Recently,rechargeable aqueous zinc-based batteries using manganese oxide as the cathode(e.g.,MnO_(2))have gained attention due to their inherent safety,environmental friendliness,and low cost.Despite their potential,a...Recently,rechargeable aqueous zinc-based batteries using manganese oxide as the cathode(e.g.,MnO_(2))have gained attention due to their inherent safety,environmental friendliness,and low cost.Despite their potential,achieving high energy density in Zn||MnO_(2)batteries remains challenging,highlighting the need to understand the electrochemical reaction mechanisms underlying these batteries more deeply and optimize battery components,including electrodes and electrolytes.This review comprehensively summarizes the latest advancements for understanding the electrochemistry reaction mechanisms and designing electrodes and electrolytes for Zn||MnO_(2)batteries in mildly and strongly acidic environments.Furthermore,we highlight the key challenges hindering the extensive application of Zn||MnO_(2)batteries,including high-voltage requirements and areal capacity,and propose innovative solutions to overcome these challenges.We suggest that MnO_(2)/Mn^(2+)conversion in neutral electrolytes is a crucial aspect that needs to be addressed to achieve high-performance Zn||MnO_(2)batteries.These approaches could lead to breakthroughs in the future development of Zn||MnO_(2)batteries,off ering a more sustainable,costeff ective,and high-performance alternative to traditional batteries.展开更多
With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption...With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption ability and provide extra active sites for Na+adsorption.However,their synchronous engineering is rarely reported.Herein,a hybrid of Co_(0.85)Se/WSe_(2) heterostructure with Se vacancies and N-doped carbon polyhedron(CoWSe/NCP)has been fabricated for the first time via a hydrothermal and subsequent selenization strategy.Spherical aberration-corrected transmission electron microscopy confirms the phase interface of the Co_(0.85)Se/WSe_(2) heterostructure and the existence of Se vacancies.Density functional theory simulations reveal the accelerated charge transfer and enhanced Na+adsorption ability,which are contributed by the Co_(0.85)Se/WSe_(2) heterostructure and Se vacancies,respectively.As expected,the CoWSe/NCP anode in sodium-ion battery achieves outstanding rate capability(339.6 mAh g^(−1) at 20 A g^(−1)),outperforming almost all Co/W-based selenides.展开更多
As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting t...As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting the mechanical strains and alleviating phase degradation upon cycling.Hereinafter,we propose a strategy using a zeolitic imidazolate framework(ZIF)as the self-sacrificing template to directionally prepare a series of LiNi_(0.1)Co_(0.9)O_(2)(LNCO)with tailorable electrochemical properties.The rational selection of sintering temperature imparts the superiority of the resultant products in lithium storage,during which the sample prepared at 700℃(LNCO-700)outperforms its counterparts in cyclability(156.8 mA h g^(-1)at 1 C for 200 cycles in half cells,1 C=275 mA g^(-1))and rate capability due to the expedited ion/electron transport and the strengthen mechanical robustness.The feasibility of proper Ni doping is also divulged by half/full cell tests and theoretical study,during which LNCO-700(167 mA h g^(-1)at 1 C for 100 cycles in full cells)surpasses LCO-700 in battery performance due to the mitigated phase deterioration,stabilized layered structu re,ameliorated electro nic co nductivity,a nd exalted lithium sto rage activity.This work systematically unveils tailorable electrochemical behaviors of LNCO to better direct their practical application.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
Taking copper doped ZnS(ZnS:Cu)nanocrystals as the main body of photocatalyst,the influence of different base transition metal ions(M^(2+)=Ni^(2+),Co^(2+),Fe^(2+)and Cd^(2+))on photocatalytic CO_(2)reduction in inorga...Taking copper doped ZnS(ZnS:Cu)nanocrystals as the main body of photocatalyst,the influence of different base transition metal ions(M^(2+)=Ni^(2+),Co^(2+),Fe^(2+)and Cd^(2+))on photocatalytic CO_(2)reduction in inorganic reaction system is investigated.Confined single-atom Ni^(2+),Co^(2+),and Cd^(2+)sites were created via cation-exchange process and enhanced CO_(2)reduction,while Fe^(2+)suppressed the photocatalytic activity for both water and CO_(2)reduction.The modified ZnS:Cu photocatalysts(M/ZnS:Cu)demonstrated tunable product selectivity,with Ni^(2+)and Co^(2+)showing high selectivity for syngas production and Cd^(2+)displaying remarkable formate selectivity.DFT calculations indicated favorable H adsorption free energy on Ni^(2+)and Co^(2+)sites,promoting the hydrogen evolution reaction.The selectivity of CO_(2)reduction products was found to be sensitive to the initial intermediate adsorption states.*COOH formed on Ni^(2+)and Co^(2+)while*OCHO formed on Cd^(2+),favoring the production of CO and HCOOH as the main products,respectively.This work provides valuable insights for developing efficient solar-to-fuel platforms with controlled CO_(2)reduction selectivity.展开更多
Solid-state batteries(SSBs)have been considered the most promising technology because of their superior energy density and safety.Among all the solid-state electrolytes(SEs),Li_(7) La_(3) Zr_(2) O_(12)(LLZO)with high ...Solid-state batteries(SSBs)have been considered the most promising technology because of their superior energy density and safety.Among all the solid-state electrolytes(SEs),Li_(7) La_(3) Zr_(2) O_(12)(LLZO)with high ionic conductivity(3×10^(−4) S/cm)has been widely investigated.However,its large-scale production in ambient air faces a challenge.After air exposure,the generated Li_(2)CO_(3) layer deteriorates the ionic conductivity and interfacial wettability,thus greatly compromising the electrochemical performance of SSBs.Many works aim to eliminate this layer to recover the pristine LLZO surface.Unfor-tunately,few articles have emphasized the merits of Li_(2)CO_(3).In this review,we focus on the two-sidedness of Li_(2)CO_(3).We discuss the various characteristics of Li_(2)CO_(3) that can be used and recapitulate the strategies that utilize Li_(2)CO_(3).Insulating Li_(2)CO_(3) is no longer an obstacle but an opportunity for realizing intimate interfacial contact,high air stability,and outstand-ing electrochemical performance.This review aims to off er insightful guidelines for treating air-induced Li_(2)CO_(3) and lead to developing the enhanced air stability and electrochemical performance of LLZO.展开更多
This work develops 2-Phenyl-1H-imidazole-1-sulfonate(PHIS)as a multi-functional electrolyte additive for H2O/HF scavenging and film formation to improve the high temperature performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_...This work develops 2-Phenyl-1H-imidazole-1-sulfonate(PHIS)as a multi-functional electrolyte additive for H2O/HF scavenging and film formation to improve the high temperature performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/graphite batteries.After 450 cycles at room temperature(25℃),the discharge capacity retentions of batteries with blank and PHIS-containing electrolyte are 56.03%and 94.92%respectively.After 230 cycles at high temperatures(45℃),their values are 75.30%and 88.38%respectively.The enhanced electrochemical performance of the batteries with PHIS-containing electrolyte is supported by the spectroscopic characterization and theoretical calculations.It is demonstrated that this PHIS electrolyte additive can facilitate the construction of the electrode interface films,remove the H2O/HF in the electrolyte,and improve the electrochemical performance of the batteries.This work not only develops a sulfonate-based electrolyte but also can stimulate new ideas of functional additives to improve the battery performance.展开更多
The overall electrochemical performances of Ni-Zn batteries are still far from satisfactory, specifically for rate performance and cycling stability Herein, we demonstrated a high-performance flexible Ni//Zn battery w...The overall electrochemical performances of Ni-Zn batteries are still far from satisfactory, specifically for rate performance and cycling stability Herein, we demonstrated a high-performance flexible Ni//Zn battery with outstanding durability and high power density based on selfsupported NiCo_2 O_4 nanosheets as cathode and Zn nanosheets as anode. This Ni//Zn battery is able to deliver a remarkable capacity of183.1 mAh g^(-1) and a good cycling performance(82.7% capacity retention after 3500 cycles). More importantly, this battery achieves an admirable power density of 49.0 kW kg^(-1) and energy density of 303.8 Wh kg^(-1), substantially higher than most recently reported batteries. With such excellent electrochemical performance, this battery will have great potential as an ultrafast power source in practical application.展开更多
文摘Recently,rechargeable aqueous zinc-based batteries using manganese oxide as the cathode(e.g.,MnO_(2))have gained attention due to their inherent safety,environmental friendliness,and low cost.Despite their potential,achieving high energy density in Zn||MnO_(2)batteries remains challenging,highlighting the need to understand the electrochemical reaction mechanisms underlying these batteries more deeply and optimize battery components,including electrodes and electrolytes.This review comprehensively summarizes the latest advancements for understanding the electrochemistry reaction mechanisms and designing electrodes and electrolytes for Zn||MnO_(2)batteries in mildly and strongly acidic environments.Furthermore,we highlight the key challenges hindering the extensive application of Zn||MnO_(2)batteries,including high-voltage requirements and areal capacity,and propose innovative solutions to overcome these challenges.We suggest that MnO_(2)/Mn^(2+)conversion in neutral electrolytes is a crucial aspect that needs to be addressed to achieve high-performance Zn||MnO_(2)batteries.These approaches could lead to breakthroughs in the future development of Zn||MnO_(2)batteries,off ering a more sustainable,costeff ective,and high-performance alternative to traditional batteries.
基金support from the Natural Science Foundation of Jilin Province(Grant No.20200201073JC)the National Natural Science Foundation of China(Grant No.52130101)+1 种基金Interdisciplinary Integration and Innovation Project of JLU(Grant No.JLUXKJC2021ZY01)the Fundamental Research Funds for the Central Universities.
文摘With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption ability and provide extra active sites for Na+adsorption.However,their synchronous engineering is rarely reported.Herein,a hybrid of Co_(0.85)Se/WSe_(2) heterostructure with Se vacancies and N-doped carbon polyhedron(CoWSe/NCP)has been fabricated for the first time via a hydrothermal and subsequent selenization strategy.Spherical aberration-corrected transmission electron microscopy confirms the phase interface of the Co_(0.85)Se/WSe_(2) heterostructure and the existence of Se vacancies.Density functional theory simulations reveal the accelerated charge transfer and enhanced Na+adsorption ability,which are contributed by the Co_(0.85)Se/WSe_(2) heterostructure and Se vacancies,respectively.As expected,the CoWSe/NCP anode in sodium-ion battery achieves outstanding rate capability(339.6 mAh g^(−1) at 20 A g^(−1)),outperforming almost all Co/W-based selenides.
基金the financial support from the Special Funds for the Cultivation of Guangdong College Students’Scientific and Technological Innovation(“Climbing Program”Special Funds,pdjh2023b0145)Guangdong Provincial International Joint Research Center for Energy Storage Materials(2023A0505090009)。
文摘As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting the mechanical strains and alleviating phase degradation upon cycling.Hereinafter,we propose a strategy using a zeolitic imidazolate framework(ZIF)as the self-sacrificing template to directionally prepare a series of LiNi_(0.1)Co_(0.9)O_(2)(LNCO)with tailorable electrochemical properties.The rational selection of sintering temperature imparts the superiority of the resultant products in lithium storage,during which the sample prepared at 700℃(LNCO-700)outperforms its counterparts in cyclability(156.8 mA h g^(-1)at 1 C for 200 cycles in half cells,1 C=275 mA g^(-1))and rate capability due to the expedited ion/electron transport and the strengthen mechanical robustness.The feasibility of proper Ni doping is also divulged by half/full cell tests and theoretical study,during which LNCO-700(167 mA h g^(-1)at 1 C for 100 cycles in full cells)surpasses LCO-700 in battery performance due to the mitigated phase deterioration,stabilized layered structu re,ameliorated electro nic co nductivity,a nd exalted lithium sto rage activity.This work systematically unveils tailorable electrochemical behaviors of LNCO to better direct their practical application.
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 from the Tangshan Talent Funding Project(A202202007)the National Natural Science Foundation of China(21703065)+3 种基金the Natural Science Foundation of Hebei Province(B2018209267)the World Premier International Research Center Initiative(WPI Initiative)on Materials Nanoarchitectonics(MANA),the MEXT(Japan)the Photoexcitonix Project in Hokkaido Universitythe JSPS KAKENHI(Grant Number JP18H02065)。
文摘Taking copper doped ZnS(ZnS:Cu)nanocrystals as the main body of photocatalyst,the influence of different base transition metal ions(M^(2+)=Ni^(2+),Co^(2+),Fe^(2+)and Cd^(2+))on photocatalytic CO_(2)reduction in inorganic reaction system is investigated.Confined single-atom Ni^(2+),Co^(2+),and Cd^(2+)sites were created via cation-exchange process and enhanced CO_(2)reduction,while Fe^(2+)suppressed the photocatalytic activity for both water and CO_(2)reduction.The modified ZnS:Cu photocatalysts(M/ZnS:Cu)demonstrated tunable product selectivity,with Ni^(2+)and Co^(2+)showing high selectivity for syngas production and Cd^(2+)displaying remarkable formate selectivity.DFT calculations indicated favorable H adsorption free energy on Ni^(2+)and Co^(2+)sites,promoting the hydrogen evolution reaction.The selectivity of CO_(2)reduction products was found to be sensitive to the initial intermediate adsorption states.*COOH formed on Ni^(2+)and Co^(2+)while*OCHO formed on Cd^(2+),favoring the production of CO and HCOOH as the main products,respectively.This work provides valuable insights for developing efficient solar-to-fuel platforms with controlled CO_(2)reduction selectivity.
基金the support from the National Natural Science Foundation of China (Nos.U2001220 and 51902223)the Haihe Laboratory of Sustainable Chemical Transformations+2 种基金the Fundamental Research Funds for the Central Universitiesthe National Key Research and Development Program of China (Nos.2021YFF0500600 and 2019YFE0118800)the Natural Science Foundation of Tianjin (No.20JCYBJC00850)
文摘Solid-state batteries(SSBs)have been considered the most promising technology because of their superior energy density and safety.Among all the solid-state electrolytes(SEs),Li_(7) La_(3) Zr_(2) O_(12)(LLZO)with high ionic conductivity(3×10^(−4) S/cm)has been widely investigated.However,its large-scale production in ambient air faces a challenge.After air exposure,the generated Li_(2)CO_(3) layer deteriorates the ionic conductivity and interfacial wettability,thus greatly compromising the electrochemical performance of SSBs.Many works aim to eliminate this layer to recover the pristine LLZO surface.Unfor-tunately,few articles have emphasized the merits of Li_(2)CO_(3).In this review,we focus on the two-sidedness of Li_(2)CO_(3).We discuss the various characteristics of Li_(2)CO_(3) that can be used and recapitulate the strategies that utilize Li_(2)CO_(3).Insulating Li_(2)CO_(3) is no longer an obstacle but an opportunity for realizing intimate interfacial contact,high air stability,and outstand-ing electrochemical performance.This review aims to off er insightful guidelines for treating air-induced Li_(2)CO_(3) and lead to developing the enhanced air stability and electrochemical performance of LLZO.
基金financially supported by the Scientific and Technological Plan Projects of Guangzhou City(202103040001)。
文摘This work develops 2-Phenyl-1H-imidazole-1-sulfonate(PHIS)as a multi-functional electrolyte additive for H2O/HF scavenging and film formation to improve the high temperature performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/graphite batteries.After 450 cycles at room temperature(25℃),the discharge capacity retentions of batteries with blank and PHIS-containing electrolyte are 56.03%and 94.92%respectively.After 230 cycles at high temperatures(45℃),their values are 75.30%and 88.38%respectively.The enhanced electrochemical performance of the batteries with PHIS-containing electrolyte is supported by the spectroscopic characterization and theoretical calculations.It is demonstrated that this PHIS electrolyte additive can facilitate the construction of the electrode interface films,remove the H2O/HF in the electrolyte,and improve the electrochemical performance of the batteries.This work not only develops a sulfonate-based electrolyte but also can stimulate new ideas of functional additives to improve the battery performance.
基金supported by the Guangdong Natural Science Funds for Distinguished Young Scholar (2014A030306048)National Natural Science Foundation of China (21403306)+3 种基金Tip-top Scientific and Technical Innovative Youth Talents of Guangdong Special Support Program (2015TQO1C205)Pearl River Nova Program of Guangzhou (201610010080)Open Fund of Jiangsu Key Laboratory of Materials and Technology for Energy Conversion (MTEC-2015M05)Training Program of Scientific and Technological Innovation for Undergraduates (pdjh2017a0003)
文摘The overall electrochemical performances of Ni-Zn batteries are still far from satisfactory, specifically for rate performance and cycling stability Herein, we demonstrated a high-performance flexible Ni//Zn battery with outstanding durability and high power density based on selfsupported NiCo_2 O_4 nanosheets as cathode and Zn nanosheets as anode. This Ni//Zn battery is able to deliver a remarkable capacity of183.1 mAh g^(-1) and a good cycling performance(82.7% capacity retention after 3500 cycles). More importantly, this battery achieves an admirable power density of 49.0 kW kg^(-1) and energy density of 303.8 Wh kg^(-1), substantially higher than most recently reported batteries. With such excellent electrochemical performance, this battery will have great potential as an ultrafast power source in practical application.
