Shu Yang, Xianshu Wang, Ruimin Li, Yiming Zhou, Haonan Huang, Mengyuan Zhou, Yunyun Gao, Wanyu Zhao, Yukui Gao, Zhenghui Pan and Xiaowei Yang
Metallic calcium (Ca) is a promising anode for rechargeable batteries; however, it is plagued by poor reversibility of Ca2+ plating/stripping due to the lack of an idealized solid/electrolyte interface (SEI). This is intrinsically related to the fact that little knowledge is available on species that may be more favourable. Herein, this study reveals that the degradation of native SEIs is attributed to organic-rich species with insufficient electrical insulation, resulting in the continuous decomposition of conventionally used carbonic ester or ether solvents. On this basis, we propose a new insight that regulating the Ca2+ solvent sheath to obtain inorganic-rich SEI is a decisive step toward developing reversible Ca metal anodes. With the screening of theoretical calculations, an aggregation (AGG) electrolyte is proposed by involving a small-sized and high-binding-energy anion (BF4−) into the Ca2+ solvation sheath to realize the preferential reductive decomposition of anions. By this method, the derived inorganic fluorides and borates improve reversible Ca plating/stripping. Consequently, the Ca‖Ca symmetric cell exhibits a long-cycling stability over 350 h with low polarization. Finally, the density functional theory confirmed that the fundamental mechanism of working the hybrid inorganic-rich SEI is a low diffusion energy barrier and high electronic insulation that ensure fast Ca2+ diffusion through the SEI film and reversible plating/stripping on the Ca metal surface.
{"title":"Revisiting the interfacial chemistry of calcium metal anodes: the importance of inorganic-rich solid/electrolyte interfaces derived from an aggregation-dominated electrolyte†","authors":"Shu Yang, Xianshu Wang, Ruimin Li, Yiming Zhou, Haonan Huang, Mengyuan Zhou, Yunyun Gao, Wanyu Zhao, Yukui Gao, Zhenghui Pan and Xiaowei Yang","doi":"10.1039/D4EE04478A","DOIUrl":"10.1039/D4EE04478A","url":null,"abstract":"<p >Metallic calcium (Ca) is a promising anode for rechargeable batteries; however, it is plagued by poor reversibility of Ca<small><sup>2+</sup></small> plating/stripping due to the lack of an idealized solid/electrolyte interface (SEI). This is intrinsically related to the fact that little knowledge is available on species that may be more favourable. Herein, this study reveals that the degradation of native SEIs is attributed to organic-rich species with insufficient electrical insulation, resulting in the continuous decomposition of conventionally used carbonic ester or ether solvents. On this basis, we propose a new insight that regulating the Ca<small><sup>2+</sup></small> solvent sheath to obtain inorganic-rich SEI is a decisive step toward developing reversible Ca metal anodes. With the screening of theoretical calculations, an aggregation (AGG) electrolyte is proposed by involving a small-sized and high-binding-energy anion (BF<small><sub>4</sub></small><small><sup>−</sup></small>) into the Ca<small><sup>2+</sup></small> solvation sheath to realize the preferential reductive decomposition of anions. By this method, the derived inorganic fluorides and borates improve reversible Ca plating/stripping. Consequently, the Ca‖Ca symmetric cell exhibits a long-cycling stability over 350 h with low polarization. Finally, the density functional theory confirmed that the fundamental mechanism of working the hybrid inorganic-rich SEI is a low diffusion energy barrier and high electronic insulation that ensure fast Ca<small><sup>2+</sup></small> diffusion through the SEI film and reversible plating/stripping on the Ca metal surface.</p>","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":" 4","pages":" 1941-1951"},"PeriodicalIF":32.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992367","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}
Han et al. claimed that a predominantly (001)-oriented BiVO4 photoanode was successfully fabricated on fluorine-doped SnO2 (FTO) polycrystals through microscale epitaxy by employing laser ablation deposition, leading to a staggering sixteen-fold increase in the efficiency of the BiVO4 photoanode for solar water oxidation compared to a spin-coated BiVO4 photoanode with random orientation. However, the assessment of crystallographic texture was inaccurately conducted through electron backscatter diffraction observations, and was then erroneously confirmed by the θ–2θ scan and pole figures of X-ray diffraction. Contrary to their assertions, our reanalysis of the presented data uncovers that the BiVO4 photoanode likely contains merely ∼6.2% of (001)-oriented grains, with the (011/101)-oriented grains constituting ∼2.9% and the (024/204)-oriented grains comprising ∼3.9% of the overall composition. The remaining grains exhibit a nearly random orientation. The existence of a mere ∼6.2% (001) texture does not seem to conclusively correspond with the sixteen-fold increase in the efficiency of the BiVO4 photoanode in solar water oxidation. The impact of various other microstructural variations (such as porosity and grain integrity) resulting from the diverse deposition techniques on the efficacy of solar water splitting necessitates thoughtful consideration. Moreover, the apparent scarcity of (101)-oriented grains in the underlying FTO layer raises doubts on its capability to facilitate (001)-textured growth of BiVO4 through the alleged microscale epitaxy, as substantial evidence substantiating this assertion is lacking.
{"title":"Comment on “Boosting the solar water oxidation performance of a BiVO4 photoanode by crystallographic orientation control” by H. S. Han, S. Shin, D. H. Kim, I. J. Park, J. S. Kim, P. Huang, J. Lee, I. S. Cho and X. Zheng, Energy Environ. Sci., 2018, 11, 1299","authors":"Chaojing Lu and Xinyu Wang","doi":"10.1039/D4EE02619E","DOIUrl":"10.1039/D4EE02619E","url":null,"abstract":"<p >Han <em>et al.</em> claimed that a predominantly (001)-oriented BiVO<small><sub>4</sub></small> photoanode was successfully fabricated on fluorine-doped SnO<small><sub>2</sub></small> (FTO) polycrystals through microscale epitaxy by employing laser ablation deposition, leading to a staggering sixteen-fold increase in the efficiency of the BiVO<small><sub>4</sub></small> photoanode for solar water oxidation compared to a spin-coated BiVO<small><sub>4</sub></small> photoanode with random orientation. However, the assessment of crystallographic texture was inaccurately conducted through electron backscatter diffraction observations, and was then erroneously confirmed by the <em>θ</em>–2<em>θ</em> scan and pole figures of X-ray diffraction. Contrary to their assertions, our reanalysis of the presented data uncovers that the BiVO<small><sub>4</sub></small> photoanode likely contains merely ∼6.2% of (001)-oriented grains, with the (011/101)-oriented grains constituting ∼2.9% and the (024/204)-oriented grains comprising ∼3.9% of the overall composition. The remaining grains exhibit a nearly random orientation. The existence of a mere ∼6.2% (001) texture does not seem to conclusively correspond with the sixteen-fold increase in the efficiency of the BiVO<small><sub>4</sub></small> photoanode in solar water oxidation. The impact of various other microstructural variations (such as porosity and grain integrity) resulting from the diverse deposition techniques on the efficacy of solar water splitting necessitates thoughtful consideration. Moreover, the apparent scarcity of (101)-oriented grains in the underlying FTO layer raises doubts on its capability to facilitate (001)-textured growth of BiVO<small><sub>4</sub></small> through the alleged microscale epitaxy, as substantial evidence substantiating this assertion is lacking.</p>","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":" 4","pages":" 1992-2002"},"PeriodicalIF":32.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990634","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}
Shenglong Li, Yunpeng Zhong, Jiangtao Huang, Guojun Lai, Le Li, Long Jiang, Xieyu Xu, Bingan Lu, Yangyang Liu, Jiang Zhou
Aqueous zinc-ion batteries (AZIBs) with low cost and inherited safety have been viewed as crucial candidates for the energy storage system, whose commercialization is hindered by the interfacial instability including the growth of dendritic zinc (Zn), passivation on electrodes from H2O-derived parasitic side-reactions, etc. Here, a kind of adjustable-kinetical electrolyte containing tetramethylene glycol with rich ethers and hydroxyl groups as co-solvent is designed to stabilize the Zn anode and achieve highly reversible and durable AZIBs. Lowering interfacial kinetics can effectively minimize the variations of Faradic current density, refining the nuclei and homogenizing the electrodeposition of Zn metal. Moreover, it can also be involved in the solvation reconstruction of Zn2+ to weaken the side-reaction and passivation on the cathode. Consequently, Zn|Zn symmetrical cells with this low-kinetical electrolyte show high reversibility and an exceptionally 7000-hour lifespan at 1.0 mA cm-2. Moreover, the NH4V4O10|Zn pouch cell delivers a capacity of 110 mAh and maintains stable cyclic stability for 450 cycles without capacity degradatio. A a proof of concept, 1.3-Ah NH4V4O10|Zn AZIB lasts more than 25 days in deep charge/discharge operation. In this contribution, lowing interfacial kinetics is certificated as a new perspective to accelerate the commercialization of AZIBs with a satisfactory lifespan.
具有低成本和遗传安全性的水性锌离子电池（azib）已被视为储能系统的重要候选材料，其商业化受到界面不稳定性的阻碍，包括枝晶锌（Zn）的生长，由水衍生的寄生副反应引起的电极钝化等。本文设计了一种含四亚二醇的可调动力学电解质，以丰富的醚和羟基为助溶剂，稳定Zn阳极，实现高可逆和耐用的AZIBs。降低界面动力学可以有效地减小法拉迪电流密度的变化，使金属锌的电沉积过程更加精细和均匀。此外，它还可以参与Zn2+的溶剂化重构，以减弱阴极上的副反应和钝化。因此，具有这种低动力学电解质的Zn|Zn对称电池具有高可逆性，并且在1.0 mA cm-2下具有异常的7000小时寿命。此外，nh4v4010 b|锌袋电池提供了110 mAh的容量，并在450次循环中保持稳定的循环稳定性，而容量没有下降。作为概念验证，1.3 ah的NH4V4O10|Zn AZIB在深度充放电操作中持续使用超过25天。在这一贡献中，低界面动力学被证明是加速azib商业化的新视角，具有令人满意的使用寿命。
{"title":"Regulating Interfacial Kinetics Boost the Durable Ah-Level Zinc-ion Batteries","authors":"Shenglong Li, Yunpeng Zhong, Jiangtao Huang, Guojun Lai, Le Li, Long Jiang, Xieyu Xu, Bingan Lu, Yangyang Liu, Jiang Zhou","doi":"10.1039/d4ee04372c","DOIUrl":"https://doi.org/10.1039/d4ee04372c","url":null,"abstract":"Aqueous zinc-ion batteries (AZIBs) with low cost and inherited safety have been viewed as crucial candidates for the energy storage system, whose commercialization is hindered by the interfacial instability including the growth of dendritic zinc (Zn), passivation on electrodes from H2O-derived parasitic side-reactions, etc. Here, a kind of adjustable-kinetical electrolyte containing tetramethylene glycol with rich ethers and hydroxyl groups as co-solvent is designed to stabilize the Zn anode and achieve highly reversible and durable AZIBs. Lowering interfacial kinetics can effectively minimize the variations of Faradic current density, refining the nuclei and homogenizing the electrodeposition of Zn metal. Moreover, it can also be involved in the solvation reconstruction of Zn2+ to weaken the side-reaction and passivation on the cathode. Consequently, Zn|Zn symmetrical cells with this low-kinetical electrolyte show high reversibility and an exceptionally 7000-hour lifespan at 1.0 mA cm-2. Moreover, the NH4V4O10|Zn pouch cell delivers a capacity of 110 mAh and maintains stable cyclic stability for 450 cycles without capacity degradatio. A a proof of concept, 1.3-Ah NH4V4O10|Zn AZIB lasts more than 25 days in deep charge/discharge operation. In this contribution, lowing interfacial kinetics is certificated as a new perspective to accelerate the commercialization of AZIBs with a satisfactory lifespan.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"18 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990914","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}
Zeheng Li, Zhengwei Wan, Zheng Lin, Mengting Zheng, Jianhui Zheng, Shangshu Qian, Yao Wang, Tinglu Song, Zhan Lin, Jun Lu
The pulverization and disintegration of silicon microparticles (SiMPs) cause additional adherend failure, rendering the highly efficient binders for Si nanoparticle anodes ineffective for SiMP anodes. Herein, we report a grafted polar polymeric binder for constructing robust and durable adhesive joints in SiMPs, preventing the occurrence of the adherend failure. The grafted structure and rich polar groups within the proposed binder empower it excellent interfacial adhesion and coverage capabilities, while strong intra/interchain interactions guarantee its high cohesive strength. These characteristics, in combination with high stretchability and elasticity, enable the binder to accommodate the substantial volume changes of SiMPs and maintain the firm coalescence of pulverized SiMPs without disintegration, resulting in a stable electrode-electrolyte interface and mechanical structure of SiMP anodes during cycling. Additionally, the high Li-ion conductivity of the proposed binder significantly reduces the hindrance to Li-ion transportation in SiMPs caused by binder coverage. Consequently, the SiMP anodes using the proposed binder exhibit impressive electrochemical performances with high initial Coulombic efficiency and superior cycling stability. Specially, the SiMP anodes demonstrate stable and consistent cycling performances in high-capacity and high-energy-density pouch cells, highlighting the practical viability of the proposed binder.
{"title":"A highly elastic and Li-ion conductive binder enables stable operation of silicon microparticle anodes in high-capacity and high-energy-density pouch cells","authors":"Zeheng Li, Zhengwei Wan, Zheng Lin, Mengting Zheng, Jianhui Zheng, Shangshu Qian, Yao Wang, Tinglu Song, Zhan Lin, Jun Lu","doi":"10.1039/d4ee04306e","DOIUrl":"https://doi.org/10.1039/d4ee04306e","url":null,"abstract":"The pulverization and disintegration of silicon microparticles (SiMPs) cause additional adherend failure, rendering the highly efficient binders for Si nanoparticle anodes ineffective for SiMP anodes. Herein, we report a grafted polar polymeric binder for constructing robust and durable adhesive joints in SiMPs, preventing the occurrence of the adherend failure. The grafted structure and rich polar groups within the proposed binder empower it excellent interfacial adhesion and coverage capabilities, while strong intra/interchain interactions guarantee its high cohesive strength. These characteristics, in combination with high stretchability and elasticity, enable the binder to accommodate the substantial volume changes of SiMPs and maintain the firm coalescence of pulverized SiMPs without disintegration, resulting in a stable electrode-electrolyte interface and mechanical structure of SiMP anodes during cycling. Additionally, the high Li-ion conductivity of the proposed binder significantly reduces the hindrance to Li-ion transportation in SiMPs caused by binder coverage. Consequently, the SiMP anodes using the proposed binder exhibit impressive electrochemical performances with high initial Coulombic efficiency and superior cycling stability. Specially, the SiMP anodes demonstrate stable and consistent cycling performances in high-capacity and high-energy-density pouch cells, highlighting the practical viability of the proposed binder.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"30 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990908","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}
Nitrate electroreduction to ammonia holds great promise in sustainable green ammonia synthesis, yet faces the dearth of competent electrocatalysts adapting varying nitrate concentrations, and the inadequate ammonia fixation. Herein, we present a high-performance Ag single-atom-decorated Cu2O nanowires catalyst (Ag1@Cu2O) that exhibits concentration-universal high-rate nitrate reduction, achieving >90% to near-unity ammonia Faradaic efficiency (FE) across nitrate concentrations from 0.01 to 0.5 M. Notably, at 0.5 M nitrate concentration, it attains a two-ampere-level current density (2.3 A cm−2) at ‒1 V vs. RHE, resulting in a leading ammonia yield rate of 184.4 mgNH3 h−1 cm−2. In-situ studies combined with theoretic calculations elucidate an Ag-Cu inter-site synergistic catalytic mechanism, in which single-atom Ag serves as an accelerator for active hydrogen generation and stabilization on Cu sites to boost the hydrogenation kinetics of N-containing intermediates, thus smoothing the energy barriers for ammonia production via the favorable *NHO pathway. Additionally, Ag1@Cu2O demonstrates near-unity formate FE for formaldehyde oxidation, reaching a 300 mA cm−2 current density at merely 0.31 V vs. RHE. Motivated by this exceptional bifunctionality, we demonstrate an innovative tandem electrochemical-chemical strategy for upgrading ammonia into high-value ammonium formate by coupling electrolysis of nitrate reduction and formaldehyde oxidation, followed by straightforward chemical combination and isolation. Practice in a membrane electrode assembly (MEA) electrolysis at 1.6 V for 100 h successfully outputs 10.7 g of high-purity ammonium formate. Furthermore, the commonality of this strategy is validated by application to various nitrate/aldehyde pairs. This work blazes a new trail for scalable, cost- and energy-efficient green ammonia production and fixation from nitrate reduction.
硝酸盐电还原制氨在可持续的绿色氨合成中具有很大的前景，但面临着缺乏适应不同硝酸盐浓度的合格电催化剂和氨固定不足的问题。在此，我们提出了一种高性能的Ag单原子修饰的Cu2O纳米线催化剂（Ag1@Cu2O），该催化剂表现出浓度通用的高速率硝酸盐还原，在0.01至0.5 M的硝酸盐浓度范围内，达到90%的近单位氨法拉第效率（FE）。值得注意的是，在0.5 M的硝酸盐浓度下，与RHE相比，它在-1 V下获得了2安培级的电流密度（2.3 a cm−2），导致氨的产率达到184.4 mgNH3 h−1 cm−2。原位研究结合理论计算阐明了Ag-Cu位点间协同催化机制，其中单原子Ag作为活性氢生成和Cu位点稳定化的加速器，提高了含n中间体的加氢动力学，从而平滑了通过有利的*NHO途径产生氨的能量障碍。此外，Ag1@Cu2O显示了甲醛氧化的近统一甲酸FE，在仅0.31 V时达到300 mA cm - 2电流密度。在这种特殊的双功能的激励下，我们展示了一种创新的串联电化学-化学策略，通过耦合硝酸还原和甲醛氧化的电解，然后是直接的化学组合和分离，将氨转化为高价值的甲酸铵。实践在膜电极组件（MEA）电解在1.6 V 100小时成功输出10.7 g高纯度甲酸铵。此外，通过应用于各种硝酸盐/醛对，验证了该策略的通用性。这项工作为大规模、低成本和节能的绿色氨生产和硝酸盐还原固定开辟了一条新的道路。
{"title":"Unlocking high-current-density nitrate reduction and formaldehyde oxidation synergy for scalable ammonia production and fixation","authors":"Linjie Zhang, Yimeng Cai, Yanghua Li, Chen Sun, Yi Xiao, Yibing Yang, Dechao Chen, Dongdong Xiao, Chi-Feng Lee, Yunjian Wang, Shiqiang Feng, Hsiao-Tsu Wang, Yu-Cheng Shao, Ting-Shan Chan, Hirofumi Ishii, Nozomu Hiraoka, Xiuyun Wang, Jun Luo, Lili Han","doi":"10.1039/d4ee04382k","DOIUrl":"https://doi.org/10.1039/d4ee04382k","url":null,"abstract":"Nitrate electroreduction to ammonia holds great promise in sustainable green ammonia synthesis, yet faces the dearth of competent electrocatalysts adapting varying nitrate concentrations, and the inadequate ammonia fixation. Herein, we present a high-performance Ag single-atom-decorated Cu2O nanowires catalyst (Ag1@Cu2O) that exhibits concentration-universal high-rate nitrate reduction, achieving >90% to near-unity ammonia Faradaic efficiency (FE) across nitrate concentrations from 0.01 to 0.5 M. Notably, at 0.5 M nitrate concentration, it attains a two-ampere-level current density (2.3 A cm−2) at ‒1 V vs. RHE, resulting in a leading ammonia yield rate of 184.4 mgNH3 h−1 cm−2. In-situ studies combined with theoretic calculations elucidate an Ag-Cu inter-site synergistic catalytic mechanism, in which single-atom Ag serves as an accelerator for active hydrogen generation and stabilization on Cu sites to boost the hydrogenation kinetics of N-containing intermediates, thus smoothing the energy barriers for ammonia production via the favorable *NHO pathway. Additionally, Ag1@Cu2O demonstrates near-unity formate FE for formaldehyde oxidation, reaching a 300 mA cm−2 current density at merely 0.31 V vs. RHE. Motivated by this exceptional bifunctionality, we demonstrate an innovative tandem electrochemical-chemical strategy for upgrading ammonia into high-value ammonium formate by coupling electrolysis of nitrate reduction and formaldehyde oxidation, followed by straightforward chemical combination and isolation. Practice in a membrane electrode assembly (MEA) electrolysis at 1.6 V for 100 h successfully outputs 10.7 g of high-purity ammonium formate. Furthermore, the commonality of this strategy is validated by application to various nitrate/aldehyde pairs. This work blazes a new trail for scalable, cost- and energy-efficient green ammonia production and fixation from nitrate reduction.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"20 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990915","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}
This reply addresses critiques on the feasibility of textured BiVO4 growth and methodological rigor in texture analysis. We provide experimental evidence demonstrating the viability of [001]-textured BiVO4 films on polycrystalline substrates via laser ablation. Comprehensive analysis confirms that crystallographic orientation significantly enhances PEC performance, reinforcing the importance of texture engineering in the development of efficient photoelectrochemical materials.
{"title":"Reply to the ‘Comment on “Boosting the solar water oxidation performance of a BiVO4 photoanode by crystallographic orientation control”’ by C. Lu and X. Wang, Energy Environ. Sci., 2025, 18, DOI: 10.1039/D4EE02619E","authors":"Hyun Soo Han, In Sun Cho and Xiaolin Zheng","doi":"10.1039/D4EE04959D","DOIUrl":"10.1039/D4EE04959D","url":null,"abstract":"<p >This reply addresses critiques on the feasibility of textured BiVO<small><sub>4</sub></small> growth and methodological rigor in texture analysis. We provide experimental evidence demonstrating the viability of [001]-textured BiVO<small><sub>4</sub></small> films on polycrystalline substrates <em>via</em> laser ablation. Comprehensive analysis confirms that crystallographic orientation significantly enhances PEC performance, reinforcing the importance of texture engineering in the development of efficient photoelectrochemical materials.</p>","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":" 4","pages":" 2003-2007"},"PeriodicalIF":32.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990912","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}
Nan Wei, Lu Hao, Yaoyao Wei, Yawen Guo, Haoming Song, Jieni Chen, Zhenyu Yang, Ziqing Bian, Yetai Cheng, Wenkai Zhang, Qiaoling Chen, Yahui Liu, Wenchao Zhao, Xinjun Xu, Zhishan Bo
We designed and synthesized three chlorinated thiazole additives, namely TZ-Cl, TZ-2Cl and TZ-3Cl, which are characterized by an increasing number of chlorine atoms. Our research findings demonstrate the presence of supramolecular interactions between these additives and both polymer donors and non-fullerene acceptors. These interactions gradually intensify with an increasing number of chlorine atoms, thereby facilitating effective modulation of the crystallinity and aggregation states of the donor and acceptor molecules. Notably, the TZ-3Cl promotes a significantly refined dual-fibril interpenetrating network structure within the blend film. This enhanced active layer structure aids in extending exciton diffusion, improving exciton dissociation, and boosting charge transport, while simultaneously minimizing energy losses within the device. As a result, OSCs incorporating TZ-Cl, TZ-2Cl, and TZ-3Cl as additives in the PM6:L8-BO binary system achieved power conversion efficiencies (PCEs) of 18.3%, 18.5%, and 19.8%, respectively. Furthermore, in the PM6:BTP-eC9-4F:DM-F ternary OSC system, we attained a remarkable PCE of 20.2%. Overall, this study introduces a practical and innovative approach for designing high-efficiency OSC additives by leveraging supramolecular principles.
{"title":"Constructing a Dual-Fiber Network in High Efficiency Organic Solar Cells via Additive-Induced Supramolecular Interactions with Both Donor and Acceptor","authors":"Nan Wei, Lu Hao, Yaoyao Wei, Yawen Guo, Haoming Song, Jieni Chen, Zhenyu Yang, Ziqing Bian, Yetai Cheng, Wenkai Zhang, Qiaoling Chen, Yahui Liu, Wenchao Zhao, Xinjun Xu, Zhishan Bo","doi":"10.1039/d4ee05375c","DOIUrl":"https://doi.org/10.1039/d4ee05375c","url":null,"abstract":"We designed and synthesized three chlorinated thiazole additives, namely TZ-Cl, TZ-2Cl and TZ-3Cl, which are characterized by an increasing number of chlorine atoms. Our research findings demonstrate the presence of supramolecular interactions between these additives and both polymer donors and non-fullerene acceptors. These interactions gradually intensify with an increasing number of chlorine atoms, thereby facilitating effective modulation of the crystallinity and aggregation states of the donor and acceptor molecules. Notably, the TZ-3Cl promotes a significantly refined dual-fibril interpenetrating network structure within the blend film. This enhanced active layer structure aids in extending exciton diffusion, improving exciton dissociation, and boosting charge transport, while simultaneously minimizing energy losses within the device. As a result, OSCs incorporating TZ-Cl, TZ-2Cl, and TZ-3Cl as additives in the PM6:L8-BO binary system achieved power conversion efficiencies (PCEs) of 18.3%, 18.5%, and 19.8%, respectively. Furthermore, in the PM6:BTP-eC9-4F:DM-F ternary OSC system, we attained a remarkable PCE of 20.2%. Overall, this study introduces a practical and innovative approach for designing high-efficiency OSC additives by leveraging supramolecular principles.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"46 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990918","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}
Chenyu Xiong, Yuefeng Meng, Yao Wang, Bingyue Ling, Mengyu Ma, Hao Yan, Feiyu Kang, Dong Zhou and Baohua Li
Pursuing safer and more durable electrolytes is imperative in the relentless quest for lithium batteries with higher energy density and longer lifespan. Unlike all-solid electrolytes, prevailing quasi-solid electrolytes exhibit satisfactory conductivity and interfacial wetting. However, excessive solvent (>60 wt%) as a plasticizer triggers safety concerns and questionable electrode compatibility. Recent studies have underscored that minimizing the liquid solvent content below 20 wt% can improve battery safety and cyclability. Unfortunately, this emerging “lean-solvent” system is often, and somewhat misleadingly, categorized under all-solid electrolytes, thereby obscuring the presence of liquid components. In this Review, we provide unprecedented comprehensive insight into the unique solvation structure, interfacial behavior, and fundamental properties of lean-solvent solid electrolytes (LSEs), including lean-solvent polymer electrolytes (polymer-LSEs), lean-solvent porous electrolytes (porous-LSEs), and lean-solvent inorganic electrolytes (inorganic-LSEs). Finally, we elucidate the dominant challenges in developing safe and durable LSE-based batteries, providing a perspective for future research and technological breakthroughs.
{"title":"Lean-solvent solid electrolytes for safer and more durable lithium batteries: a crucial review†","authors":"Chenyu Xiong, Yuefeng Meng, Yao Wang, Bingyue Ling, Mengyu Ma, Hao Yan, Feiyu Kang, Dong Zhou and Baohua Li","doi":"10.1039/D4EE05293E","DOIUrl":"10.1039/D4EE05293E","url":null,"abstract":"<p >Pursuing safer and more durable electrolytes is imperative in the relentless quest for lithium batteries with higher energy density and longer lifespan. Unlike all-solid electrolytes, prevailing quasi-solid electrolytes exhibit satisfactory conductivity and interfacial wetting. However, excessive solvent (>60 wt%) as a plasticizer triggers safety concerns and questionable electrode compatibility. Recent studies have underscored that minimizing the liquid solvent content below 20 wt% can improve battery safety and cyclability. Unfortunately, this emerging “lean-solvent” system is often, and somewhat misleadingly, categorized under all-solid electrolytes, thereby obscuring the presence of liquid components. In this Review, we provide unprecedented comprehensive insight into the unique solvation structure, interfacial behavior, and fundamental properties of lean-solvent solid electrolytes (LSEs), including lean-solvent polymer electrolytes (polymer-LSEs), lean-solvent porous electrolytes (porous-LSEs), and lean-solvent inorganic electrolytes (inorganic-LSEs). Finally, we elucidate the dominant challenges in developing safe and durable LSE-based batteries, providing a perspective for future research and technological breakthroughs.</p>","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":" 4","pages":" 1612-1629"},"PeriodicalIF":32.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990913","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}
Moisture and thermal stability of flexible transparent electrodes are important for fabricating efficient large-area flexible organic photovoltaic (OPV) modules. Recently, silver nanowires (AgNWs) embedded polyvinyl alcohol (PVA) has been fabricated with excellent optoelectronic properties, mechanical flexibility and surface smoothness for efficient large-area flexible OPV modules. However, the PVA is vulnerable to moisture and heat that cause narrow processing window for large-area flexible modules. In this work, we embed AgNWs into a crosslinked PVA matrix (denoted as AgNWs-em-cPVA) that shows substantially enhanced thermal and moisture thermal stability. The AgNWs-em-cPVA could withstand temperature up to 200 °C and the moisture adsorption is as low as 1.12 ± 0.19% at a relative humidity (R.H.) of 60% and a temperature of 25 °C for 168 h. The flexible large-area OPV module achieved an efficiency of 14.78% (active area: 52.3 cm2), which is the highest for flexible large-area OPV modules on non-ITO electrodes. The flexible large-area OPV modules maintained 92.76 ± 2.5% of their initial efficiencies after continuous AM1.5 illumination with UV filter for 1,008 hours.
{"title":"Enhanced moisture and thermal stability of transparent electrodes via crosslinking for large-area flexible organic photovoltaic modules","authors":"Xin Lu, Yang Liu, Ruiyu Tian, Xinjie Liu, Yuanyuan Wang, Yinhua Zhou","doi":"10.1039/d4ee05154h","DOIUrl":"https://doi.org/10.1039/d4ee05154h","url":null,"abstract":"Moisture and thermal stability of flexible transparent electrodes are important for fabricating efficient large-area flexible organic photovoltaic (OPV) modules. Recently, silver nanowires (AgNWs) embedded polyvinyl alcohol (PVA) has been fabricated with excellent optoelectronic properties, mechanical flexibility and surface smoothness for efficient large-area flexible OPV modules. However, the PVA is vulnerable to moisture and heat that cause narrow processing window for large-area flexible modules. In this work, we embed AgNWs into a crosslinked PVA matrix (denoted as AgNWs-em-cPVA) that shows substantially enhanced thermal and moisture thermal stability. The AgNWs-em-cPVA could withstand temperature up to 200 °C and the moisture adsorption is as low as 1.12 ± 0.19% at a relative humidity (R.H.) of 60% and a temperature of 25 °C for 168 h. The flexible large-area OPV module achieved an efficiency of 14.78% (active area: 52.3 cm2), which is the highest for flexible large-area OPV modules on non-ITO electrodes. The flexible large-area OPV modules maintained 92.76 ± 2.5% of their initial efficiencies after continuous AM1.5 illumination with UV filter for 1,008 hours.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"31 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990920","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}
H2-producing zinc batteries hold promise as an electrochemical energy technology due to their unique ability to simultaneously generate electricity and hydrogen. However, their widespread adoption and commercialization have been hindered by low power density and limited hydrogen yield rates. This study tackles these challenges by developing a high-entropy alloy (HEA) catalyst (FeNiCuWRu), which is implemented by virtue of computational high-throughput screening to select appropriate element combinations from the vast conformational space of HEAs. Theoretical calculations based on machine learning potentials further identify Cu and Ni as the primary active sites for the hydrogen evolution reaction (HER). This theoretical prediction is validated by the newly developed FeNiCuWRu high-entropy alloy (HEA) electrocatalyst, which exhibits highly desirable activity for both acidic HER and alkaline OER. Inspired by this, we established an innovative rechargeable hybrid alkali/acid zinc-based battery using the FeNiCuWRu HEA as the electrocatalyst. This hybrid battery not only achieves industrial-grade hydrogen production at high current densities but also delivers a maximum power density of 537 mW cm-2, surpassing the vast majority of previously reported alkaline Zn-air batteries. A pilot battery stack capable of simultaneously generating electricity and hydrogen has been constructed, demonstrating the practical feasibility of potential applications in various scenarios.
{"title":"High-Entropy Alloy Catalysts for Advanced Hydrogen-Production Zinc-Based Batteries","authors":"zhiwen lu, Wei Sun, Pingwei Cai, Linfeng Fan, Kai Chen, Jiyuan Gao, Hao Zhang, Junxiang Chen, Zhenhai Wen","doi":"10.1039/d4ee05500d","DOIUrl":"https://doi.org/10.1039/d4ee05500d","url":null,"abstract":"H2-producing zinc batteries hold promise as an electrochemical energy technology due to their unique ability to simultaneously generate electricity and hydrogen. However, their widespread adoption and commercialization have been hindered by low power density and limited hydrogen yield rates. This study tackles these challenges by developing a high-entropy alloy (HEA) catalyst (FeNiCuWRu), which is implemented by virtue of computational high-throughput screening to select appropriate element combinations from the vast conformational space of HEAs. Theoretical calculations based on machine learning potentials further identify Cu and Ni as the primary active sites for the hydrogen evolution reaction (HER). This theoretical prediction is validated by the newly developed FeNiCuWRu high-entropy alloy (HEA) electrocatalyst, which exhibits highly desirable activity for both acidic HER and alkaline OER. Inspired by this, we established an innovative rechargeable hybrid alkali/acid zinc-based battery using the FeNiCuWRu HEA as the electrocatalyst. This hybrid battery not only achieves industrial-grade hydrogen production at high current densities but also delivers a maximum power density of 537 mW cm-2, surpassing the vast majority of previously reported alkaline Zn-air batteries. A pilot battery stack capable of simultaneously generating electricity and hydrogen has been constructed, demonstrating the practical feasibility of potential applications in various scenarios.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":"56 1","pages":""},"PeriodicalIF":32.5,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990154","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号