Effectively extracting lithium at a relatively low temperature from the slag produced by the pyrometallurgical treatment of spent lithium-ion batteries remains a great challenge,which limits the acquirement of lithium...Effectively extracting lithium at a relatively low temperature from the slag produced by the pyrometallurgical treatment of spent lithium-ion batteries remains a great challenge,which limits the acquirement of lithium.Herein,we proposed a eutectic system to roast slag at a lower temperature based on sodium sulfate-sodium chloride(Na_(2)SO_(4)-NaCl)binary eutectic salts.The optimal roasting conditions are as follows:the slag was roasted at 750℃with a(SO_(4)^(2-)+Cl^(-))/Li+molar ratio of 5:1 for 120 min.Followed by aqueous leaching 5 min at room temperature with a water/roasted samples mass ratio of 30:1,it can get 97.07%lithium extraction efficiency.展开更多
In this paper,a novel ternary eutectic salt Na_(2)CO_(3)-Li_(2)CO_(3)-LiF was designed and investigated for concentrated solar power(CSP).The FactSage software was used to predict the composition and eutectic point of...In this paper,a novel ternary eutectic salt Na_(2)CO_(3)-Li_(2)CO_(3)-LiF was designed and investigated for concentrated solar power(CSP).The FactSage software was used to predict the composition and eutectic point of Na_(2)CO_(3)-Li_(2)CO_(3)-LiF.The microstructure,thermophysical properties,and thermal stability of eutectic salts were experimentally measured using various analytical methods.With a mass ratio of 57%:32%:11%,the eutectic salt exhibited excellent thermal storage properties with a fusion enthalpy of 413 J/g and a melting point of 426.8℃.The excellent thermal stability of the eutectic salt was reflected by a weight loss of only 0.8% at 600℃.展开更多
Spinel metal oxides containing Mn,Co,or Fe(AB_(2)O_(4),A/B=Mn/Fe/Co)are one of the most promising nonPt electrocatalysts for oxygen reduction reaction(ORR)in alkaline conditions.However,the low conductivity of metal o...Spinel metal oxides containing Mn,Co,or Fe(AB_(2)O_(4),A/B=Mn/Fe/Co)are one of the most promising nonPt electrocatalysts for oxygen reduction reaction(ORR)in alkaline conditions.However,the low conductivity of metal oxides and the poor intrinsic activities of transition metal sites lead to unsatisfactory ORR performance.In this study,eutectic molten salt(EMS)treatment is employed to reconstruct the atomic arrangement of MnFe_(2)O_(4)electrocatalyst as a prototype for enhancing ORR performance.Comprehensive analyses by using XAFS,soft XAS,XPS,and electrochemical methods reveal that the EMS treatment reduces the oxygen vacancies and spinel inverse in MnFe_(2)O_(4)effectively,which improves the electric conductivity and increases the population of more catalytically active Mn^(2+)sites with tetrahedral coordination.Moreover,the enhanced Mn-O interaction after EMS treatment is conducive to the adsorption and activation of O_(2),which promotes the first electron transfer step(generally considered as the ratedetermining step)of the ORR process.As a result,the EMS treated MnFe_(2)O_(4)catalyst delivers a positive shift of 40 mV in the ORR half-wave potential and a two-fold enhanced mass/specific activity.This work provides a convenient approach to manipulate the atomic architecture and local electronic structure of spinel oxides as ORR electrocatalysts and a comprehensive understanding of the structureperformance relationship from the molecular/atomic scale.展开更多
Through orthogonal experiment, a new type of LiClO4-LiNO3-LiBr eutectic salt with optimum mole ratio of n(LiClO4)∶n(LiNO3)∶n(LiBr)=1.6∶3.8∶1.0 was prepared. The poly(lithium acrylate-acrylonitrile)/LiClO4-...Through orthogonal experiment, a new type of LiClO4-LiNO3-LiBr eutectic salt with optimum mole ratio of n(LiClO4)∶n(LiNO3)∶n(LiBr)=1.6∶3.8∶1.0 was prepared. The poly(lithium acrylate-acrylonitrile)/LiClO4-LiNO3-LiBr solid polymer electrolytes were prepared with poly(lithium acrylate-acrylonitrile) and (LiClO4-LiNO3-LiBr) eutectic salts. The effect of LiClO4-LiNO3-LiBr eutectic salts content on the conductivity of solid polymer electrolytes was studied by alternating current impedance method, and the structures of eutectic salts and solid polymer electrolytes were characterized by differential thermal analysis, infrared spectroscopy and X-ray diffractometry. The results show that the room temperature conductivity of LiClO4-LiNO3-LiBr eutectic salts reaches (3.11×10-4 S·cm-1.) The poly(lithium acrylate-acrylonitrile)/LiClO4-LiNO3-LiBr solid polymer electrolytes possess the highest room temperature conductivity at 70% LiClO4-LiNO3-LiBr eutectic salts content, and exhibit lower glass transition temperature of 75 ℃ compared with that of poly(lithium acrylate-acrylonitrile) of 105 ℃. A complex may be formed in the solid polymer electrolytes from the differential thermal analysis and infrared spectroscopy analysis. X-ray diffraction results show that the poly(lithium acrylate-acrylonitrile) can suppress the crystallization of eutectic salts in this system.展开更多
Al-Cu-Y alloys were prepared by molten salt electrolysis in fluoride-oxide system composed of electrolyte(Na3 AlF6-AlF3-LiF-MgF2) and oxide(Al2 O3-CuO-Y2 O3). Cathodic reduction process of Al2 O3,CuO and Y2 O3 wer...Al-Cu-Y alloys were prepared by molten salt electrolysis in fluoride-oxide system composed of electrolyte(Na3 AlF6-AlF3-LiF-MgF2) and oxide(Al2 O3-CuO-Y2 O3). Cathodic reduction process of Al2 O3,CuO and Y2 O3 were analyzed by cyclic voltammetry and chronoamperometry. Components and phase composition of alloy samples prepared by potentiostatic electrolysis were characterized by scanning electron microscopy and energy dispersive spectroscopy. The results show that the Al-Cu-Y alloy can be prepared in the AIF3-NaF-5 wt%LiF-5 wt%MgF2(NaF/AlF3 = 2.2, molecular ratio) eutectic system with mixed oxide(Al2 O3-CuO-Y2 O3) through 2 h at the conditions of a temperature of 1208 K, cell voltage3.0 V, cathode current density 0.7 A/cm^2. Al(Ⅲ) and Cu(Ⅱ) ions can be reduced to zero valence Al(0) and Cu(0) directly on carbonaceous electrode surface by instantaneous nucleation, respectively, the reduction process is controlled by diffusion. The reduction potential of Y(Ⅲ) ions is close to the active ions of fluoride melts, but strengthened phase AI3 Y can be formed through electrochemical reduction and alloyed process with active Al(Ⅲ) and Cu(Ⅱ) ions, meanwhile, the Al2 Cu and Al3 Y phases are distributed at the grain boundary of Al matrix.展开更多
The electrochemical formation of Sc-Cu alloy was investigated in LiF-CaF_(2) eutectic molten salt employing various electrochemical methods.Cyclic voltammetry and square wave voltammetry indicate that the reduction of...The electrochemical formation of Sc-Cu alloy was investigated in LiF-CaF_(2) eutectic molten salt employing various electrochemical methods.Cyclic voltammetry and square wave voltammetry indicate that the reduction of scandium(Ⅲ) on the tungsten electrode is a one-step reduction process with three electrons transfer.And underpotential deposition of scandium on the copper electrode occurs owing to the depolarization effect,i.e.,forming Sc-Cu intermetallic compounds.The thermodynamic properties of the Sc-Cu intermetallic compounds ScCu_(4),ScCu_(2),and ScCu in the temperature range of 1153-1223 K were estimated by open-circuit chronopotentiometry.Moreover,the Sc-Cu alloys were prepared by potentiostatic electrolysis and characterized by optical microscope,X-ray diffraction,scanning electron microscopy,and energy dispersive spectroscopy.The results reveal that only Sc-Cu alloy composed of Cu-ScCu_(4) can be synthesized at low cathodic current density and above eutectic temperature.展开更多
Lithium-iodine(Li-I_(2))battery exhibits high potential to match with high-rate property and large energy density.However,problems of the system,such as evident sublimation of iodine elements,dissolution of iodine spe...Lithium-iodine(Li-I_(2))battery exhibits high potential to match with high-rate property and large energy density.However,problems of the system,such as evident sublimation of iodine elements,dissolution of iodine species in electrolyte,and lithium anode corrosion,prevent the practical use of rechargeable Li-I_(2)batteries.In this work,a molten Li-I_(2)typical cell design which has distinct advantages based on the solid-state garnet electrolyte with the eutectic iodate cathode is firstly developed.The U-shaped ceramic electrolyte tube can separate Li anode from the eutectic iodate cathode,so as to better tackle the above-mentioned inherent challenges for the liquid electrolyte systems.Without self-discharging and lithium anode corrosion,this solid-state battery system demonstrates high safety margin and excellent electrochemical performance.Also,the simple battery structure also indicates the easy assembly process and recycling of electrode materials.With the cathode loading of 593 mg in a single cell,an energy density of~506.7 Wh·kg^(-1)was achieved at 1 C and a long-term cycling life for 2,000 cycles also displays negligible capacity decay.展开更多
基金supported by the National Natural Science Foun-dation of China(21276022).
文摘Effectively extracting lithium at a relatively low temperature from the slag produced by the pyrometallurgical treatment of spent lithium-ion batteries remains a great challenge,which limits the acquirement of lithium.Herein,we proposed a eutectic system to roast slag at a lower temperature based on sodium sulfate-sodium chloride(Na_(2)SO_(4)-NaCl)binary eutectic salts.The optimal roasting conditions are as follows:the slag was roasted at 750℃with a(SO_(4)^(2-)+Cl^(-))/Li+molar ratio of 5:1 for 120 min.Followed by aqueous leaching 5 min at room temperature with a water/roasted samples mass ratio of 30:1,it can get 97.07%lithium extraction efficiency.
基金the funding support from the National Key Research and Development Plan of China (2018YFA0702300)National Natural Science Foundation of China (NSFC 2151802156)+3 种基金Natural Science Foundation of Jiangsu Province (BK20181302)the Fundamental Research Funds for the Central Universities (30920041107)UK Engineering and Physical Sciences Research Council (EPSRC) for partial support to this project (Grants EP/T022981/1,EP/S032622/1 and EP/P003435/1)the British Council (2020-RLWK12-10478 and 2019-RLWK11-10724)。
文摘In this paper,a novel ternary eutectic salt Na_(2)CO_(3)-Li_(2)CO_(3)-LiF was designed and investigated for concentrated solar power(CSP).The FactSage software was used to predict the composition and eutectic point of Na_(2)CO_(3)-Li_(2)CO_(3)-LiF.The microstructure,thermophysical properties,and thermal stability of eutectic salts were experimentally measured using various analytical methods.With a mass ratio of 57%:32%:11%,the eutectic salt exhibited excellent thermal storage properties with a fusion enthalpy of 413 J/g and a melting point of 426.8℃.The excellent thermal stability of the eutectic salt was reflected by a weight loss of only 0.8% at 600℃.
基金supported by the National Natural Science Foundation of China (12241502,52002367)the Fundamental Research Funds for the Central Universities (20720220010)the National Key Research and Development Program of China (2019YFA0405602)。
文摘Spinel metal oxides containing Mn,Co,or Fe(AB_(2)O_(4),A/B=Mn/Fe/Co)are one of the most promising nonPt electrocatalysts for oxygen reduction reaction(ORR)in alkaline conditions.However,the low conductivity of metal oxides and the poor intrinsic activities of transition metal sites lead to unsatisfactory ORR performance.In this study,eutectic molten salt(EMS)treatment is employed to reconstruct the atomic arrangement of MnFe_(2)O_(4)electrocatalyst as a prototype for enhancing ORR performance.Comprehensive analyses by using XAFS,soft XAS,XPS,and electrochemical methods reveal that the EMS treatment reduces the oxygen vacancies and spinel inverse in MnFe_(2)O_(4)effectively,which improves the electric conductivity and increases the population of more catalytically active Mn^(2+)sites with tetrahedral coordination.Moreover,the enhanced Mn-O interaction after EMS treatment is conducive to the adsorption and activation of O_(2),which promotes the first electron transfer step(generally considered as the ratedetermining step)of the ORR process.As a result,the EMS treated MnFe_(2)O_(4)catalyst delivers a positive shift of 40 mV in the ORR half-wave potential and a two-fold enhanced mass/specific activity.This work provides a convenient approach to manipulate the atomic architecture and local electronic structure of spinel oxides as ORR electrocatalysts and a comprehensive understanding of the structureperformance relationship from the molecular/atomic scale.
文摘Through orthogonal experiment, a new type of LiClO4-LiNO3-LiBr eutectic salt with optimum mole ratio of n(LiClO4)∶n(LiNO3)∶n(LiBr)=1.6∶3.8∶1.0 was prepared. The poly(lithium acrylate-acrylonitrile)/LiClO4-LiNO3-LiBr solid polymer electrolytes were prepared with poly(lithium acrylate-acrylonitrile) and (LiClO4-LiNO3-LiBr) eutectic salts. The effect of LiClO4-LiNO3-LiBr eutectic salts content on the conductivity of solid polymer electrolytes was studied by alternating current impedance method, and the structures of eutectic salts and solid polymer electrolytes were characterized by differential thermal analysis, infrared spectroscopy and X-ray diffractometry. The results show that the room temperature conductivity of LiClO4-LiNO3-LiBr eutectic salts reaches (3.11×10-4 S·cm-1.) The poly(lithium acrylate-acrylonitrile)/LiClO4-LiNO3-LiBr solid polymer electrolytes possess the highest room temperature conductivity at 70% LiClO4-LiNO3-LiBr eutectic salts content, and exhibit lower glass transition temperature of 75 ℃ compared with that of poly(lithium acrylate-acrylonitrile) of 105 ℃. A complex may be formed in the solid polymer electrolytes from the differential thermal analysis and infrared spectroscopy analysis. X-ray diffraction results show that the poly(lithium acrylate-acrylonitrile) can suppress the crystallization of eutectic salts in this system.
基金Project supported by the National Natural Science Foundation of China(51564015)
文摘Al-Cu-Y alloys were prepared by molten salt electrolysis in fluoride-oxide system composed of electrolyte(Na3 AlF6-AlF3-LiF-MgF2) and oxide(Al2 O3-CuO-Y2 O3). Cathodic reduction process of Al2 O3,CuO and Y2 O3 were analyzed by cyclic voltammetry and chronoamperometry. Components and phase composition of alloy samples prepared by potentiostatic electrolysis were characterized by scanning electron microscopy and energy dispersive spectroscopy. The results show that the Al-Cu-Y alloy can be prepared in the AIF3-NaF-5 wt%LiF-5 wt%MgF2(NaF/AlF3 = 2.2, molecular ratio) eutectic system with mixed oxide(Al2 O3-CuO-Y2 O3) through 2 h at the conditions of a temperature of 1208 K, cell voltage3.0 V, cathode current density 0.7 A/cm^2. Al(Ⅲ) and Cu(Ⅱ) ions can be reduced to zero valence Al(0) and Cu(0) directly on carbonaceous electrode surface by instantaneous nucleation, respectively, the reduction process is controlled by diffusion. The reduction potential of Y(Ⅲ) ions is close to the active ions of fluoride melts, but strengthened phase AI3 Y can be formed through electrochemical reduction and alloyed process with active Al(Ⅲ) and Cu(Ⅱ) ions, meanwhile, the Al2 Cu and Al3 Y phases are distributed at the grain boundary of Al matrix.
基金Project supported by the National Key Research and Development Program (2020YFC1909100)。
文摘The electrochemical formation of Sc-Cu alloy was investigated in LiF-CaF_(2) eutectic molten salt employing various electrochemical methods.Cyclic voltammetry and square wave voltammetry indicate that the reduction of scandium(Ⅲ) on the tungsten electrode is a one-step reduction process with three electrons transfer.And underpotential deposition of scandium on the copper electrode occurs owing to the depolarization effect,i.e.,forming Sc-Cu intermetallic compounds.The thermodynamic properties of the Sc-Cu intermetallic compounds ScCu_(4),ScCu_(2),and ScCu in the temperature range of 1153-1223 K were estimated by open-circuit chronopotentiometry.Moreover,the Sc-Cu alloys were prepared by potentiostatic electrolysis and characterized by optical microscope,X-ray diffraction,scanning electron microscopy,and energy dispersive spectroscopy.The results reveal that only Sc-Cu alloy composed of Cu-ScCu_(4) can be synthesized at low cathodic current density and above eutectic temperature.
文摘Lithium-iodine(Li-I_(2))battery exhibits high potential to match with high-rate property and large energy density.However,problems of the system,such as evident sublimation of iodine elements,dissolution of iodine species in electrolyte,and lithium anode corrosion,prevent the practical use of rechargeable Li-I_(2)batteries.In this work,a molten Li-I_(2)typical cell design which has distinct advantages based on the solid-state garnet electrolyte with the eutectic iodate cathode is firstly developed.The U-shaped ceramic electrolyte tube can separate Li anode from the eutectic iodate cathode,so as to better tackle the above-mentioned inherent challenges for the liquid electrolyte systems.Without self-discharging and lithium anode corrosion,this solid-state battery system demonstrates high safety margin and excellent electrochemical performance.Also,the simple battery structure also indicates the easy assembly process and recycling of electrode materials.With the cathode loading of 593 mg in a single cell,an energy density of~506.7 Wh·kg^(-1)was achieved at 1 C and a long-term cycling life for 2,000 cycles also displays negligible capacity decay.