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
Aqueous rechargeable zinc-based batteries have attracted increasing interest and been considered potential alternatives for state-of-the-art lithium-ion batteries because of the low cost and high safety.Many cathode m...Aqueous rechargeable zinc-based batteries have attracted increasing interest and been considered potential alternatives for state-of-the-art lithium-ion batteries because of the low cost and high safety.Many cathode materials have been gradually developed and demonstrated excellent electrochemical performances.However,the complex electrochemistry,inevitable hydrogen release,and zinc corrosion severely hinder the practical application.The most concerned Zn-MnO_(2)batteries still suffer from the Mn dissolution and formation of byproducts.By adding organic solvents to inhibit the activity of water molecules,the hydrous organic electrolytes provide a sound solution for eliminating the unfavorable factors.Here we report a tetraethylene glycol dimethyl ether-based hydrous organic electrolyte consisting of LiClO_(4)·3H_(2)O and Zn(ClO4)2·6H2O,and a birnessite-type MnO_(2)cathode material for Zn-MnO_(2)batteries.The Li+/Zn2+ions co-(de)insertion mechanism is ascertained by the structural and morphological analyses.The electrostatic interaction between inserted ions and crystal structure is reduced effectively by employment of monovalent Li+ions,which ensures structural stability of cathode materials.Hydrous tetraglyme electrolyte inhibits the activity of water molecules and thus avoids the formation of byproduct Zn_(4)ClO_(4)(OH)7·Meanwhile,highly stable Zn plating/stripping for over 1500 h,an average coulombic efficiency of>99%in long-term cycling,and ultralong storage life(the cells can work well after stored over 1 year)are simultaneously realized in the novel electrolyte.Benefitting from these aspects,the Zn-MnO_(2)batteries manifest high specific capacity of 132 mA h g^(-1),an operating voltage of 1.25 V,and a capacity retention of>98%after 1000 cycles at a current density of 200 mA g^(-1).展开更多
Manganese dioxide(MnO_(2)) is considered as a potential cathode material for aqueous magnesium-ion batteries. However, the charge/discharge mechanism of MnO_(2)in aqueous electrolyte is still unclear. In present study...Manganese dioxide(MnO_(2)) is considered as a potential cathode material for aqueous magnesium-ion batteries. However, the charge/discharge mechanism of MnO_(2)in aqueous electrolyte is still unclear. In present study, highly porous δ-MnO_(2) is investigated, which delivers a high capacity of 252.1 m Ah g^(-1) at 0.05 A g^(-1) and excellent rate capability, i.e., 109.7 m Ah g^(-1) at 1 A g^(-1), but a low-capacity retention of 54.4% after 800 cycles at 1 A g^(-1). The two-step discharging process, namely a consequent H^(+) and Mg^(2+) insertion reaction, is verified, by comparing the electrochemical performance of δ-MnO_(2) in 1 M MgCl_(2) and 1 M MnCl_(2) aqueous electrolyte and analyzing detailedly the Mg content and the bonding state of Mn at different charge/discharge state. Furthermore, partial irreversibility of Mg^(-1) ion insertion/extraction is observed, which may be one of the major reasons leading to capacity decay.展开更多
The low energy efficiency and poor cycle stability arising from the high aggressivity of discharge products toward organic electrolytes limit the practical applications of Li-O_(2)batteries(LOBs).Compared with the typ...The low energy efficiency and poor cycle stability arising from the high aggressivity of discharge products toward organic electrolytes limit the practical applications of Li-O_(2)batteries(LOBs).Compared with the typical discharge product Li_(2)O_(2),LiOH shows better chemical and electrochemical stability.In this study,a free-standing cathode composed of hydrangea-likeδ-MnO_(2)with Ag nanoparticles(NPs)embedded in carbon paper(CP)(Ag/δ-MnO_(2)@CP)is fabricated and used as the catalyst for the reversible formation and decomposition of LiOH.The possible discharge mechanism is investigated by in situ Raman measurement and density functional theory calculation.Results confirm thatδ-MnO_(2)dominantly catalyzes the conversion reaction of discharge intermediate LiO_(2)*to LiOH and that Ag particles promote its catalytic ability.In the presence of Ag/δ-MnO_(2)@CP cathode,the LOB exhibits enhanced specific capacity and a high discharge voltage plateau under humid O_(2)atmosphere.At a current density of 200 mA g^(−1),the LOB with the Ag/δ-MnO_(2)@CP cathode presents an overpotential of 0.5 V and an ultra-long cycle life of 867 cycles with a limited specific capacity of 500 mA h g^(−1).This work provides a fresh view on the role of solid catalysts in LOBs and promotes the development of LOBs based on LiOH discharge product for practical applications.展开更多
Paper-based sensing platform is a point of need analytical toolkit for safety testing.However,the sensitivity,specificity,and simplicity are still challenging.Herein,we report a novel strategy(Au/δ-MnO_(2) hollow nan...Paper-based sensing platform is a point of need analytical toolkit for safety testing.However,the sensitivity,specificity,and simplicity are still challenging.Herein,we report a novel strategy(Au/δ-MnO_(2) hollow nanosphere and 3,3′,5,5′-tetramethylbenzidine(TMB)induced test strips for signal-on detection)that can be utilized for hexavalent chromium(Cr^(6+))detection.Interestingly,Cr^(6+)(CrO_(4)^(2−)) as a smart switch can remarkably enhance the oxidase-like activity of Au/δ-MnO_(2) hollow nanosphere.The presence of Cr^(6+) can regulate the surface electronic redistribution of Au/δ-MnO_(2) and adjust the geometric configuration,which leads to the improvement in oxidase-like activity of Au/δ-MnO_(2).As a proof-of-concept application,a visual paper-based sensing platform of Cr^(6+) along with quantitative analysis by the test strips was successfully constructed.This paper-based sensing platform exhibits a linear range with excellent selectivity for other interfering substances and lower limit of detection of 0.09μmol·L^(−1),providing a promising toolkit at-home Cr^(6+) measurement and environmental monitoring.展开更多
In recent years,manganese-based oxides as an advanced class of cathode materials for zinc-ion batteries(ZIBs)have attracted a great deal of attentions from numerous researchers.However,their slow reaction kinetics,lim...In recent years,manganese-based oxides as an advanced class of cathode materials for zinc-ion batteries(ZIBs)have attracted a great deal of attentions from numerous researchers.However,their slow reaction kinetics,limited active sites and poor electrical conductivity inevitably give rise to the severe performance degradation.To solve these problems,herein,we introduce abundant oxygen vacancies into the flower-likeδ-MnO_(2)nanostructure and effectively modulate the vacancy defects to reach the optimal level(δ-MnO_(2)-x-2.0).The smart design intrinsically tunes the electronic structure,guarantees ion chemisorption-desorption equilibrium and increases the electroactive sites,which not only effectively accelerates charge transfer rate during reaction processes,but also endows more redox reactions,as verified by first-principle calculations.These merits can help the fabricatedδ-MnO_(2)-x-2.0 cathode to present a large specific capacity of 551.8 mAh g^(-1) at 0.5 A g^(-1),high-rate capability of 262.2 mAh g^(-1) at 10 A g^(-1) and an excellent cycle lifespan(83%of capacity retention after 1500 cycles),which is far superior to those of the other metal compound cathodes.In addition,the charge/discharge mechanism of theδ-MnO_(2)-x-2.0 cathode has also been elaborated through ex situ techniques.This work opens up a new pathway for constructing the next-generation high-performance ZIBs cathode materials.展开更多
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supported by the National Natural Science Foundation of China(U1801255,91963210)the National Natural Science Foundation of Guangzhou,China(202201011414)。
文摘Aqueous rechargeable zinc-based batteries have attracted increasing interest and been considered potential alternatives for state-of-the-art lithium-ion batteries because of the low cost and high safety.Many cathode materials have been gradually developed and demonstrated excellent electrochemical performances.However,the complex electrochemistry,inevitable hydrogen release,and zinc corrosion severely hinder the practical application.The most concerned Zn-MnO_(2)batteries still suffer from the Mn dissolution and formation of byproducts.By adding organic solvents to inhibit the activity of water molecules,the hydrous organic electrolytes provide a sound solution for eliminating the unfavorable factors.Here we report a tetraethylene glycol dimethyl ether-based hydrous organic electrolyte consisting of LiClO_(4)·3H_(2)O and Zn(ClO4)2·6H2O,and a birnessite-type MnO_(2)cathode material for Zn-MnO_(2)batteries.The Li+/Zn2+ions co-(de)insertion mechanism is ascertained by the structural and morphological analyses.The electrostatic interaction between inserted ions and crystal structure is reduced effectively by employment of monovalent Li+ions,which ensures structural stability of cathode materials.Hydrous tetraglyme electrolyte inhibits the activity of water molecules and thus avoids the formation of byproduct Zn_(4)ClO_(4)(OH)7·Meanwhile,highly stable Zn plating/stripping for over 1500 h,an average coulombic efficiency of>99%in long-term cycling,and ultralong storage life(the cells can work well after stored over 1 year)are simultaneously realized in the novel electrolyte.Benefitting from these aspects,the Zn-MnO_(2)batteries manifest high specific capacity of 132 mA h g^(-1),an operating voltage of 1.25 V,and a capacity retention of>98%after 1000 cycles at a current density of 200 mA g^(-1).
基金financial support by the National Natural Science Foundation of China (21975168)the Sichuan Science and Technology Program (2021JDJQ0020)the Fundamental Research Funds for the Central Universities (No. 1082204112219)。
文摘Manganese dioxide(MnO_(2)) is considered as a potential cathode material for aqueous magnesium-ion batteries. However, the charge/discharge mechanism of MnO_(2)in aqueous electrolyte is still unclear. In present study, highly porous δ-MnO_(2) is investigated, which delivers a high capacity of 252.1 m Ah g^(-1) at 0.05 A g^(-1) and excellent rate capability, i.e., 109.7 m Ah g^(-1) at 1 A g^(-1), but a low-capacity retention of 54.4% after 800 cycles at 1 A g^(-1). The two-step discharging process, namely a consequent H^(+) and Mg^(2+) insertion reaction, is verified, by comparing the electrochemical performance of δ-MnO_(2) in 1 M MgCl_(2) and 1 M MnCl_(2) aqueous electrolyte and analyzing detailedly the Mg content and the bonding state of Mn at different charge/discharge state. Furthermore, partial irreversibility of Mg^(-1) ion insertion/extraction is observed, which may be one of the major reasons leading to capacity decay.
基金financially supported by the High-level Talents’Discipline Construction Fund of Shandong University(31370089963078)the School Research Startup Expenses of Harbin Institute of Technology(Shenzhen)(20190037 and 20210028)+3 种基金China Postdoctoral Science Foundation(2019M661276 and 2021T140150)Guangdong Basic and Applied Basic Research Foundation(2019A1515110756)the National Natural Science Foundation of China(52002094)the Open Fund of Guangdong Provincial Key laboratory of Advanced Energy Storage Materials(AESM202107)。
文摘The low energy efficiency and poor cycle stability arising from the high aggressivity of discharge products toward organic electrolytes limit the practical applications of Li-O_(2)batteries(LOBs).Compared with the typical discharge product Li_(2)O_(2),LiOH shows better chemical and electrochemical stability.In this study,a free-standing cathode composed of hydrangea-likeδ-MnO_(2)with Ag nanoparticles(NPs)embedded in carbon paper(CP)(Ag/δ-MnO_(2)@CP)is fabricated and used as the catalyst for the reversible formation and decomposition of LiOH.The possible discharge mechanism is investigated by in situ Raman measurement and density functional theory calculation.Results confirm thatδ-MnO_(2)dominantly catalyzes the conversion reaction of discharge intermediate LiO_(2)*to LiOH and that Ag particles promote its catalytic ability.In the presence of Ag/δ-MnO_(2)@CP cathode,the LOB exhibits enhanced specific capacity and a high discharge voltage plateau under humid O_(2)atmosphere.At a current density of 200 mA g^(−1),the LOB with the Ag/δ-MnO_(2)@CP cathode presents an overpotential of 0.5 V and an ultra-long cycle life of 867 cycles with a limited specific capacity of 500 mA h g^(−1).This work provides a fresh view on the role of solid catalysts in LOBs and promotes the development of LOBs based on LiOH discharge product for practical applications.
基金This work was financially supported by Xuzhou science and technology plan project of China(No.KC21294).
文摘Paper-based sensing platform is a point of need analytical toolkit for safety testing.However,the sensitivity,specificity,and simplicity are still challenging.Herein,we report a novel strategy(Au/δ-MnO_(2) hollow nanosphere and 3,3′,5,5′-tetramethylbenzidine(TMB)induced test strips for signal-on detection)that can be utilized for hexavalent chromium(Cr^(6+))detection.Interestingly,Cr^(6+)(CrO_(4)^(2−)) as a smart switch can remarkably enhance the oxidase-like activity of Au/δ-MnO_(2) hollow nanosphere.The presence of Cr^(6+) can regulate the surface electronic redistribution of Au/δ-MnO_(2) and adjust the geometric configuration,which leads to the improvement in oxidase-like activity of Au/δ-MnO_(2).As a proof-of-concept application,a visual paper-based sensing platform of Cr^(6+) along with quantitative analysis by the test strips was successfully constructed.This paper-based sensing platform exhibits a linear range with excellent selectivity for other interfering substances and lower limit of detection of 0.09μmol·L^(−1),providing a promising toolkit at-home Cr^(6+) measurement and environmental monitoring.
基金supported by the National Natural Science Foundation of China under Grant Nos. 52072196, 52002200, 52102106 and 52002199Major Basic Research Program of the Natural Science Foundation of Shandong Province under Grant No. ZR2020ZD09+2 种基金the Natural Science Foundation of Shandong Province under Grant No. ZR2020QE063the Innovation and Technology Program of Shandong Province under Grant No. 2020KJA004the Taishan Scholars Program of Shandong Province under Grant No. ts201511034
文摘In recent years,manganese-based oxides as an advanced class of cathode materials for zinc-ion batteries(ZIBs)have attracted a great deal of attentions from numerous researchers.However,their slow reaction kinetics,limited active sites and poor electrical conductivity inevitably give rise to the severe performance degradation.To solve these problems,herein,we introduce abundant oxygen vacancies into the flower-likeδ-MnO_(2)nanostructure and effectively modulate the vacancy defects to reach the optimal level(δ-MnO_(2)-x-2.0).The smart design intrinsically tunes the electronic structure,guarantees ion chemisorption-desorption equilibrium and increases the electroactive sites,which not only effectively accelerates charge transfer rate during reaction processes,but also endows more redox reactions,as verified by first-principle calculations.These merits can help the fabricatedδ-MnO_(2)-x-2.0 cathode to present a large specific capacity of 551.8 mAh g^(-1) at 0.5 A g^(-1),high-rate capability of 262.2 mAh g^(-1) at 10 A g^(-1) and an excellent cycle lifespan(83%of capacity retention after 1500 cycles),which is far superior to those of the other metal compound cathodes.In addition,the charge/discharge mechanism of theδ-MnO_(2)-x-2.0 cathode has also been elaborated through ex situ techniques.This work opens up a new pathway for constructing the next-generation high-performance ZIBs cathode materials.
