Membrane electrode assemblies (MEAs) have been developed for electrochemical conversion of CO2 to high-value multi-carbon (C2+) products at industrial current densities (j>200 mA cm-2). However, the effective and simultaneous modulation of CO₂ and H₂O mass transfer within MEA remains a critical issue, particularly at the three-phase interface. Herein, CO2 and H2O channels are designed in the catalyst layer network to benefit the micro-environment. The balance of local CO2 and H2O at the reaction interface is attained by regulating the catalyst-coated ionomer. In-situ DEMS further confirms that the rational routes are successfully established for mass transfer management. The interfacial distribution of CO2 and H2O are in-depth investigated by in-situ ATR-SEIRAS and molecular dynamics (MD) simulation. By reasonable catalyst layers design, CO2-to-C2+ performance is substantially enhanced, which exhibits remarkable selectivity to C2+ products with a faradaic efficiency (FE) of 89.4±0.69% and a partial current density of 536±4.14 mA cm-2. The optimized Cu-GDE also exhibits excellent stability of >10h at a total current of 2 A.
{"title":"Rational Catalyst Layers Design Enables Tailored Transport Channels for Efficient CO2 Electrochemical Reduction to Multi-carbon Products","authors":"Jiping Sun, Bichao Wu, Zhixing Wang, Huajun Guo, Guochun Yan, Hui Duan, Guangchao Li, Ying Wang, Jiexi Wang","doi":"10.1039/d4ee03743j","DOIUrl":"https://doi.org/10.1039/d4ee03743j","url":null,"abstract":"Membrane electrode assemblies (MEAs) have been developed for electrochemical conversion of CO2 to high-value multi-carbon (C2+) products at industrial current densities (j>200 mA cm-2). However, the effective and simultaneous modulation of CO₂ and H₂O mass transfer within MEA remains a critical issue, particularly at the three-phase interface. Herein, CO2 and H2O channels are designed in the catalyst layer network to benefit the micro-environment. The balance of local CO2 and H2O at the reaction interface is attained by regulating the catalyst-coated ionomer. In-situ DEMS further confirms that the rational routes are successfully established for mass transfer management. The interfacial distribution of CO2 and H2O are in-depth investigated by in-situ ATR-SEIRAS and molecular dynamics (MD) simulation. By reasonable catalyst layers design, CO2-to-C2+ performance is substantially enhanced, which exhibits remarkable selectivity to C2+ products with a faradaic efficiency (FE) of 89.4±0.69% and a partial current density of 536±4.14 mA cm-2. The optimized Cu-GDE also exhibits excellent stability of >10h at a total current of 2 A.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"17 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777091","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fakang Xie, Yu Du, Mengfei Lu, Shicheng Yan, Zhigang Zou
The sluggish kinetics of the oxygen evolution reaction (OER) greatly limits the efficiency of water splitting. The high OER overpotentials would originate from the high electron transfer barriers in the electrolyte/catalytic layer/catalyst core interfaces during the water oxidation reactions. Here, we assemble the temperature-dependent magnetic YFe1-xMnxO3 core and the paramagnetic YFeOOH shell to form a YFe1-xMnxO3@YFeOOH core-shell structured catalyst to explore the effects of thermal-stimulated magnetic state of catalytic materials on OER kinetics. We find that the thermal-stimulated paramagnetic state of YFe1-xMnxO3 core contributes to the accelerated electron transfer at the YFe1-xMnxO3@YFeOOH core-catalytic layer interface. Meanwhile, it improves the intrinsic OER activities of the YFeOOH catalytic layer. The thermal-stimulated magnetic transition of YFe1-xMnxO3 (from antiferromagnetic to paramagnetic) enlarges the magnetic disorder at the YFe1-xMnxO3@YFeOOH interface to reduce the spin flipping barriers and induces to produce the highly OER-active electronic states for YFeOOH catalytic layer due to the strong interactions between YFe1-xMnxO3 core and YFeOOH catalytic layer, thus breaking the linear Arrhenius relationship. Our findings provide a new low-barrier OER route by thermal-stimulated magnetic disordering.
{"title":"Thermal-stimulated spin disordering accelerates water electrolysis","authors":"Fakang Xie, Yu Du, Mengfei Lu, Shicheng Yan, Zhigang Zou","doi":"10.1039/d4ee04597a","DOIUrl":"https://doi.org/10.1039/d4ee04597a","url":null,"abstract":"The sluggish kinetics of the oxygen evolution reaction (OER) greatly limits the efficiency of water splitting. The high OER overpotentials would originate from the high electron transfer barriers in the electrolyte/catalytic layer/catalyst core interfaces during the water oxidation reactions. Here, we assemble the temperature-dependent magnetic YFe1-xMnxO3 core and the paramagnetic YFeOOH shell to form a YFe1-xMnxO3@YFeOOH core-shell structured catalyst to explore the effects of thermal-stimulated magnetic state of catalytic materials on OER kinetics. We find that the thermal-stimulated paramagnetic state of YFe1-xMnxO3 core contributes to the accelerated electron transfer at the YFe1-xMnxO3@YFeOOH core-catalytic layer interface. Meanwhile, it improves the intrinsic OER activities of the YFeOOH catalytic layer. The thermal-stimulated magnetic transition of YFe1-xMnxO3 (from antiferromagnetic to paramagnetic) enlarges the magnetic disorder at the YFe1-xMnxO3@YFeOOH interface to reduce the spin flipping barriers and induces to produce the highly OER-active electronic states for YFeOOH catalytic layer due to the strong interactions between YFe1-xMnxO3 core and YFeOOH catalytic layer, thus breaking the linear Arrhenius relationship. Our findings provide a new low-barrier OER route by thermal-stimulated magnetic disordering.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"27 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777092","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The single atom electrocatalysts with the typical metal-nitrogen-carbon sites possess good oxygen reduction reaction (ORR) activity, yet challenges remain in fabricating rechargeable Zn-air batteries (ZABs) due to their poor oxygen evolution reaction (OER) performance. Herein, we demonstrated the in-situ anchoring of indium clusters on carbon matrix with iron-nitrogen-carbon sites via the pyrolysis of supermolecule aggregation coordinated with indium and iron ions, aimed to prepare advanced bifunctional electrocatalysts for ORR and OER. With the detailed atomic structure analysis, the modulation on coordination environment between indium cluster and iron-nitrogen-carbon sites induces asymmetrical charge distribution to reduce the reaction barrier via the the p-d orbital hybridization, thus achieving superior bifunctional electrocatalytic activity. Consequently, the rechargeable ZABs demonstrated a cycling durability of 1650 h. Moreover, the solid-state batteries also exhibited a large power density of 220.0 mWcm-2. The work provides a feasible guide for rational incorporation of metal clusters with single atom sites to enhance bifunctional electrocatalysis.
{"title":"Coupling of Indium Clusters with Atomic Fe-N4 on Carbon for Long-term Rechargeable Zn-Air Batteries","authors":"Xinxin Shu, Xueying Cao, Bowen He, Xunyi Chen, Lanling Zhao, Chengdong Yang, Jizhen Ma, Jintao Zhang","doi":"10.1039/d4ee04465g","DOIUrl":"https://doi.org/10.1039/d4ee04465g","url":null,"abstract":"The single atom electrocatalysts with the typical metal-nitrogen-carbon sites possess good oxygen reduction reaction (ORR) activity, yet challenges remain in fabricating rechargeable Zn-air batteries (ZABs) due to their poor oxygen evolution reaction (OER) performance. Herein, we demonstrated the in-situ anchoring of indium clusters on carbon matrix with iron-nitrogen-carbon sites via the pyrolysis of supermolecule aggregation coordinated with indium and iron ions, aimed to prepare advanced bifunctional electrocatalysts for ORR and OER. With the detailed atomic structure analysis, the modulation on coordination environment between indium cluster and iron-nitrogen-carbon sites induces asymmetrical charge distribution to reduce the reaction barrier via the the p-d orbital hybridization, thus achieving superior bifunctional electrocatalytic activity. Consequently, the rechargeable ZABs demonstrated a cycling durability of 1650 h. Moreover, the solid-state batteries also exhibited a large power density of 220.0 mWcm<small><sup>-2</sup></small>. The work provides a feasible guide for rational incorporation of metal clusters with single atom sites to enhance bifunctional electrocatalysis.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"79 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777094","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We demonstrated a facile electrochemical treatment for in-situ anchoring subnanometric Cu4 clusters in graphitic C3N5 framework (Cu4/C3N5), leading to remarkable improvements of photocatalytic reactivity and selectivity for CO2 reduction into ethanol. In the absence of sacrificial reagent, a record ethanol production activity of 32.2 μmol•g-1•h-1 with 98.6% selectivity has been achieved under visible light irradiation (λ ≥ 420 nm). In-situ characterizations and theoretical calculations reveal that the significant improvement of reactivity and selectivity should be attributed to the coexisted Cu+ and Cu0 double active-sites in Cu4/C3N5 catalysts for highly efficient C-C coupling process. More specifically, the electron enriched Cu0 active sites could efficiently promote adsorption/activation of CO2 molecules to form *CO intermediates, which partially transferred to adjacent Cu+ sites for preferential C-C coupling to generate *COCO intermediates. After the subsequent hydrogenation process, the photocatalytic CO2-to-ethanol conversion has been achieved.
{"title":"Anchoring subnanometric Cu4 clusters in graphitic-C3N5 for highly efficient CO2 photoreduction to ethanol","authors":"Entian Cui, Yulian Lu, Xiuli Yang, Guojun Dong, Yajun Zhang, Yingpu Bi","doi":"10.1039/d4ee02449d","DOIUrl":"https://doi.org/10.1039/d4ee02449d","url":null,"abstract":"We demonstrated a facile electrochemical treatment for in-situ anchoring subnanometric Cu4 clusters in graphitic C3N5 framework (Cu4/C3N5), leading to remarkable improvements of photocatalytic reactivity and selectivity for CO2 reduction into ethanol. In the absence of sacrificial reagent, a record ethanol production activity of 32.2 μmol•g-1•h-1 with 98.6% selectivity has been achieved under visible light irradiation (λ ≥ 420 nm). In-situ characterizations and theoretical calculations reveal that the significant improvement of reactivity and selectivity should be attributed to the coexisted Cu+ and Cu0 double active-sites in Cu4/C3N5 catalysts for highly efficient C-C coupling process. More specifically, the electron enriched Cu0 active sites could efficiently promote adsorption/activation of CO2 molecules to form *CO intermediates, which partially transferred to adjacent Cu+ sites for preferential C-C coupling to generate *COCO intermediates. After the subsequent hydrogenation process, the photocatalytic CO2-to-ethanol conversion has been achieved.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"174 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Optimization of the charging reaction for zinc-air batteries remains a significant challenge. Here, we report a series of zinc-alcohol-air batteries that replace the oxygen evolution reaction with more thermodynamically favorable alcohol oxidation reactions for the charging reaction, using AuPd@C as the model catalyst. These batteries reduce the voltage window between charge and discharge by two orders of magnitude, achieving a remarkable round-trip efficiency (RTE) of over 99 % at 0.1 mA cm-2. This design demonstrates low charging voltage, high energy density (1020.6 kWh kg-1Zn) and excellent cyclic stability (over 1000 h), making it highly valuable for practical applications. The zinc-alcohol-air batteries utilizing C1-C4 alcohols show significant improvements in overall efficiency, offering great potential for biomass energy utilization and further development of zinc-air batteries.
{"title":"Zinc-Alcohol-Air Batteries with Ultra-Narrow Cyclic Voltage Windows","authors":"Zilong Li, Shunlian Ning, Yanshuo Jin, Nan Wang, Shuhui Sun, Hui Meng","doi":"10.1039/d4ee04691a","DOIUrl":"https://doi.org/10.1039/d4ee04691a","url":null,"abstract":"Optimization of the charging reaction for zinc-air batteries remains a significant challenge. Here, we report a series of zinc-alcohol-air batteries that replace the oxygen evolution reaction with more thermodynamically favorable alcohol oxidation reactions for the charging reaction, using AuPd@C as the model catalyst. These batteries reduce the voltage window between charge and discharge by two orders of magnitude, achieving a remarkable round-trip efficiency (RTE) of over 99 % at 0.1 mA cm-2. This design demonstrates low charging voltage, high energy density (1020.6 kWh kg-1Zn) and excellent cyclic stability (over 1000 h), making it highly valuable for practical applications. The zinc-alcohol-air batteries utilizing C1-C4 alcohols show significant improvements in overall efficiency, offering great potential for biomass energy utilization and further development of zinc-air batteries.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"20 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777095","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ruqian Zhang, Tao Shui, An Li, Huan Xia, Gang Xu, Lingfeng Ji, Chengjie Lu, Wei Zhang, Zhengming Sun
Aqueous zinc-ion batteries (AZIBs) offer significant advantages, including low cost, inherent safety, and high theoretical capacity. However, they are prone to surface corrosion and uncontrolled dendrite growth on zinc anode, particularly under high current densities. Herein, we propose an artificial solid electrolyte interphase (SEI) composed of complex Zn2+ salts to alter the de-solvation process and homogenize the electric field, thereby enabling stable circulation of AZIBs. This SEI is formed through the excitation of iminodiacetonitrile (IDAN) into Iminodiacetic acid (IDA) on the surface of the zinc anode during electroplating. Simultaneously, the generated IDAs conjugate with flowing zinc ions thus creating a dense protective layer embedded into the anode surface. The obtained SEI exhibits superior Zn2+ conductivity, super-hydrophilic property, electrical insulation and negligible interfacial resistance, imparting outstanding durability to the zinc anode even at an ultra-high current density (100 mA·cm-2, over 630 h) without dendrite growth, giving a cumulative plating capacity exceeding 31.5 Ah·cm−2. Moreover, the favorable zinc plating/stripping behavior facilitated by the SEI enables stable operation under harsh conditions (90% depth of discharge, 440 h of Zn||Zn and 20 A g-1, 2000 cycles of Zn||NH4V4O10). The current density tolerance provided by the complex SEI, achieved through a novel in-situ excitation/conjugation fabrication process, promises to enrich SEI strategies and expand the application of AZIBs, particularly in fast-charging/discharging battery systems.
{"title":"Novel In-Situ SEI Fabrication on Zn Anodes for Ultra-High Current Density Tolerance Enabled by Electrical Excitation-Conjugation of Iminoacetonitriles","authors":"Ruqian Zhang, Tao Shui, An Li, Huan Xia, Gang Xu, Lingfeng Ji, Chengjie Lu, Wei Zhang, Zhengming Sun","doi":"10.1039/d4ee03624g","DOIUrl":"https://doi.org/10.1039/d4ee03624g","url":null,"abstract":"Aqueous zinc-ion batteries (AZIBs) offer significant advantages, including low cost, inherent safety, and high theoretical capacity. However, they are prone to surface corrosion and uncontrolled dendrite growth on zinc anode, particularly under high current densities. Herein, we propose an artificial solid electrolyte interphase (SEI) composed of complex Zn2+ salts to alter the de-solvation process and homogenize the electric field, thereby enabling stable circulation of AZIBs. This SEI is formed through the excitation of iminodiacetonitrile (IDAN) into Iminodiacetic acid (IDA) on the surface of the zinc anode during electroplating. Simultaneously, the generated IDAs conjugate with flowing zinc ions thus creating a dense protective layer embedded into the anode surface. The obtained SEI exhibits superior Zn2+ conductivity, super-hydrophilic property, electrical insulation and negligible interfacial resistance, imparting outstanding durability to the zinc anode even at an ultra-high current density (100 mA·cm-2, over 630 h) without dendrite growth, giving a cumulative plating capacity exceeding 31.5 Ah·cm−2. Moreover, the favorable zinc plating/stripping behavior facilitated by the SEI enables stable operation under harsh conditions (90% depth of discharge, 440 h of Zn||Zn and 20 A g-1, 2000 cycles of Zn||NH4V4O10). The current density tolerance provided by the complex SEI, achieved through a novel in-situ excitation/conjugation fabrication process, promises to enrich SEI strategies and expand the application of AZIBs, particularly in fast-charging/discharging battery systems.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"12 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142763154","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Closing the efficiency gap between organic solar cells and their inorganic and perovskite counterparts requires a detailed understanding of the exciton dissociation and charge separation processes, energy loss mechanisms, and influence of disorder effects. In addition, the roles played by excitations delocalized over two or more (macro)molecules and by localized triplet states remain to be well-defined. To address these issues, we have combined molecular dynamics simulations with density functional theory calculations to provide a comprehensive analysis of charge generation and charge recombination in the representative PM6:Y6 blend, describe loss mechanisms, and assess the influence of disorder on the electronic processes. The results allowed the identification of Y6 excimer-like states that can efficiently dissociate into states with hole-electron separation distances larger than those in conventional donor:acceptor interfacial charge-transfer states. They also point to the appearance of low-energy defect states upon formation of Y6 twisted conformations, which can negatively impact the Y6 chemical stability and device performance. Importantly, it is found that the local triplet states formed via non-geminate recombination can efficiently transfer back to triplet CT states, opening the way to eventual dissociation into free charges. Overall, our work provides valuable insight into the charge dynamics within PM6:Y6 active layers.
{"title":"Analysis of the Charge Generation and Recombination Processes in the PM6:Y6 Organic Solar Cell","authors":"Saied Md Pratik, Grit Kupgan, Jean-Luc Bredas, Veaceslav Coropceanu","doi":"10.1039/d4ee03815k","DOIUrl":"https://doi.org/10.1039/d4ee03815k","url":null,"abstract":"Closing the efficiency gap between organic solar cells and their inorganic and perovskite counterparts requires a detailed understanding of the exciton dissociation and charge separation processes, energy loss mechanisms, and influence of disorder effects. In addition, the roles played by excitations delocalized over two or more (macro)molecules and by localized triplet states remain to be well-defined. To address these issues, we have combined molecular dynamics simulations with density functional theory calculations to provide a comprehensive analysis of charge generation and charge recombination in the representative PM6:Y6 blend, describe loss mechanisms, and assess the influence of disorder on the electronic processes. The results allowed the identification of Y6 excimer-like states that can efficiently dissociate into states with hole-electron separation distances larger than those in conventional donor:acceptor interfacial charge-transfer states. They also point to the appearance of low-energy defect states upon formation of Y6 twisted conformations, which can negatively impact the Y6 chemical stability and device performance. Importantly, it is found that the local triplet states formed via non-geminate recombination can efficiently transfer back to triplet CT states, opening the way to eventual dissociation into free charges. Overall, our work provides valuable insight into the charge dynamics within PM6:Y6 active layers.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"7 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142763156","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xin Wang, Yameng Fan, Jia-Yang Li, Xinghan Li, Weijie Li, Jiazhao Wang, Wei Kong Pang
All solid-state sodium metal batteries (ASSSMBs) emerge as promising candidates to be a key technology in large-scale energy storage systems relative to mature Li/Na-ion batteries using flammable liquid electrolytes, owing to their abundant sodium resources, robust safety performance, desirable energy density, favorable reliability, and stability. A series of solid-state electrolytes (SSEs), regarded as an essential component of ASSSMBs, have been extensively developed in recent years. Among them, the Na superionic conductor (NASICON)-structure Na1+xZr2SixP3-xO12 (0≤x≤3, defined as NZSP) materials have attracted overwhelming attention as the most appropriate SSEs for the next-generation high energy density ASSSMBs. Herein, this review seeks to provide a comprehensive and in-depth understanding of NZSP SSEs, starting by investigating their fundamentals, including composition, crystal structure, Na+-ion conduction mechanism, synthetic methods, and the key challenges associated with the NZSP-based ASSSMBs. Subsequently, comprehensive constructive modification strategies are proposed to optimize integrated NZSP SSEs-based ASSSMBs. Finally, informed and strategic perspectives from various angles are summarized, providing potential guidance and possible avenues for further research aimed at achieving exceptional NZSP SSEs-based ASSSMBs for practical applications.
{"title":"Comprehensive understanding of Na1+xZr2SixP3-xO12 solid-state electrolyte in advanced sodium metal batteries: A critical review","authors":"Xin Wang, Yameng Fan, Jia-Yang Li, Xinghan Li, Weijie Li, Jiazhao Wang, Wei Kong Pang","doi":"10.1039/d4ee04323e","DOIUrl":"https://doi.org/10.1039/d4ee04323e","url":null,"abstract":"All solid-state sodium metal batteries (ASSSMBs) emerge as promising candidates to be a key technology in large-scale energy storage systems relative to mature Li/Na-ion batteries using flammable liquid electrolytes, owing to their abundant sodium resources, robust safety performance, desirable energy density, favorable reliability, and stability. A series of solid-state electrolytes (SSEs), regarded as an essential component of ASSSMBs, have been extensively developed in recent years. Among them, the Na superionic conductor (NASICON)-structure Na1+xZr2SixP3-xO12 (0≤x≤3, defined as NZSP) materials have attracted overwhelming attention as the most appropriate SSEs for the next-generation high energy density ASSSMBs. Herein, this review seeks to provide a comprehensive and in-depth understanding of NZSP SSEs, starting by investigating their fundamentals, including composition, crystal structure, Na+-ion conduction mechanism, synthetic methods, and the key challenges associated with the NZSP-based ASSSMBs. Subsequently, comprehensive constructive modification strategies are proposed to optimize integrated NZSP SSEs-based ASSSMBs. Finally, informed and strategic perspectives from various angles are summarized, providing potential guidance and possible avenues for further research aimed at achieving exceptional NZSP SSEs-based ASSSMBs for practical applications.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"214 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142763155","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kai Du, Jiaqi Guo, Chenxi Song, Xin Liu, Mingjun Chen, Dachao Yuan, Runping Ye, Xingyuan San, Yaguang Li, Jinhua Ye
Photothermal CO2 methanation is crucial for carbon neutralization and long-term space exploration, but the reliance on sunlight irradiation limits its practical application. Herein, a fluorite two-dimensional solid solution of NiO and CeO2 (2D Ni1Ce1O3) is synthesized for low-temperature CO2 methanation, resulting in 80±4 and 2125±43 mmol g-1 h-1 of CH4 production rates at 200 and 300 °C respectively, with 99.58±0.12% CH4 selectivity. It is attributed to that 2D Ni1Ce1O3 strengthens the CO2 adsorption and changes the CO2 methanation paths. When we used a homemade TiC/Cu based device to absorb sunlight to heat the catalyst, the 2D Ni1Ce1O3 shows a photothermal CO2 methanation rate of 2901 mmol g-1 h-1 under weak sunlight irradiation and more interestingly a robust CO2 methanation rate of ~830 mmol h-1 under dark environments. Consequently, the outdoor demonstration could drive CO2 methanation for five continuous outdoor days and nights with a total CH4 yield of 898 m3 and 10 tons of boiled water, showing the industrial potential of photothermal CO2 methanation.
{"title":"Persistent photothermal CO2 methanation without external energy input","authors":"Kai Du, Jiaqi Guo, Chenxi Song, Xin Liu, Mingjun Chen, Dachao Yuan, Runping Ye, Xingyuan San, Yaguang Li, Jinhua Ye","doi":"10.1039/d4ee04849k","DOIUrl":"https://doi.org/10.1039/d4ee04849k","url":null,"abstract":"Photothermal CO2 methanation is crucial for carbon neutralization and long-term space exploration, but the reliance on sunlight irradiation limits its practical application. Herein, a fluorite two-dimensional solid solution of NiO and CeO2 (2D Ni1Ce1O3) is synthesized for low-temperature CO2 methanation, resulting in 80±4 and 2125±43 mmol g-1 h-1 of CH4 production rates at 200 and 300 °C respectively, with 99.58±0.12% CH4 selectivity. It is attributed to that 2D Ni1Ce1O3 strengthens the CO2 adsorption and changes the CO2 methanation paths. When we used a homemade TiC/Cu based device to absorb sunlight to heat the catalyst, the 2D Ni1Ce1O3 shows a photothermal CO2 methanation rate of 2901 mmol g-1 h-1 under weak sunlight irradiation and more interestingly a robust CO2 methanation rate of ~830 mmol h-1 under dark environments. Consequently, the outdoor demonstration could drive CO2 methanation for five continuous outdoor days and nights with a total CH4 yield of 898 m3 and 10 tons of boiled water, showing the industrial potential of photothermal CO2 methanation.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"66 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760427","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jintu Qi, Yongchao Tang, Yue Wei, Guigui Liu, Jianping Yan, ZhenFeng Feng, Zixin Han, Minghui Ye, Wencheng Du, Qi Yang, Yufei Zhang, Zhipeng Wen, Xiaoqing Liu, Cheng Chao Li
Hypervalent Te redox (Te0/Te4+) in ionic liquid electrolytes (ILEs) is promising for energetic Zn batteries. However, the energy contribution of Te0/Te4+ is only one-third of the total redox-amphoteric conversion, which entails the contribution maximization for energy upgradation. The underlying kinetics-limited factor is vital but usually overlooked in previous explorations. Herein, we unlock a halogen-bond chemistry-rectified Te0/Te4+ redox with an almost maximized contribution for 700-Wh kgTe-1 Zn batteries. The Zn-X bond barriers in ZnX42- (X = Cl, Br) species from ILEs play crucial roles in rectifying the Te0/Te4+ redox kinetics, especially in localized concentrated ILEs, resulting in sharply different redox conversion depth. When the ZnBr42- with weak Zn-Br bond (34.96 kcal mol-1) as the activator, the Te0/Te4+ redox contribution can be maximized to ~90.0% over 5000 cycles at 5 A g-1, 1.8-fold higher than that with ZnCl42- activator via strong Zn-Cl bond (102.81 kcal mol-1), surpassing those in most aqueous systems (ca. 33.0%). This work decodes halogen-bond chemistry-rectified kinetics to maximize hypervalent redox contribution towards high-energy Zn batteries, which could apply to other chalcogen conversion batteries.
{"title":"Halogen-Bond Chemistry-Rectified Hypervalent Tellurium Redox Kinetics towards High-Energy Zn Batteries","authors":"Jintu Qi, Yongchao Tang, Yue Wei, Guigui Liu, Jianping Yan, ZhenFeng Feng, Zixin Han, Minghui Ye, Wencheng Du, Qi Yang, Yufei Zhang, Zhipeng Wen, Xiaoqing Liu, Cheng Chao Li","doi":"10.1039/d4ee04806g","DOIUrl":"https://doi.org/10.1039/d4ee04806g","url":null,"abstract":"Hypervalent Te redox (Te0/Te4+) in ionic liquid electrolytes (ILEs) is promising for energetic Zn batteries. However, the energy contribution of Te0/Te4+ is only one-third of the total redox-amphoteric conversion, which entails the contribution maximization for energy upgradation. The underlying kinetics-limited factor is vital but usually overlooked in previous explorations. Herein, we unlock a halogen-bond chemistry-rectified Te0/Te4+ redox with an almost maximized contribution for 700-Wh kgTe-1 Zn batteries. The Zn-X bond barriers in ZnX42- (X = Cl, Br) species from ILEs play crucial roles in rectifying the Te0/Te4+ redox kinetics, especially in localized concentrated ILEs, resulting in sharply different redox conversion depth. When the ZnBr42- with weak Zn-Br bond (34.96 kcal mol-1) as the activator, the Te0/Te4+ redox contribution can be maximized to ~90.0% over 5000 cycles at 5 A g-1, 1.8-fold higher than that with ZnCl42- activator via strong Zn-Cl bond (102.81 kcal mol-1), surpassing those in most aqueous systems (ca. 33.0%). This work decodes halogen-bond chemistry-rectified kinetics to maximize hypervalent redox contribution towards high-energy Zn batteries, which could apply to other chalcogen conversion batteries.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"18 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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