences battery stability.Herein,a coating of poly(ionic liquid)(PIL)with poly(diallyldimethylammonium bis(trifluoromethanesulfonyl)imide)(PDADMA^(+)TFSI^(−))on a commercial polypropylene(PP)separator serves as an anion exchange membrane for a 3.3 V copper–lithium battery.The PIL has a positively charged polymer backbone that can block the migration of copper ions,thus improving Coulombic efficiency,long-term cycling stability and inhibiting self-discharge of the battery.It can also facilitate the conduction of anions through the membrane and reduce polarization,especially for fast charging/discharging.Bruce-Vincent method gives the transport number in the electrolyte to be 0.25 and 0.04 for PP separator without and with PIL coating,respectively.This suggests that the PIL layer reduces the contribution of the internal current due to cation transport.The use of PIL as a coating layer for commercial PP separator is a cost-effective way to improve overall electrochemical performance of copper–lithium batteries.Compared to PP and polyacrylic acid(PAA)/PP separators,the PIL/PP membrane raises the Coulombic efficiency to 99%and decreases the average discharge voltage drop to about 0.09 V when the current density is increased from 0.1 to 1 mA cm^(−2).展开更多
Copper sulfide(CuS)is a promising cathode for lithium-ion batteries(LIBs)due to its impeccable theoretical energy density(~1015 Wh·kg^(−1) and 4743 Wh·L^(−1)).However,it suffers from voltage decay leaded ene...Copper sulfide(CuS)is a promising cathode for lithium-ion batteries(LIBs)due to its impeccable theoretical energy density(~1015 Wh·kg^(−1) and 4743 Wh·L^(−1)).However,it suffers from voltage decay leaded energy density loss and low energy efficiency,which hinders its application.In this work,with combined ex-situ/in-situ X-ray diffraction(XRD)and electrochemical analysis,we explore detailed degradation mechanisms.For the voltage decay,it is attributed to a spontaneous reaction between CuS cathode and copper current collector(Cu CC).This reaction leads to energy density loss and active materials degradation(CuS→Cu_(1.81)S).As for energy efficiency,CuS undergoes a series of phase transformations.The main phase transition processes are CuS→α-LiCuS→Li_(2−x)Cu_(x)S+Cu→Li_(2)S+Cu for discharge;Li_(2)S+Cu→Li_(2−x)Cu_(x)S→β-LiCuS→CuS for charge.Here,α-LiCuS,β-LiCuS,and Li_(2−x)CuxS are newly identified phases.These phase changes are driven by topotactic-reaction-related copper diffusion and rearrangement.This work demonstrates the significance of transition-metal diffusion in the intermediates formation and phase change in conversion-type materials.展开更多
基金Funded by the National Natural Science Foundation of China (No.52078394)the Key Research and Development Program of Hubei Provincial (No.2020BAB081)。
文摘The present work uses PEO solution to well disperse carbon fiber and identifies percolation thresholds of carbon fiber and carbon black which are used as conductive fillers.The resultant cathode plates have an average compressive strength of 27.3 MPa and flexural strength of 29.09 MPa,which demonstrate excellent mechanical properties.The Cu^(2+)removal efficiency was measured at different current densities in EC process with cement-based cathode plate,while the voltage changes were recorded.The results showed that the cement-based cathode plate operated stably and achieved 99.7%removal of 1 L of simulated wastewater with a Cu^(2+)concentration of 200 ppm at a current density of 8 m A/cm^(2)for 1 h.Characterization of floc and tested cathode plates,SEM and EDS analyses,and repeatability testing of the tested plates demonstrate the reusability of the plates,proving that cement-based plates can effectively replace metal cathode plates,reduce the cost of EC and improve the applicability of EC devices.
基金supported by the Korea Evaluation Institute of Industrial Technology funded by the Korean Ministry of Industry in Korea (Project No.:20000970, 20–9805)Basic Research Project (22–3803) of the Korea Institute of Geoscience and Mineral Resources (KIGAM) funded by the Ministry of Science and ICT of Korea。
文摘A green and effective electrolytic process was developed to produce high-purity Mg metal using primary and secondary resources containing Mg O as a feedstock. The electrolysis of various Mg O resources was conducted using a Cu cathode in MgF2– LiF – KCl molten salt at 1043 K by applying an average current of 1.44 A for 12.5 h. The electrolysis of calcined North Korean magnesite and seawater Mg O clinker yielded Mg alloys of MgCu2and(Cu) phases with current efficiencies of 89.6–92.4%. The electrolysis of oxidized Mg O-C refractory brick, aged ferronickel slag, and ferronickel slag yielded Mg alloys of MgCu2and(Cu) phases with current efficiencies of 59.3–92.3%. The vacuum distillation of Mg alloys obtained was conducted at 1300 K for 10 h to produce high-purity Mg metal. After vacuum distillation, Mg metal with a purity of above 99.994% was obtained. Therefore, this study demonstrates the feasibility of the production of high-purity Mg metal from various Mg O resources using a novel electrolytic process with a Cu cathode, followed by vacuum distillation.
基金supported by the National Natural Science Foundation of China(Grant Nos.51222210 and 11234013)the One Hundred Talent Project of the Chinese Academy of Sciences
文摘Layered oxides of P2-type Nao.68Cuo.34Mno.6602, P2-type Nao.68Cuo.34Mno.50Tio.1602, and O＇3-type NaCuo.67Sbo.3302 were synthesized and evaluated as cathode materials for room-temperature sodium-ion batteries. The first two materials can deliver a capacity of around 70 mAh/g. The Cu2＋ is oxidized to Cu3＋ during charging, and the Cu3＋ goes back to Cu2＋ upon discharging. This is the first demonstration of the highly reversible change of the redox couple of Cu2＋/Cu3＋ with high storage potential in secondary batteries.
基金supported by the National Research Councile of Science and Technology funded by the Korean Ministry of Industry in Korea(Project Nos.:1711173260,22-3803)the Korea Evaluation Institute of Industrial Technology funded by the Korean Ministry of Industry in Korea(Project Nos.:1415179713,20011157).
文摘In this study,a novel Mg production process for producing high-purity Mg metal from dolomite was developed.When the electrolysis of calcined dolomite was conducted using Cu cathode and C anode in MgF_(2)–LiF molten salt at 1083–1173 K by applying an average current of 1.42–1.46 A for 9.50–21.0 h,the current efficiency of 66.4–88.6%was obtained.The produced Mg alloys consisted of MgCu_(2)and Cu(Mg)or MgCu_(2)and CuMg_(2)phases,depending on the Mg concentration in the Mg alloy.When the electrolysis of calcined dolomite was conducted in MgF_(2)–LiF–CaF_(2)molten salt at 1083 K,the current efficiency was 40.9–71.4%,owing to undesired reactions such as electroreduction of Ca^(2+)or/and CO_(3)^(2−)ions.Meanwhile,the current efficiency increased from 40.9%to 63.2%by utilizing a Pt anode,because the occurrence of CO_(3)^(2−)ions in the molten salt was prevented.After vacuum distillation of the obtained Mg alloys at 1300 K for 10 h,Mg metal with a purity of 99.9996–99.9998%was produced.Therefore,the feasibility of this novel process for the production of high-purity Mg metal from dolomite was demonstrated.
基金supported by the National Natural Science Foundation of China(21805157,51972187)the Project funded by China Postdoctoral Science Foundation(2021M701817)+2 种基金the Natural Science Foundation of Shandong Provincial(ZR2021QE166)the National Natural Science Foundation for Distinguished Young Scholars of China(51625204)the Major Basic Research Program of Natural Science Foundation of Shandong Province(ZR2020ZD09)。
文摘Rechargeable Mg batteries potentially display lower cost and competitive energy density compared with their Li-ion counterparts.However,the practical implementation of high area-capacity cathodes still remains a formidably challenging task.This work presents the sulfur/copper integrated cathodes fabricated by the conventional blade-coating process and slurry-dipping method.The sulfur/copper foil integrated cathodes deliver a high area-capacity of 2.6 mAh cm^(-2)after 40 cycles,while the sulfur/copperfoam integrated cathode exhibits an ultrahigh area-capacity of 35.4 mAh cm^(-2),corresponding to 743.1 Wh L^(-1)at the electrode level(1.5 times higher than the LiCoO_(2)-graphite system).The in-situ formed copper sulfide intermediates with sufficient cation defects can act as functional intermediates to regulate the sulfur electrochemistry during the first discharge process.The subsequent cycles are operated by the reversible displacement reaction between Mg-ions and copper sulfide active substances.In particular,the copper ions prefer to extrude along the[001]direction in copper sulfides lattice and simultaneously the rock-salt MgS crystals are generated.Besides,the nonuniform surface topography of the cycled Mgmetal anode,caused by the spatial inhomogeneity in current distribution,is demonstrated to lead to the battery performance degradation for high area-capacity Mg batteries.
文摘The cyclic voltammetry was used to study the electrochemical reaction of Sm(III) in NaCl-KCl equimolar mixture on the Co and Cu cathodes. It is reasonable to presume that the reduction of Sm(III) to Sm(II) was realized on Co and Cu electrodes respectively at first step. Sm(II) was subject to the reduction and formed alloys with Co and Cu on the electrode surface.
基金supported by the National Natural Science Foundation of China(Grant Nos.51725206,52122214,and 52072403)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDA21070500)+1 种基金Youth Innovation Promotion Association of the Chinese Academy of Sciences(Grant No.2020006)Beijing Municipal Natural Science Foundation,China(Grant No.2212022)。
文摘Na-ion batteries(NIBs)are regarding as the optimum complement for Li-ion batteries along with the rapid development of stationary energy storage systems.In order to meet the commercial demands of cathodes for NIBs,O3-type Cu containing layered oxide Na_(0.9)0Cu_(0.22)Fe_(0.30)Mn_(0.48O_(2))with good comprehensive performance and low-cost element components is very promising for the practical use.However,only part of the Cu^(3+)/Cu^(2+)redox couple participated in the redox reaction,thus impairing the specific capacity of the cathode materials.Herein,Mg2+-doped O3-Na0.90Mg0.08Cu0.22Fe0.30Mn0.40O_(2)layered oxide without Mn3+was synthesized successfully,which exhibited improved reversible specific capacity of 118 mAh/g in the voltage range of 2.4-4.0 V at 0.2 C,corresponding to the intercalation/deintercalation of 0.47 Na+(0.1 more than that of Na_(0.9)0Cu_(0.22)Fe_(0.30)Mn_(0.48O_(2))).This work demonstrates an important strategy to obtain advanced layered oxide cathodes for NIBs.
文摘Recently, the hydrometallurgy for metal refining is getting more and more popularin China. During a traditional hydrometallurgical process sulphuric acid is often used. In many cases, the working conditions in the solvent extraction and electro winning processes could be very tough for the commonly used material of different equipment and components, such as, austenitic stainless steels of 304/304L and 316L. In a copper refinery, a permanent cathode plate made of 316L was taken out of production due to heavy corrosion. The samples from the corroded plate were investigated thoroughly, possible reasons were pointed out and new material was suggested in this work. It is expected this research could help the copper refineries and Sanmen Sanyou to select the proper cathode plates in complicated working conditions.
基金supported by grant from the Research Grants Council(City U 11305220)of the Hong Kong Special Administrative Region,China
文摘Metal–metal battery bears great potential for next-generation large-scale energy storage system because of its simple manufacture process and low production cost.However,the cross-over of metal cations from the cathode to the anode causes a loss in capacity and influences battery stability.Herein,a coating of poly(ionic liquid)(PIL)with poly(diallyldimethylammonium bis(trifluoromethanesulfonyl)imide)(PDADMA^(+)TFSI^(−))on a commercial polypropylene(PP)separator serves as an anion exchange membrane for a 3.3 V copper–lithium battery.The PIL has a positively charged polymer backbone that can block the migration of copper ions,thus improving Coulombic efficiency,long-term cycling stability and inhibiting self-discharge of the battery.It can also facilitate the conduction of anions through the membrane and reduce polarization,especially for fast charging/discharging.Bruce-Vincent method gives the transport number in the electrolyte to be 0.25 and 0.04 for PP separator without and with PIL coating,respectively.This suggests that the PIL layer reduces the contribution of the internal current due to cation transport.The use of PIL as a coating layer for commercial PP separator is a cost-effective way to improve overall electrochemical performance of copper–lithium batteries.Compared to PP and polyacrylic acid(PAA)/PP separators,the PIL/PP membrane raises the Coulombic efficiency to 99%and decreases the average discharge voltage drop to about 0.09 V when the current density is increased from 0.1 to 1 mA cm^(−2).
基金supported by the National Natural Science Foundation of China(No.52072061)the Natural Science Foundation of Sichuan,China(No.2023NSFSC1914).
文摘Copper sulfide(CuS)is a promising cathode for lithium-ion batteries(LIBs)due to its impeccable theoretical energy density(~1015 Wh·kg^(−1) and 4743 Wh·L^(−1)).However,it suffers from voltage decay leaded energy density loss and low energy efficiency,which hinders its application.In this work,with combined ex-situ/in-situ X-ray diffraction(XRD)and electrochemical analysis,we explore detailed degradation mechanisms.For the voltage decay,it is attributed to a spontaneous reaction between CuS cathode and copper current collector(Cu CC).This reaction leads to energy density loss and active materials degradation(CuS→Cu_(1.81)S).As for energy efficiency,CuS undergoes a series of phase transformations.The main phase transition processes are CuS→α-LiCuS→Li_(2−x)Cu_(x)S+Cu→Li_(2)S+Cu for discharge;Li_(2)S+Cu→Li_(2−x)Cu_(x)S→β-LiCuS→CuS for charge.Here,α-LiCuS,β-LiCuS,and Li_(2−x)CuxS are newly identified phases.These phase changes are driven by topotactic-reaction-related copper diffusion and rearrangement.This work demonstrates the significance of transition-metal diffusion in the intermediates formation and phase change in conversion-type materials.
