Since the electrochemical energy storage was invented, mobile has brought us a new world without wires for more electronic devices [1–4]. Aluminum ion batteries(AIBs) were born with the requirements of electrochemica...Since the electrochemical energy storage was invented, mobile has brought us a new world without wires for more electronic devices [1–4]. Aluminum ion batteries(AIBs) were born with the requirements of electrochemical energy storage towards high capacity, safe and low cost.展开更多
The exertion of superior high-energy density based on multivalent ions transfer of rechargeable aluminum batteries is greatly hindered by limited electrochemical stability window of typical water in salt electrolyte(W...The exertion of superior high-energy density based on multivalent ions transfer of rechargeable aluminum batteries is greatly hindered by limited electrochemical stability window of typical water in salt electrolyte(Wi SE). Recently, it is reported that a second salt addition to the Wi SE can offer further suppression of water activities, and achieves a much wider electrochemical window compared with aqueous Wi SE electrolytes. Hence, we demonstrate a class of water in bi-salt electrolyte containing the trifluoromethanesulfonate(OTF), which exhibits an ultra-wide electrochemical window of 4.35 V and a very low overpotential of 14.6 m V. Moreover, the interface chemistry between cathode and electrolyte is also confirmed via kinetic analysis. Surprisingly, we find the electrolyte can effectively suppress Mn dissolution from the cathode, alleviate self-discharge behavior, and ensure a stable electrode–electrolyte interface based on the interface concentrated-confinement effect. Owing to these unique merits of water in bi-salt electrolyte, the AlxMnO_(2)·nH_(2)O material delivers a high capacity of 364 m Ah g;and superb long-term cycling performance > 150 cycles with a capacity decay rate of 0.37% per cycle with coulombic efficiency at ca. 95%.展开更多
Al metal possesses ultrahigh theoretical volumetric capacity of 8,040 m Ah cm^(-3),and gravimetric capacity of 2,980 m Ah g^(-1),and thus is highly attractive for electrochemical energy storage.However,it suffers from...Al metal possesses ultrahigh theoretical volumetric capacity of 8,040 m Ah cm^(-3),and gravimetric capacity of 2,980 m Ah g^(-1),and thus is highly attractive for electrochemical energy storage.However,it suffers from several issues,such as the dendrite formation,during Al stripping-deposition cycling,which has been verified to account for the short circuit and limited cyclic performance.Herein,we use a facile and applicable method to in-situ reconstruct the Al anode surface with F-Al-O chemical bonds,which could preferentially induce the planar growth of Al along the interface plane,thus leading to the dendrite-free morphology evolution during the cycling.Benefiting from F-Al-O chemical bonds on the surface of Al anodes,long lifespan of symmetric cells can be realized even under 1 m A cm^(-2)and 1 m Ah cm^(-2).Coupling the F-Al anode with graphite-based cathodes,high-voltage dual-ion Al metal batteries can be achieved with long-term cycle stability up to 1,200 cycles(at 0.5 m A cm^(-2)),surpassing the counterparts using pristine Al metal anode.Furthermore,the effectiveness of this surficial modification strategy is also elucidated with the aid of theoretical calculation.This work provides novel insights on low-cost and facile strategies against the Al dendrite growth in aluminum batteries.展开更多
Rechargeable aluminum batteries with multi-electron reaction have a high theoretical capacity for next generation of energy storage devices. However, the diffusion mechanism and intrinsic property of Al insertion into...Rechargeable aluminum batteries with multi-electron reaction have a high theoretical capacity for next generation of energy storage devices. However, the diffusion mechanism and intrinsic property of Al insertion into MnO_(2) are not clear. Hence, based on the first-principles calculations, key influencing factors of slow Al-ions diffusion are narrow pathways, unstable Al-O bonds and Mn^(3+) type polaron have been identified by investigating four types of δ-MnO_(2)(O3, O'3, P2 and T1). Although Al insert into δ-MnO_(2) leads to a decrease in the spacing of the Mn-Mn layer, P2 type MnO_(2) keeps the long(spacious pathways)and stable(2.007–2.030 A) Al-O bonds resulting in the lower energy barrier of Al diffusion of 0.56 e V. By eliminated the influence of Mn^(3+)(low concentration of Al insertion), the energy barrier of Al migration achieves 0.19 e V in P2 type, confirming the obviously effect of Mn^(3+) polaron. On the contrary, although the T1 type MnO_(2) has the sluggish of Al-ions diffusion, the larger interlayer spacing of Mn-Mn layer,causing by H_(2)O could assist Al-ions diffusion. Furthermore, it is worth to notice that the multilayer δ-MnO_(2) achieves multi-electron reaction of 3|e|. Considering the requirement of high energy density, the average voltage of P2(1.76 V) is not an obstacle for application as cathode in RABs. These discover suggest that layered MnO_(2) should keep more P2-type structure in the synthesis of materials and increase the interlayer spacing of Mn-Mn layer for providing technical support of RABs in large-scale energy storage.展开更多
As a new 2-dimensional material,borophene is expected to be used in energy storage devices because of its unique electronic properties.However,its utilization in rechargeable aluminum batteries(RABs)is limited by high...As a new 2-dimensional material,borophene is expected to be used in energy storage devices because of its unique electronic properties.However,its utilization in rechargeable aluminum batteries(RABs)is limited by high valence of Al(3s^(2)3p^(1)).Namely,the Al adsorption borophene is too weak to carry on a multielectron reaction.Here,we investigate the origin of unfavorable Al adsorption on borophene that lies at the repulsion of lone pair electrons of 3s orbital with electron-gaining borophene.Because of the existing AlCl_(n) compounds during the charging and discharging,we introduce AlCl_(4)^(-),AlCl^(2+),and AlCl^(2+)ions as possible redox carrier in RABs for the first time.In sharp contrast,multielectron(over 2 electrons per Al)reaction and high capacity(841 mAh/g for[AlCl]_(0.33)B)can be achieved as a result of Cl coordination.In addition,the diffusion barrier of AlCl^(2+)compound is only 0.08 eV.Notably,the binding of Al and Cl in the form of coordinations liberates the electrons in stable states of 3s orbital,breaking the limit of electron transfer on borophene as cathode materials,thus promoting the adsorption of AlCl_(n) compounds.In addition,the energy barrier of the reaction between Al 3s electrons and borophene is decreased in the degenerated orbital.Because of the effect of Cl coordination,borophene is suitable for AlCl_(n) storage,not Al3+.These results offer a new insight of the interplay of AlCl_(n) carrier and multielectron reactions in RABs.展开更多
The advancement of supercapacitors(SCs)is closely bound up with the breakthrough of rational design of energy materials.Freestanding and thick carbon(FTC)materials with well-organized porous structure is promising SC ...The advancement of supercapacitors(SCs)is closely bound up with the breakthrough of rational design of energy materials.Freestanding and thick carbon(FTC)materials with well-organized porous structure is promising SC electrode delivering high areal capacitive performance.However,controllable and sustainable fabrication of such FTC electrode is still of great challenges.Inspired by natural honeycombs with cross-linked multichannel structure,herein,an innovative molecular-cooperative-interaction strategy is elaborately provided to realize honeycomb-like FTC electrodes.The nitrogen-doped porous carbon monolith(N-PCM)is obtained with advantages of interconnect pore structure and abundant nitrogen doping.Such strategy is based on naturally abundant molecular precursors,and free of pore-templates,expensive polymerization catalyst,and dangerous reaction solvent,rendering it a sustainable and cost-effective process.Systematic control experiments reveal that strong interactions among molecular precursors promise the structural stability of N-PCM during carbonization,and rational selection of molecular precursors with chemical blowing features is key step for well-developed honeycomb-like pore structure.Interestingly,the optimized sample exhibits hierarchical pore structure with specific surface area of 626.4 m^(2)g^(-1)and rational N-doping of 7.01 wt%.The derived SC electrode with high mass loading of 40.1 mg cm^(-2)shows an excellent areal capacitance of 3621 mF cm^(-2)at 1 mA cm^(-2)and good rate performance with 2920 mF cm^(-2)at 25 mA cm^(-2).Moreover,the constructed aqueous symmetric SC and quasi-solid-state SC produce high energy densities of 0.32 and 0.27 mWh cm^(-2),respectively.We believe that such a composition/microstructure controllable method can promote the fabrication and development of other thick electrodes for energy storage devices.展开更多
具备低价、优异倍率性能、长寿命、高安全性的水系锌离子混合电容器(ZHSCs)是理想的下一代能量存储器件.高比表面积、多级孔、富缺陷的掺杂分级多孔碳(HD-HPCs)是非常有前景的ZHSCs正极材料.但是,可持续且可控原位构筑同时具备多种结构...具备低价、优异倍率性能、长寿命、高安全性的水系锌离子混合电容器(ZHSCs)是理想的下一代能量存储器件.高比表面积、多级孔、富缺陷的掺杂分级多孔碳(HD-HPCs)是非常有前景的ZHSCs正极材料.但是,可持续且可控原位构筑同时具备多种结构组分优势的HDHPCs仍然面临挑战.本文提出一种新的分子工程化策略,即直接碳化富含多种异质原子的超分子前驱体,便可实现原位构筑多元掺杂HDHPCs.该绿色可持续策略具有多种优势,包括不需要额外的成孔技术、活化剂、模板剂、以及复杂且危险的清洗过程.由于富杂原子超分子前驱体具有较高的活性,高温碳化过程中杂原子以及邻近杂原子的碳原子很容易从碳骨架中脱离,形成丰富的微介孔结构.因此,活性结构与组分优化后的正极材料在水系ZHSCs中0.5和20 A g^(-1)下容量分别达到139.2和88.9 mA h g^(-1),在准固态ZHSCs中0.5 A g^(-1)下容量也能够达到111.5 mA h g^(-1).此外,水系和准固态ZHSCs也具备高能量和功率密度,以及长循环稳定性.理论计算表明多原子掺杂能够协同提升碳材料的导电性,且降低锌离子与碳之间的相互作用能垒,因而提升锌离子的吸附性能.本工作为直接制备HD-HPCs及其电化学储能应用提供了新思路.展开更多
基金supported by the National Natural Science Foundation of China (Grant No. 22075028)。
文摘Since the electrochemical energy storage was invented, mobile has brought us a new world without wires for more electronic devices [1–4]. Aluminum ion batteries(AIBs) were born with the requirements of electrochemical energy storage towards high capacity, safe and low cost.
基金supported by the National Natural Science Foundation of China(22075028)。
文摘The exertion of superior high-energy density based on multivalent ions transfer of rechargeable aluminum batteries is greatly hindered by limited electrochemical stability window of typical water in salt electrolyte(Wi SE). Recently, it is reported that a second salt addition to the Wi SE can offer further suppression of water activities, and achieves a much wider electrochemical window compared with aqueous Wi SE electrolytes. Hence, we demonstrate a class of water in bi-salt electrolyte containing the trifluoromethanesulfonate(OTF), which exhibits an ultra-wide electrochemical window of 4.35 V and a very low overpotential of 14.6 m V. Moreover, the interface chemistry between cathode and electrolyte is also confirmed via kinetic analysis. Surprisingly, we find the electrolyte can effectively suppress Mn dissolution from the cathode, alleviate self-discharge behavior, and ensure a stable electrode–electrolyte interface based on the interface concentrated-confinement effect. Owing to these unique merits of water in bi-salt electrolyte, the AlxMnO_(2)·nH_(2)O material delivers a high capacity of 364 m Ah g;and superb long-term cycling performance > 150 cycles with a capacity decay rate of 0.37% per cycle with coulombic efficiency at ca. 95%.
基金supported by the National Natural Science Foundation of China(22075028)the Beijing Institute of Technology Research Fund Program for Young Scholars(XSQD202108005)。
文摘Al metal possesses ultrahigh theoretical volumetric capacity of 8,040 m Ah cm^(-3),and gravimetric capacity of 2,980 m Ah g^(-1),and thus is highly attractive for electrochemical energy storage.However,it suffers from several issues,such as the dendrite formation,during Al stripping-deposition cycling,which has been verified to account for the short circuit and limited cyclic performance.Herein,we use a facile and applicable method to in-situ reconstruct the Al anode surface with F-Al-O chemical bonds,which could preferentially induce the planar growth of Al along the interface plane,thus leading to the dendrite-free morphology evolution during the cycling.Benefiting from F-Al-O chemical bonds on the surface of Al anodes,long lifespan of symmetric cells can be realized even under 1 m A cm^(-2)and 1 m Ah cm^(-2).Coupling the F-Al anode with graphite-based cathodes,high-voltage dual-ion Al metal batteries can be achieved with long-term cycle stability up to 1,200 cycles(at 0.5 m A cm^(-2)),surpassing the counterparts using pristine Al metal anode.Furthermore,the effectiveness of this surficial modification strategy is also elucidated with the aid of theoretical calculation.This work provides novel insights on low-cost and facile strategies against the Al dendrite growth in aluminum batteries.
基金supported financially by the National Natural Science Foundation of China (No.22075028)。
文摘Rechargeable aluminum batteries with multi-electron reaction have a high theoretical capacity for next generation of energy storage devices. However, the diffusion mechanism and intrinsic property of Al insertion into MnO_(2) are not clear. Hence, based on the first-principles calculations, key influencing factors of slow Al-ions diffusion are narrow pathways, unstable Al-O bonds and Mn^(3+) type polaron have been identified by investigating four types of δ-MnO_(2)(O3, O'3, P2 and T1). Although Al insert into δ-MnO_(2) leads to a decrease in the spacing of the Mn-Mn layer, P2 type MnO_(2) keeps the long(spacious pathways)and stable(2.007–2.030 A) Al-O bonds resulting in the lower energy barrier of Al diffusion of 0.56 e V. By eliminated the influence of Mn^(3+)(low concentration of Al insertion), the energy barrier of Al migration achieves 0.19 e V in P2 type, confirming the obviously effect of Mn^(3+) polaron. On the contrary, although the T1 type MnO_(2) has the sluggish of Al-ions diffusion, the larger interlayer spacing of Mn-Mn layer,causing by H_(2)O could assist Al-ions diffusion. Furthermore, it is worth to notice that the multilayer δ-MnO_(2) achieves multi-electron reaction of 3|e|. Considering the requirement of high energy density, the average voltage of P2(1.76 V) is not an obstacle for application as cathode in RABs. These discover suggest that layered MnO_(2) should keep more P2-type structure in the synthesis of materials and increase the interlayer spacing of Mn-Mn layer for providing technical support of RABs in large-scale energy storage.
基金This work was supported financially by the National Natural Science Foundation of China(22075028).Author con-tributions:Y.B.and C.W.proposed the research idea.L.Z.,H.Y.,and C.W.designed the modeling.L.Z.did the calculations.Y.B.and C.W.supervised the research work.L.Z.,Y.B.,and C.W.wrote the manuscript.All authors discussed the results and com-mented on the manuscript.Competing interests:The authors declare that they have no competing interests.
文摘As a new 2-dimensional material,borophene is expected to be used in energy storage devices because of its unique electronic properties.However,its utilization in rechargeable aluminum batteries(RABs)is limited by high valence of Al(3s^(2)3p^(1)).Namely,the Al adsorption borophene is too weak to carry on a multielectron reaction.Here,we investigate the origin of unfavorable Al adsorption on borophene that lies at the repulsion of lone pair electrons of 3s orbital with electron-gaining borophene.Because of the existing AlCl_(n) compounds during the charging and discharging,we introduce AlCl_(4)^(-),AlCl^(2+),and AlCl^(2+)ions as possible redox carrier in RABs for the first time.In sharp contrast,multielectron(over 2 electrons per Al)reaction and high capacity(841 mAh/g for[AlCl]_(0.33)B)can be achieved as a result of Cl coordination.In addition,the diffusion barrier of AlCl^(2+)compound is only 0.08 eV.Notably,the binding of Al and Cl in the form of coordinations liberates the electrons in stable states of 3s orbital,breaking the limit of electron transfer on borophene as cathode materials,thus promoting the adsorption of AlCl_(n) compounds.In addition,the energy barrier of the reaction between Al 3s electrons and borophene is decreased in the degenerated orbital.Because of the effect of Cl coordination,borophene is suitable for AlCl_(n) storage,not Al3+.These results offer a new insight of the interplay of AlCl_(n) carrier and multielectron reactions in RABs.
基金Guangdong Science and Technology Department,Grant/Award Number:2020B0909030004National Natural Science Foundation of China,Grant/Award Number:21975026。
文摘The advancement of supercapacitors(SCs)is closely bound up with the breakthrough of rational design of energy materials.Freestanding and thick carbon(FTC)materials with well-organized porous structure is promising SC electrode delivering high areal capacitive performance.However,controllable and sustainable fabrication of such FTC electrode is still of great challenges.Inspired by natural honeycombs with cross-linked multichannel structure,herein,an innovative molecular-cooperative-interaction strategy is elaborately provided to realize honeycomb-like FTC electrodes.The nitrogen-doped porous carbon monolith(N-PCM)is obtained with advantages of interconnect pore structure and abundant nitrogen doping.Such strategy is based on naturally abundant molecular precursors,and free of pore-templates,expensive polymerization catalyst,and dangerous reaction solvent,rendering it a sustainable and cost-effective process.Systematic control experiments reveal that strong interactions among molecular precursors promise the structural stability of N-PCM during carbonization,and rational selection of molecular precursors with chemical blowing features is key step for well-developed honeycomb-like pore structure.Interestingly,the optimized sample exhibits hierarchical pore structure with specific surface area of 626.4 m^(2)g^(-1)and rational N-doping of 7.01 wt%.The derived SC electrode with high mass loading of 40.1 mg cm^(-2)shows an excellent areal capacitance of 3621 mF cm^(-2)at 1 mA cm^(-2)and good rate performance with 2920 mF cm^(-2)at 25 mA cm^(-2).Moreover,the constructed aqueous symmetric SC and quasi-solid-state SC produce high energy densities of 0.32 and 0.27 mWh cm^(-2),respectively.We believe that such a composition/microstructure controllable method can promote the fabrication and development of other thick electrodes for energy storage devices.
基金supported by the National Natural Science Foundation of China(21975026)the Science and Technology Program of Guangdong Province(2020B0909030004)the Graduate Interdisciplinary Innovation Project of Yangtze Delta Region Academy of Beijing Institute of Technology(Jiaxing,GIIP2021-002)。
文摘具备低价、优异倍率性能、长寿命、高安全性的水系锌离子混合电容器(ZHSCs)是理想的下一代能量存储器件.高比表面积、多级孔、富缺陷的掺杂分级多孔碳(HD-HPCs)是非常有前景的ZHSCs正极材料.但是,可持续且可控原位构筑同时具备多种结构组分优势的HDHPCs仍然面临挑战.本文提出一种新的分子工程化策略,即直接碳化富含多种异质原子的超分子前驱体,便可实现原位构筑多元掺杂HDHPCs.该绿色可持续策略具有多种优势,包括不需要额外的成孔技术、活化剂、模板剂、以及复杂且危险的清洗过程.由于富杂原子超分子前驱体具有较高的活性,高温碳化过程中杂原子以及邻近杂原子的碳原子很容易从碳骨架中脱离,形成丰富的微介孔结构.因此,活性结构与组分优化后的正极材料在水系ZHSCs中0.5和20 A g^(-1)下容量分别达到139.2和88.9 mA h g^(-1),在准固态ZHSCs中0.5 A g^(-1)下容量也能够达到111.5 mA h g^(-1).此外,水系和准固态ZHSCs也具备高能量和功率密度,以及长循环稳定性.理论计算表明多原子掺杂能够协同提升碳材料的导电性,且降低锌离子与碳之间的相互作用能垒,因而提升锌离子的吸附性能.本工作为直接制备HD-HPCs及其电化学储能应用提供了新思路.
