Lithium-sulfur(Li-S)batteries have been regarded as the candidate for the next-generation energy storage system due to the high theoretical specific capacity(1675 m Ah/g), energy density(2600 Wh/kg)and the abundance o...Lithium-sulfur(Li-S)batteries have been regarded as the candidate for the next-generation energy storage system due to the high theoretical specific capacity(1675 m Ah/g), energy density(2600 Wh/kg)and the abundance of elemental sulfur, but the application of Li-S batteries is impeded by a series of problems. Recently, all-solid-state Li-S batteries(ASSLSBs) have drawn great attention because many drawbacks such as safety issues caused by metallic lithium anodes and organic liquid electrolytes can be overcome through the use of solid-state electrolytes(SEs). However, not only the problems brought by sulfur cathodes still exist, but more trouble arouses from the interfaces between SEs and cathodes, hampering the practical application of ASSLSBs. Therefore, in order to deal with the problems, enormous endeavors have been done on ASSLSB cathodes during the past few decades, including engineering of cathode active materials, cathode host materials, cathode binder materials and cathode structures. In this review, the electrochemical mechanism and existing problems of ASSLSBs are briefly introduced. Subsequently, the strategies for developing cathode materials and designing cathode structures are presented. Then there follows a brief discussion of SE problems and expectations, and finally, the challenges and perspectives of ASSLSBs are summarized.展开更多
A series of perovskite-type complex oxides LaNi1-xRuxO3 were prepared and studied by means of XRD. The effects of some factors on th complex oxides were discussed. Each kind of those perovskite-type complex oxides was...A series of perovskite-type complex oxides LaNi1-xRuxO3 were prepared and studied by means of XRD. The effects of some factors on th complex oxides were discussed. Each kind of those perovskite-type complex oxides was used to prepare cathode by composite-electroplating technique. The cathodes were electrochemically charactrized. The results show that these novel cathode exhibit high activities and excellent stabilities during long-term continuous electrolysis with some current interruptions.展开更多
To meet the developing requirements of rechargeable batteries,cathode materials should have light masses,high densities,low costs,low toxicity,small oxidation potentials,and good electronic conductivities.As the catho...To meet the developing requirements of rechargeable batteries,cathode materials should have light masses,high densities,low costs,low toxicity,small oxidation potentials,and good electronic conductivities.As the cathode active material for lithium storage,sulfur(S)has high theoretical density and cost effectiveness.However,its conductivity is poor.The heavier analogue of S,viz.Se,however,has much larger electronic conductivity and higher density.Combining the advantages of S and Se,a new type of cathode material,namely,Se_(x)S_(y),has attracted much interest in recent years.Though Se_(x)S_(y)has good conductivity and high volumetric capacity,the issues of shuttle effects,electrolyte suitability,and volume change during cycling still exist.To alleviate these issues,many groups have made versatile efforts to address Se_(x)S_(y).However,hitherto,there has been no systematic summary of this topic.Convinced by its promising synergetic effect and constructive supplement for S cathodes in rechargeable batteries,we here review the recent progress on Se_(x)S_(y)as a cathode material for Li and Na batteries.Their syntheses,structures,electrochemical performances,and the structure-property relationships are referred to.As Se_(x)S_(y)is a type of relatively young cathode,the electrolytes for Li-Se_(x)S_(y)are also addressed.Finally,the challenges and perspectives for Li/Na-Se_(x)S_(y)batteries are given.展开更多
Layered transition metal oxides(LTMOs),such as the LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)family,are the primary class of cathode active materials(CAMs)commercialized and studied for conventional lithium-ion(LIB)and solid-state...Layered transition metal oxides(LTMOs),such as the LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)family,are the primary class of cathode active materials(CAMs)commercialized and studied for conventional lithium-ion(LIB)and solid-state battery(SSB)application.Despite nearly three decades of progress in improving stability,capacity,and cost,research has intensified to match global demand for high-performance materials.Nevertheless,(de)lithiation leads to irreversible degradation and subsequent capacity fading due to(chemo)mechanical particle disintegration and(electro)chemical side reactions.In this regard,surface and bulk modifications of CAMs by coating and doping/substitution are common strategies to enhance and support the electrochemical performance.Niobium has been featured in many studies exhibiting its advantages as a bulk dopant,where its ionic radius and unique valence character with respect to the metals used in LTMOs help prevent different degradation phenomena and therefore enhance performance.In addition,several niobium-based oxides(LiNbO_(3),Li_(3)NbO_(4),Nb_(2)O^(5),etc.)have been employed as a coating to increase cycling stability and rate capability through reduced surface degradation.Herein we illustrate how niobium serves as a coating constituent and a dopant,and discuss current understanding of underlying mechanisms,gaps in knowledge,and considerations for its use in a coating and/or as dopant in LTMO cathodes.展开更多
In the present study,to understand the mechanism of Mn on inhibiting Fe-caused Mg corrosion,the corrosion behaviour of commercial pure Mg and Mg-6 Mn alloy in 0.6 M NaCl solution is investigated.It is found that in Mg...In the present study,to understand the mechanism of Mn on inhibiting Fe-caused Mg corrosion,the corrosion behaviour of commercial pure Mg and Mg-6 Mn alloy in 0.6 M NaCl solution is investigated.It is found that in Mg-6 Mn alloy,Fe impurity is incorporated into Mn to form Mn(Fe)phase with Fe as solid solute.The initial galvanic corrosion cannot be reduced through converting Fe-rich phase to Mn(Fe)phase,since Mn(Fe)phase also has relatively strong cathodic activity and has much larger volume fraction than Fe-rich phase.However,the cathodic activation behaviour of pure Mg is inhibited.The cathodic activity even decreases for Mg-Mn alloy with increased exposure time,due to the reduced cathodic HER at the Mn(Fe)particles.Mn can be oxidized at the OCP of Mg-6 Mn alloy,resulting in relatively dense Mn-rich corrosion film on particle surface,which separates the particle from the electrolyte and,consequently,inhibits HER.展开更多
Rechargeable aqueous zinc-ion batteries are recently gaining incremental attention because of low cost and material abundance,but their development is plagued by limited choices of cathode materials with satisfactory ...Rechargeable aqueous zinc-ion batteries are recently gaining incremental attention because of low cost and material abundance,but their development is plagued by limited choices of cathode materials with satisfactory cycling performance.The polyoxometalates perform formidable redox stability and able to participate in multi-electron transfer,which was well-suited for energy storage.Herein,a bicomponent polyoxometalate-derivative KNiVO(K_(2)[Ni(H_(2)O)_(6)]_(2)[V_(10)O_(28)]·_(4)H_(2)O polyoxometalates after annealing)is firstly demonstrated as a cathode material for aqueous ZIBs.The layered KV_(3)O_(8)(KVO)In the bi-component material constitutes Zn^(2+) migration and storage channels(K^(+) were substantially replaced by Zn^(2+) in the activation phase),and the three-dimensional NiV_(3)O_(8)(NiVO)part acts as skeleton to stabilize the ion channels,which assist the cell to demonstrate a high-rate capacity and specific energy of229.4 mAh/g and satisfactory cyclability(capacity retention of 99.1%after 4500 cycles at a current density of 4 A/g).These results prove the feasibility of POM as cathode materials precursor and put forward a novel pattern of the Zn^(2+)storage mechanism in the activated-KNiVO clusters,which also provide a new route for selecting or designing high-performance cathode for aqueous ZIBs and other advanced battery systems.展开更多
The high corrosion sensitivity and the potential bio-toxicity of Mg-Ag alloys limit their wide applications for the production of implanted devices. In the present work, Mn is added into the Mg-Ag alloy to optimize it...The high corrosion sensitivity and the potential bio-toxicity of Mg-Ag alloys limit their wide applications for the production of implanted devices. In the present work, Mn is added into the Mg-Ag alloy to optimize its corrosion behaviour. The corrosion behaviour of Mg-Ag-Mn alloys is investigated with the underlying microstructural factors examined. The Mg-Ag alloy with 2 wt% Mn exhibits the highest corrosion resistance after post-casting heat treatment at 440 ℃. The addition of Mn results in α-Mn phase with the incorporation of Fe, which suppresses the cathodic activity of impurity Fe. Further, heat treatment of the cast alloys homogenizes the distribution of Ag and promotes the precipitation of α-Mn phase. The former removes Ag segregations as potential cathodes;the latter promotes a more uniform distribution of cathodes and, therefore, prevents localized corrosion.展开更多
In order to enhance Ni-EDTA decomplexation and Ni recovery via photoelectrocatalytic (PEC)process,TiO_(2)/Ni-Sb-SnO_(2)bifunctional electrode was fabricated as the photoanode and activated carbon fiber (ACF) was intro...In order to enhance Ni-EDTA decomplexation and Ni recovery via photoelectrocatalytic (PEC)process,TiO_(2)/Ni-Sb-SnO_(2)bifunctional electrode was fabricated as the photoanode and activated carbon fiber (ACF) was introduced as the cathode.At a cell voltage of 3.5 V and initial solution pH of 6.3,the TiO_(2)/Ni-Sb-SnO_(2)bifunctional photoanode exhibited a synergetic effect on the decomplexation of Ni-EDTA with the pseudo-first-order rate constant of 0.01068 min^(-1)with 180 min by using stainless steel (SS) cathode,which was 1.5 and 2.4times higher than that of TiO_(2)photoanode and Ni-Sb-SnO_(2)anode,respectively.Moreover,both the efficiencies of Ni-EDTA decomplexation and Ni recovery were improved to 98%from 86%and 73%from 41%after replacing SS cathode with ACF cathode,respectively.Influencing factors on Ni-EDTA decomplexation and Ni recovery were investigated and the efficiencies were favored at acidic condition,higher cell voltage and lower initial Ni-EDTA concentration.Ni-EDTA was mainly decomposed via·OH radicals which generated via the interaction of O_(3),H_(2)O_(2),and UV irradiation in the contrasted PEC system.Then,the liberated Ni^(2+)ions which liberated from Ni-EDTA decomplexation were eventually reduced to metallic Ni on the ACF cathode surface.Finally,the stability of the constructed PEC system on Ni-EDTA decomplexation and Ni recovery was exhibited.展开更多
Fe-N-C catalysts represent the most promising class of platinum group metal-free(PGM-free)catalysts for the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs),exhibiting intrinsic activity po...Fe-N-C catalysts represent the most promising class of platinum group metal-free(PGM-free)catalysts for the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs),exhibiting intrinsic activity potentially competitive with commercial Pt/C benchmarks.However,critical challenges persist[1].As revealed by theoretical calculations,the enhancement of intrinsic activity in Fe-N-C catalysts is constrained by inherent scaling relations among the adsorption free energies of ORR intermediates on the catalyst surface.展开更多
基金supported by the National Natural Science Foundation of China (Nos. 51874110 and 51604089)Natural Science Foundation of Heilongjiang Province (No. LH2021B011)Open Project of State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology (No. QA202138)。
文摘Lithium-sulfur(Li-S)batteries have been regarded as the candidate for the next-generation energy storage system due to the high theoretical specific capacity(1675 m Ah/g), energy density(2600 Wh/kg)and the abundance of elemental sulfur, but the application of Li-S batteries is impeded by a series of problems. Recently, all-solid-state Li-S batteries(ASSLSBs) have drawn great attention because many drawbacks such as safety issues caused by metallic lithium anodes and organic liquid electrolytes can be overcome through the use of solid-state electrolytes(SEs). However, not only the problems brought by sulfur cathodes still exist, but more trouble arouses from the interfaces between SEs and cathodes, hampering the practical application of ASSLSBs. Therefore, in order to deal with the problems, enormous endeavors have been done on ASSLSB cathodes during the past few decades, including engineering of cathode active materials, cathode host materials, cathode binder materials and cathode structures. In this review, the electrochemical mechanism and existing problems of ASSLSBs are briefly introduced. Subsequently, the strategies for developing cathode materials and designing cathode structures are presented. Then there follows a brief discussion of SE problems and expectations, and finally, the challenges and perspectives of ASSLSBs are summarized.
基金Funding from the U.S.Army Research Laboratory under agreement No.W911NF-14–2–0005 with Dr.Joe Labukas as project manager supported co-author JMFFunding by the Office of Naval Research grant No.N000141210967 with Dr.David A.Shifler as scientific officer supported co-author LGBThe Bruker Dimension Icon AFM utilized in this work is located in the Boise State University Surface Science Laboratory(SSL),which is part of the FaCT Core Facility,RRID:SCR_024733,that receives support from the National Institutes of Health under the Institutional Development Awards Program of the National Institute of General Medical Sciences via grants#P20GM148321 and P20GM103408,the former of which also partially supports co-authors CME and PHD.
文摘A series of perovskite-type complex oxides LaNi1-xRuxO3 were prepared and studied by means of XRD. The effects of some factors on th complex oxides were discussed. Each kind of those perovskite-type complex oxides was used to prepare cathode by composite-electroplating technique. The cathodes were electrochemically charactrized. The results show that these novel cathode exhibit high activities and excellent stabilities during long-term continuous electrolysis with some current interruptions.
基金financial support from the NSF of China(21673203 and 21771159)the Qing Lan Project,and the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘To meet the developing requirements of rechargeable batteries,cathode materials should have light masses,high densities,low costs,low toxicity,small oxidation potentials,and good electronic conductivities.As the cathode active material for lithium storage,sulfur(S)has high theoretical density and cost effectiveness.However,its conductivity is poor.The heavier analogue of S,viz.Se,however,has much larger electronic conductivity and higher density.Combining the advantages of S and Se,a new type of cathode material,namely,Se_(x)S_(y),has attracted much interest in recent years.Though Se_(x)S_(y)has good conductivity and high volumetric capacity,the issues of shuttle effects,electrolyte suitability,and volume change during cycling still exist.To alleviate these issues,many groups have made versatile efforts to address Se_(x)S_(y).However,hitherto,there has been no systematic summary of this topic.Convinced by its promising synergetic effect and constructive supplement for S cathodes in rechargeable batteries,we here review the recent progress on Se_(x)S_(y)as a cathode material for Li and Na batteries.Their syntheses,structures,electrochemical performances,and the structure-property relationships are referred to.As Se_(x)S_(y)is a type of relatively young cathode,the electrolytes for Li-Se_(x)S_(y)are also addressed.Finally,the challenges and perspectives for Li/Na-Se_(x)S_(y)batteries are given.
基金supported by BASF SE.The authors are grateful to the Federal Ministry of Education and Research(Bundesministerium für Bildung und Forschung,BMBF)for funding within the projects SUSTRAB(03XP0415D),UNIKAM(03XP0484B),and MELLi(03XP0447).
文摘Layered transition metal oxides(LTMOs),such as the LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)family,are the primary class of cathode active materials(CAMs)commercialized and studied for conventional lithium-ion(LIB)and solid-state battery(SSB)application.Despite nearly three decades of progress in improving stability,capacity,and cost,research has intensified to match global demand for high-performance materials.Nevertheless,(de)lithiation leads to irreversible degradation and subsequent capacity fading due to(chemo)mechanical particle disintegration and(electro)chemical side reactions.In this regard,surface and bulk modifications of CAMs by coating and doping/substitution are common strategies to enhance and support the electrochemical performance.Niobium has been featured in many studies exhibiting its advantages as a bulk dopant,where its ionic radius and unique valence character with respect to the metals used in LTMOs help prevent different degradation phenomena and therefore enhance performance.In addition,several niobium-based oxides(LiNbO_(3),Li_(3)NbO_(4),Nb_(2)O^(5),etc.)have been employed as a coating to increase cycling stability and rate capability through reduced surface degradation.Herein we illustrate how niobium serves as a coating constituent and a dopant,and discuss current understanding of underlying mechanisms,gaps in knowledge,and considerations for its use in a coating and/or as dopant in LTMO cathodes.
基金financial support by the National Nature Science Foundation of China(No.51601036 and U1737102)the Fundamental Research Funds for the Central Universities(N170204010 and N162410002-2-4)Young Elite Scientists Sponsorship Program by CAST(2017QNRC001)
文摘In the present study,to understand the mechanism of Mn on inhibiting Fe-caused Mg corrosion,the corrosion behaviour of commercial pure Mg and Mg-6 Mn alloy in 0.6 M NaCl solution is investigated.It is found that in Mg-6 Mn alloy,Fe impurity is incorporated into Mn to form Mn(Fe)phase with Fe as solid solute.The initial galvanic corrosion cannot be reduced through converting Fe-rich phase to Mn(Fe)phase,since Mn(Fe)phase also has relatively strong cathodic activity and has much larger volume fraction than Fe-rich phase.However,the cathodic activation behaviour of pure Mg is inhibited.The cathodic activity even decreases for Mg-Mn alloy with increased exposure time,due to the reduced cathodic HER at the Mn(Fe)particles.Mn can be oxidized at the OCP of Mg-6 Mn alloy,resulting in relatively dense Mn-rich corrosion film on particle surface,which separates the particle from the electrolyte and,consequently,inhibits HER.
基金supported by the Natural Science Foundation of Hunan Province(No.2020JJ4684)the Fundamental Research Funds for the Central Universities of Central South University(No.2021zzts0522)the Recruitment Program of Global Youth Experts。
文摘Rechargeable aqueous zinc-ion batteries are recently gaining incremental attention because of low cost and material abundance,but their development is plagued by limited choices of cathode materials with satisfactory cycling performance.The polyoxometalates perform formidable redox stability and able to participate in multi-electron transfer,which was well-suited for energy storage.Herein,a bicomponent polyoxometalate-derivative KNiVO(K_(2)[Ni(H_(2)O)_(6)]_(2)[V_(10)O_(28)]·_(4)H_(2)O polyoxometalates after annealing)is firstly demonstrated as a cathode material for aqueous ZIBs.The layered KV_(3)O_(8)(KVO)In the bi-component material constitutes Zn^(2+) migration and storage channels(K^(+) were substantially replaced by Zn^(2+) in the activation phase),and the three-dimensional NiV_(3)O_(8)(NiVO)part acts as skeleton to stabilize the ion channels,which assist the cell to demonstrate a high-rate capacity and specific energy of229.4 mAh/g and satisfactory cyclability(capacity retention of 99.1%after 4500 cycles at a current density of 4 A/g).These results prove the feasibility of POM as cathode materials precursor and put forward a novel pattern of the Zn^(2+)storage mechanism in the activated-KNiVO clusters,which also provide a new route for selecting or designing high-performance cathode for aqueous ZIBs and other advanced battery systems.
基金supported by the National Natural Science Foundation of China(Nos.52001128 and 52371065)the Hubei Provincial Natural Science Foundation of China(No.2023AFB637).
文摘The high corrosion sensitivity and the potential bio-toxicity of Mg-Ag alloys limit their wide applications for the production of implanted devices. In the present work, Mn is added into the Mg-Ag alloy to optimize its corrosion behaviour. The corrosion behaviour of Mg-Ag-Mn alloys is investigated with the underlying microstructural factors examined. The Mg-Ag alloy with 2 wt% Mn exhibits the highest corrosion resistance after post-casting heat treatment at 440 ℃. The addition of Mn results in α-Mn phase with the incorporation of Fe, which suppresses the cathodic activity of impurity Fe. Further, heat treatment of the cast alloys homogenizes the distribution of Ag and promotes the precipitation of α-Mn phase. The former removes Ag segregations as potential cathodes;the latter promotes a more uniform distribution of cathodes and, therefore, prevents localized corrosion.
基金supported by the China Postdoctoral Science Foundation (No.2020M680710)the National Natural Science Foundation of China (No.22106173)。
文摘In order to enhance Ni-EDTA decomplexation and Ni recovery via photoelectrocatalytic (PEC)process,TiO_(2)/Ni-Sb-SnO_(2)bifunctional electrode was fabricated as the photoanode and activated carbon fiber (ACF) was introduced as the cathode.At a cell voltage of 3.5 V and initial solution pH of 6.3,the TiO_(2)/Ni-Sb-SnO_(2)bifunctional photoanode exhibited a synergetic effect on the decomplexation of Ni-EDTA with the pseudo-first-order rate constant of 0.01068 min^(-1)with 180 min by using stainless steel (SS) cathode,which was 1.5 and 2.4times higher than that of TiO_(2)photoanode and Ni-Sb-SnO_(2)anode,respectively.Moreover,both the efficiencies of Ni-EDTA decomplexation and Ni recovery were improved to 98%from 86%and 73%from 41%after replacing SS cathode with ACF cathode,respectively.Influencing factors on Ni-EDTA decomplexation and Ni recovery were investigated and the efficiencies were favored at acidic condition,higher cell voltage and lower initial Ni-EDTA concentration.Ni-EDTA was mainly decomposed via·OH radicals which generated via the interaction of O_(3),H_(2)O_(2),and UV irradiation in the contrasted PEC system.Then,the liberated Ni^(2+)ions which liberated from Ni-EDTA decomplexation were eventually reduced to metallic Ni on the ACF cathode surface.Finally,the stability of the constructed PEC system on Ni-EDTA decomplexation and Ni recovery was exhibited.
文摘Fe-N-C catalysts represent the most promising class of platinum group metal-free(PGM-free)catalysts for the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs),exhibiting intrinsic activity potentially competitive with commercial Pt/C benchmarks.However,critical challenges persist[1].As revealed by theoretical calculations,the enhancement of intrinsic activity in Fe-N-C catalysts is constrained by inherent scaling relations among the adsorption free energies of ORR intermediates on the catalyst surface.
