Electrolytic Zn-MnO_(2)batteries arepromising candidates for safe and sustainable energystorage owing to their high voltage,environmentalbenignity,and cost-effectiveness.However,practicalapplications are hindered by t...Electrolytic Zn-MnO_(2)batteries arepromising candidates for safe and sustainable energystorage owing to their high voltage,environmentalbenignity,and cost-effectiveness.However,practicalapplications are hindered by the poor conductivity andthe irreversible dissolution of conventionalε-MnO_(2)deposits.Herein,we report a scalable semisolid slurryelectrode architecture that enables stable MnO_(2)deposition/dissolution using a three-dimensional percolatingnetwork of carbon nanotubes(CNTs)as both conductivematrix and deposition host.The slurry systempromotes the formation of highly conductiveγ-MnO_(2)owing to enhanced charge transfer kinetics,enablingoverall dissolution rather than the localized separationtypically seen in traditional electrodes.The Zn-MnO_(2)slurry cell exhibits a reversible areal capacity approaching 60 mAh cm^(-2).Moreover,theflowable nature of the slurry allows electrochemically inactive MnO_(2)formed during dissolution to be reconnected and reactivated by CNTs inthe rheological network,ensuring deep utilization and cycling stability.This work establishes a slurry electrode strategy to improve electrolyticMnO_(2)reactions and offers a viable pathway toward renewable aqueous batteries for grid-scale applications.展开更多
Developing advanced electrocatalysts to convert CO_(2) into liquid fuels such as C_(2)H_(5)OH is critical for utilizing intermittent renewable energy.The formation of C_(2)H_(5)OH,however,is generally less favored com...Developing advanced electrocatalysts to convert CO_(2) into liquid fuels such as C_(2)H_(5)OH is critical for utilizing intermittent renewable energy.The formation of C_(2)H_(5)OH,however,is generally less favored compared with the other hydrocarbon products from Cu-based electrocatalysts.In this work,an alkanethiolmodified Cu_(2)O nanowire array(OTT-Cu_(2)O) was constructed with asymmetric Cu sites consisting of paired Cu-O and Cu-S motifs to overcome previous limitations of C_(2)H_(5)OH electrosynthesis via CO_(2)RR pathway.This catalyst achieves a high Faradaic efficiency of 45 % for CO_(2)-to-C_(2)H_(5)OH conversion at 300 m A/cm^(2),representing a more than two-fold enhancement over the Cu_(2)O electrode.Mechanistic investigations reveal that the Cu-S site exhibits distinct C-binding capability that stabilizes key intermediates(^(*)OCH_(2) and ^(*)CO),in contrast to the O-affinitive Cu-O site.The asymmetric S-Cu-O configuration promotes thermodynamically favorable asymmetric C-C coupling between ^(*)CO and ^(*)OCH_(2),forming the critical CO-OCH_(2) intermediate and facilitating C_(2)H_(5)OH production,as opposed to symmetric O-Cu-O sites that mainly generate HCOOH.This work offers an effective strategy for designing multi-active-site catalysts toward highly selective CO_(2) reduction to C_(2)H_(5)OH and provides fundamental insight into the reaction mechanism.展开更多
基金supported by the National Natural Science Foundation of China(No.22109181,U24A2060,22279023,and 22309031)the National Key R&D Program of China(2024YFE0101100)+6 种基金the Hunan Provincial Science and Technology Plan Projects of China(No.2017TP1001)the Hunan Provincial Natural Science Foundation of China(No.2025JJ40011)the Fundamental Research Funds for the Central Universities(20720250005)the Science and Technology Commission of Shanghai Municipality(25DZ3002901,2024ZDSYS02,25PY2600100)the Shanghai Pilot Program for Basic Research-Fudan University 21TQ1400100(25TQ012)the AI for Science Foundation of Fudan University(FudanX24A1035)the National Research Foundation,Singapore,under its Singapore-China Joint Flagship Project(Clean Energy).
文摘Electrolytic Zn-MnO_(2)batteries arepromising candidates for safe and sustainable energystorage owing to their high voltage,environmentalbenignity,and cost-effectiveness.However,practicalapplications are hindered by the poor conductivity andthe irreversible dissolution of conventionalε-MnO_(2)deposits.Herein,we report a scalable semisolid slurryelectrode architecture that enables stable MnO_(2)deposition/dissolution using a three-dimensional percolatingnetwork of carbon nanotubes(CNTs)as both conductivematrix and deposition host.The slurry systempromotes the formation of highly conductiveγ-MnO_(2)owing to enhanced charge transfer kinetics,enablingoverall dissolution rather than the localized separationtypically seen in traditional electrodes.The Zn-MnO_(2)slurry cell exhibits a reversible areal capacity approaching 60 mAh cm^(-2).Moreover,theflowable nature of the slurry allows electrochemically inactive MnO_(2)formed during dissolution to be reconnected and reactivated by CNTs inthe rheological network,ensuring deep utilization and cycling stability.This work establishes a slurry electrode strategy to improve electrolyticMnO_(2)reactions and offers a viable pathway toward renewable aqueous batteries for grid-scale applications.
基金financial supports of the National Natural Science Foundation of China (NSFC,Nos.52394202,52476056,and 52301232)the Natural Science Foundation of Chongqing Province (No.2024NSCQ-MSX1109)。
文摘Developing advanced electrocatalysts to convert CO_(2) into liquid fuels such as C_(2)H_(5)OH is critical for utilizing intermittent renewable energy.The formation of C_(2)H_(5)OH,however,is generally less favored compared with the other hydrocarbon products from Cu-based electrocatalysts.In this work,an alkanethiolmodified Cu_(2)O nanowire array(OTT-Cu_(2)O) was constructed with asymmetric Cu sites consisting of paired Cu-O and Cu-S motifs to overcome previous limitations of C_(2)H_(5)OH electrosynthesis via CO_(2)RR pathway.This catalyst achieves a high Faradaic efficiency of 45 % for CO_(2)-to-C_(2)H_(5)OH conversion at 300 m A/cm^(2),representing a more than two-fold enhancement over the Cu_(2)O electrode.Mechanistic investigations reveal that the Cu-S site exhibits distinct C-binding capability that stabilizes key intermediates(^(*)OCH_(2) and ^(*)CO),in contrast to the O-affinitive Cu-O site.The asymmetric S-Cu-O configuration promotes thermodynamically favorable asymmetric C-C coupling between ^(*)CO and ^(*)OCH_(2),forming the critical CO-OCH_(2) intermediate and facilitating C_(2)H_(5)OH production,as opposed to symmetric O-Cu-O sites that mainly generate HCOOH.This work offers an effective strategy for designing multi-active-site catalysts toward highly selective CO_(2) reduction to C_(2)H_(5)OH and provides fundamental insight into the reaction mechanism.
