Pub Date : 2025-11-20DOI: 10.1016/j.jechem.2025.11.018
Zehua Liu , Caiyi Liu , Shenghe Si , Ying-Ao Liu , Xuhui Shao , Dong Liu
Photoelectrochemical (PEC) oxidation provides a promising strategy to convert solar energy into high-value-added products. The oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is of particular interest, but efficient PEC conversion remains challenging due to the limitations of selectivity, stability, and energy conversion efficiency. Although n-type silicon offers the highest theoretical photocurrent, its practical application is hindered by insufficient photovoltage and sluggish interfacial catalysis. Here, we report a NiOx/Ga2O3/n-Si photoanode integrated with a Ni(OH)2 cocatalyst for efficient HMF oxidation. The ultrathin Ga2O3 interlayer facilitates the built-in electric field, thus leading to enhanced photovoltage and enabling superior HMF oxidation performance. When coupled with a commercial Pt/C cathode, the system achieves stable, bias-free FDCA production under simulated solar illumination. This work highlights the potential of engineered silicon photoanodes for sustainable light-driven biomass valorization.
{"title":"Bias-free photoelectrochemical system for efficient 5-hydroxymethylfurfural oxidation using engineered silicon-based photoanode","authors":"Zehua Liu , Caiyi Liu , Shenghe Si , Ying-Ao Liu , Xuhui Shao , Dong Liu","doi":"10.1016/j.jechem.2025.11.018","DOIUrl":"10.1016/j.jechem.2025.11.018","url":null,"abstract":"<div><div>Photoelectrochemical (PEC) oxidation provides a promising strategy to convert solar energy into high-value-added products. The oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is of particular interest, but efficient PEC conversion remains challenging due to the limitations of selectivity, stability, and energy conversion efficiency. Although n-type silicon offers the highest theoretical photocurrent, its practical application is hindered by insufficient photovoltage and sluggish interfacial catalysis. Here, we report a NiO<em><sub>x</sub></em>/Ga<sub>2</sub>O<sub>3</sub>/n-Si photoanode integrated with a Ni(OH)<sub>2</sub> cocatalyst for efficient HMF oxidation. The ultrathin Ga<sub>2</sub>O<sub>3</sub> interlayer facilitates the built-in electric field, thus leading to enhanced photovoltage and enabling superior HMF oxidation performance. When coupled with a commercial Pt/C cathode, the system achieves stable, bias-free FDCA production under simulated solar illumination. This work highlights the potential of engineered silicon photoanodes for sustainable light-driven biomass valorization.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 25-32"},"PeriodicalIF":14.9,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692962","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-20DOI: 10.1016/j.jechem.2025.11.017
Weihuang Wang , Weiyu Wang , Junjie Lin , Zixian Cai , Nuoyan Sun , Ye Huang , Qiqiang Zhu , Qiao Zheng , Jionghua Wu , Hui Deng , Shuying Cheng
Sb2Se3 has been developing as one of the most excellent new emerging candidates for photovoltaic devices. However, the knock-on negative effect induced by the unideal quality of the CdS contacting layer largely restricts the power conversion efficiency (PCE) of Sb2Se3 thin film solar cells, especially for the vacuum-processed ones. Herein, to improve the carrier transportation of the CdS/Sb2Se3 interface and the PCE of Sb2Se3 solar cells, distinguished from the traditional chemical bath deposition (CBD) method, a spin-coated CdS film was adopted as the contacting layer for the Sb2Se3 thin film. The results revealed that the spin-coated CdS film possesses better crystallinity and conductivity than CBD-CdS films, which not only can induce better [hk1] orientated Sb2Se3 film but also contribute to the spike-like bandgap alignment of CdS/Sb2Se3 interface. Therefore, the defect level and concentration in Sb2Se3 solar cells were greatly reduced. Interestingly, the elemental migration during the post-annealing process can further optimize the heterojunction quality, the crystallinity, and vertical growth of Sb2Se3 films and covert VSe1 defects into SbSe3 defects with lower concentration, leading to the widened depletion region, decreased defect concentration, enhanced carrier lifetime, and built-in voltage for the Sb2Se3 device. The vapor transport deposition (VTD)-processed Sb2Se3 solar cells achieved a remarkable enhancement of 63.5% in PCE compared to devices based on CBD-derived CdS films, reaching a champion PCE of 8.65% with a VOC of 0.42 V, JSC of 32.33 mA/cm2, and FF of 63.68%—the highest reported PCE for Sb2Se3 solar cells based on spin-coated CdS films to date. The results shed new light on solution-processed CdS films for fabricating high-efficiency Sb2Se3 solar cells, and highlighted the critical role of self-passivation induced by elemental migration during the post-annealing process.
{"title":"Elemental migration motivating efficient carrier transportation in Sb2Se3 solar cells with spin-coated CdS film","authors":"Weihuang Wang , Weiyu Wang , Junjie Lin , Zixian Cai , Nuoyan Sun , Ye Huang , Qiqiang Zhu , Qiao Zheng , Jionghua Wu , Hui Deng , Shuying Cheng","doi":"10.1016/j.jechem.2025.11.017","DOIUrl":"10.1016/j.jechem.2025.11.017","url":null,"abstract":"<div><div>Sb<sub>2</sub>Se<sub>3</sub> has been developing as one of the most excellent new emerging candidates for photovoltaic devices. However, the knock-on negative effect induced by the unideal quality of the CdS contacting layer largely restricts the power conversion efficiency (PCE) of Sb<sub>2</sub>Se<sub>3</sub> thin film solar cells, especially for the vacuum-processed ones. Herein, to improve the carrier transportation of the CdS/Sb<sub>2</sub>Se<sub>3</sub> interface and the PCE of Sb<sub>2</sub>Se<sub>3</sub> solar cells, distinguished from the traditional chemical bath deposition (CBD) method, a spin-coated CdS film was adopted as the contacting layer for the Sb<sub>2</sub>Se<sub>3</sub> thin film. The results revealed that the spin-coated CdS film possesses better crystallinity and conductivity than CBD-CdS films, which not only can induce better [<em>hk</em>1] orientated Sb<sub>2</sub>Se<sub>3</sub> film but also contribute to the spike-like bandgap alignment of CdS/Sb<sub>2</sub>Se<sub>3</sub> interface. Therefore, the defect level and concentration in Sb<sub>2</sub>Se<sub>3</sub> solar cells were greatly reduced. Interestingly, the elemental migration during the post-annealing process can further optimize the heterojunction quality, the crystallinity, and vertical growth of Sb<sub>2</sub>Se<sub>3</sub> films and covert V<sub>Se1</sub> defects into Sb<sub>Se3</sub> defects with lower concentration, leading to the widened depletion region, decreased defect concentration, enhanced carrier lifetime, and built-in voltage for the Sb<sub>2</sub>Se<sub>3</sub> device. The vapor transport deposition (VTD)-processed Sb<sub>2</sub>Se<sub>3</sub> solar cells achieved a remarkable enhancement of 63.5% in PCE compared to devices based on CBD-derived CdS films, reaching a champion PCE of 8.65% with a <em>V</em><sub>OC</sub> of 0.42 V, <em>J</em><sub>SC</sub> of 32.33 mA/cm<sup>2</sup>, and FF of 63.68%—the highest reported PCE for Sb<sub>2</sub>Se<sub>3</sub> solar cells based on spin-coated CdS films to date. The results shed new light on solution-processed CdS films for fabricating high-efficiency Sb<sub>2</sub>Se<sub>3</sub> solar cells, and highlighted the critical role of self-passivation induced by elemental migration during the post-annealing process.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 110-120"},"PeriodicalIF":14.9,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692963","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organic semiconductors are uniquely featured with narrow optical bands that allow them to exhibit selective near-infrared absorption compared to silicon and halide perovskite analogues, making them a favorite for constructing semitransparent photovoltaics. Often, achieving a high power conversion efficiency while maintaining an excellent visible light transmittance remains a grand challenge. In semitransparent organic solar cells (ST-OSCs), the donor-dilute strategy offers a simpler means than incorporating optical coupling layers to strike a delicate balance between transparency and efficiency, yet facing the issues of exciton splitting and hole transfer. This study newly incorporates a polymer acceptor PYIT into an optimal PM6(30 wt%):L8-BO blend to form entangled dual-acceptor phases and delocalize excited states, which promote exciton dissociation and elongate exciton lifetime within the acceptor phases, thus reducing the dependence on donor/acceptor interfaces for charge separation. By further substitution with a lower-bandgap PTB7-Th donor layer and a better hole-selective layer of [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz) while introducing an antireflective layer of TeO2 to enhance device transparency, the overall light utilization efficiency reached a champion 5.63%. This contribution represents an environmentally benign, operationally scalable, and universally applicable strategy, offering practical prospects for future sustainable building-integrated photovoltaic systems.
{"title":"Delocalizing excited states of entangled dual-acceptor phases consolidates donor-dilute semitransparent organic solar cells","authors":"Xiaoxiao Zhang , Zhiyuan Wu , Jiaqi Xie , Weihua Lin , Kaibo Zheng , Ziqi Liang","doi":"10.1016/j.jechem.2025.11.015","DOIUrl":"10.1016/j.jechem.2025.11.015","url":null,"abstract":"<div><div>Organic semiconductors are uniquely featured with narrow optical bands that allow them to exhibit selective near-infrared absorption compared to silicon and halide perovskite analogues, making them a favorite for constructing semitransparent photovoltaics. Often, achieving a high power conversion efficiency while maintaining an excellent visible light transmittance remains a grand challenge. In semitransparent organic solar cells (ST-OSCs), the donor-dilute strategy offers a simpler means than incorporating optical coupling layers to strike a delicate balance between transparency and efficiency, yet facing the issues of exciton splitting and hole transfer. This study newly incorporates a polymer acceptor PYIT into an optimal PM6(30 wt%):L8-BO blend to form entangled dual-acceptor phases and delocalize excited states, which promote exciton dissociation and elongate exciton lifetime within the acceptor phases, thus reducing the dependence on donor/acceptor interfaces for charge separation. By further substitution with a lower-bandgap PTB7-Th donor layer and a better hole-selective layer of [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz) while introducing an antireflective layer of TeO<sub>2</sub> to enhance device transparency, the overall light utilization efficiency reached a champion 5.63%. This contribution represents an environmentally benign, operationally scalable, and universally applicable strategy, offering practical prospects for future sustainable building-integrated photovoltaic systems.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 65-75"},"PeriodicalIF":14.9,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692912","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-19DOI: 10.1016/j.jechem.2025.11.016
Ran Wang , Yingxin Wang , Kunpeng Yang , Jiahao Li , Yuxuan Jiang , Huan Pang
The electrocatalytic oxidation of biomass-derived alcohols and aldehydes represents a sustainable route for converting abundant renewable feedstocks into value-added chemicals while simultaneously generating hydrogen or fuels through paired reduction reactions. This review summarizes recent progress in reaction mechanisms, catalyst design strategies, and coupled system integration for these electrooxidation processes. Mechanistic analyses distinguishing direct and indirect oxidation pathways are discussed, with emphasis on key intermediates and rate-determining steps. Advances in strategies such as alloying, defect engineering, single-atom catalysis (SACs), and heterointerface construction are highlighted to reveal how electronic structure modulation governs adsorption behaviors, selectivity, and stability. The discussion further extends to coupled anodic-cathodic systems, such as those integrated with hydrogen evolution reaction (HER), CO2 reduction reaction (CO2RR), and nitrate reduction reaction (NO3RR), enabling energy-efficient co-production of chemicals and fuels. Correlations established between in situ/operando characterizations and theoretical modeling provide a unified mechanism-structure-activity framework that links catalytic dynamics with product selectivity. Remaining challenges and future opportunities are identified, particularly the development of scalable, earth-abundant catalysts and techno-economic analyses to bridge the gap between laboratory research and industrial application. Overall, this review delivers conceptual and practical insights toward the design of efficient, low-carbon electrosynthetic platforms based on alcohol and aldehyde oxidation.
{"title":"Electrocatalytic valorization of biomass-derived alcohols and aldehydes: Mechanistic insights and innovative catalyst design","authors":"Ran Wang , Yingxin Wang , Kunpeng Yang , Jiahao Li , Yuxuan Jiang , Huan Pang","doi":"10.1016/j.jechem.2025.11.016","DOIUrl":"10.1016/j.jechem.2025.11.016","url":null,"abstract":"<div><div>The electrocatalytic oxidation of biomass-derived alcohols and aldehydes represents a sustainable route for converting abundant renewable feedstocks into value-added chemicals while simultaneously generating hydrogen or fuels through paired reduction reactions. This review summarizes recent progress in reaction mechanisms, catalyst design strategies, and coupled system integration for these electrooxidation processes. Mechanistic analyses distinguishing direct and indirect oxidation pathways are discussed, with emphasis on key intermediates and rate-determining steps. Advances in strategies such as alloying, defect engineering, single-atom catalysis (SACs), and heterointerface construction are highlighted to reveal how electronic structure modulation governs adsorption behaviors, selectivity, and stability. The discussion further extends to coupled anodic-cathodic systems, such as those integrated with hydrogen evolution reaction (HER), CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR), and nitrate reduction reaction (NO<sub>3</sub>RR), enabling energy-efficient co-production of chemicals and fuels. Correlations established between in situ/operando characterizations and theoretical modeling provide a unified mechanism-structure-activity framework that links catalytic dynamics with product selectivity. Remaining challenges and future opportunities are identified, particularly the development of scalable, earth-abundant catalysts and techno-economic analyses to bridge the gap between laboratory research and industrial application. Overall, this review delivers conceptual and practical insights toward the design of efficient, low-carbon electrosynthetic platforms based on alcohol and aldehyde oxidation.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 85-109"},"PeriodicalIF":14.9,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145749657","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-19DOI: 10.1016/j.jechem.2025.11.013
Jun Li , Haotian Tan , Jingjing Jia , Chao Wang , Weichang Hao , Xiao Yan , Wenping Si , Yunrui Tian , Feng Hou , Lichang Yin , Ji Liang
Electrocatalytic ammonia oxidation reaction (AOR) represents a sustainable synthesis approach for valuable nitrogen-containing compounds like nitrites and nitrates. However, the numerous AOR intermediates often complicate the precise regulation of target intermediate adsorption, hindering the efficient and selective nitrate/nitrite production. We herein present a NiCu-BDC MOF with tunable AOR product selectivity, which undergoes a controllable in situ reconstruction into Cu-β-NiOOH at 1.7 V vs. RHE, enabling the shift of the reaction pathway from NH4+-to-NO2− to NH4+-to-NO3−. The unique restructuring behavior of this material, combined with its dense active sites, enables highly selective production of nitrites and nitrates (94.9% NO2− selectivity at 1.60 V vs. RHE and 92.6% NO3− selectivity at 1.95 V vs. RHE). Theoretical simulations reveal that the Cu incorporation in NiCu-BDC modulates the electronic configuration of Ni sites, facilitating moderate adsorption of key *NO and *NOOH intermediates, thus promoting efficient nitrite generation at low potentials. At higher potentials, NiCu-BDC undergoes reconstruction to Cu-β-NiOOH, stabilizing the conversion of *NO2 to *NO2OH, making nitrate formation thermodynamically favorable and a rapid selectivity shift. This potential-driven selectivity control not only provides a new strategy for efficient nitrites/nitrates synthesis by simply adjusting applied potentials but also provides fundamental insights into regulating selectivity in multi-product electrochemical reactions.
电催化氨氧化反应（AOR）是一种可持续合成亚硝酸盐和硝酸盐等有价值的含氮化合物的方法。然而，AOR中间体数量众多，往往使目标中间体吸附的精确调控复杂化，阻碍了高效、选择性地生产硝酸盐/亚硝酸盐。在此，我们提出了一种具有可调AOR产物选择性的NiCu-BDC MOF，该MOF在1.7 V vs. RHE下可控地原位重构为Cu-β-NiOOH，从而使反应途径从NH4+到no2−转变为NH4+到no3−。这种材料独特的重组行为，结合其致密的活性位点，使亚硝酸盐和硝酸盐的生产具有高度选择性（在1.60 V时NO2 -选择性为94.9%，在1.95 V时NO3 -选择性为92.6%）。理论模拟表明，Cu在NiCu-BDC中的掺入调节了Ni位点的电子构型，促进了关键的*NO和*NOOH中间体的适度吸附，从而促进了低电位下亚硝酸盐的高效生成。在高电位下，NiCu-BDC重构为Cu-β-NiOOH，稳定了*NO2到*NO2OH的转化，使得硝酸盐生成热力学有利，选择性快速转移。这种由电位驱动的选择性控制不仅提供了通过调节应用电位来高效合成亚硝酸盐/硝酸盐的新策略，而且为多产物电化学反应的选择性调节提供了基础性的见解。
{"title":"Potential-driven precise selectivity tuning for ammonia electrooxidation over NiCu-BDC metal organic framework","authors":"Jun Li , Haotian Tan , Jingjing Jia , Chao Wang , Weichang Hao , Xiao Yan , Wenping Si , Yunrui Tian , Feng Hou , Lichang Yin , Ji Liang","doi":"10.1016/j.jechem.2025.11.013","DOIUrl":"10.1016/j.jechem.2025.11.013","url":null,"abstract":"<div><div>Electrocatalytic ammonia oxidation reaction (AOR) represents a sustainable synthesis approach for valuable nitrogen-containing compounds like nitrites and nitrates. However, the numerous AOR intermediates often complicate the precise regulation of target intermediate adsorption, hindering the efficient and selective nitrate/nitrite production. We herein present a NiCu-BDC MOF with tunable AOR product selectivity, which undergoes a controllable in situ reconstruction into Cu-β-NiOOH at 1.7 V vs. RHE, enabling the shift of the reaction pathway from NH<sub>4</sub><sup>+</sup>-to-NO<sub>2</sub><sup>−</sup> to NH<sub>4</sub><sup>+</sup>-to-NO<sub>3</sub><sup>−</sup>. The unique restructuring behavior of this material, combined with its dense active sites, enables highly selective production of nitrites and nitrates (94.9% NO<sub>2</sub><sup>−</sup> selectivity at 1.60 V vs. RHE and 92.6% NO<sub>3</sub><sup>−</sup> selectivity at 1.95 V vs. RHE). Theoretical simulations reveal that the Cu incorporation in NiCu-BDC modulates the electronic configuration of Ni sites, facilitating moderate adsorption of key *NO and *NOOH intermediates, thus promoting efficient nitrite generation at low potentials. At higher potentials, NiCu-BDC undergoes reconstruction to Cu-β-NiOOH, stabilizing the conversion of *NO<sub>2</sub> to *NO<sub>2</sub>OH, making nitrate formation thermodynamically favorable and a rapid selectivity shift. This potential-driven selectivity control not only provides a new strategy for efficient nitrites/nitrates synthesis by simply adjusting applied potentials but also provides fundamental insights into regulating selectivity in multi-product electrochemical reactions.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 54-64"},"PeriodicalIF":14.9,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692914","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-19DOI: 10.1016/j.jechem.2025.11.014
Liu Yang , Yisha Wang , Haoteng Sun , Mingtong Zhang , Tianxiang Yang , Hanqi Zhang , Jixin Zhu
Lithium metal batteries (LMBs) offer remarkable energy density and theoretical capacity, positioning them as critical enablers for next-generation electric vehicles and high-power devices. However, persistent commercialization hurdles arise from uncontrolled lithium nucleation dynamics that trigger dendritic architectures and interfacial incompatibility, which degrade cycling performance and escalate safety risks. Here, an electrospinning method was proposed to fabricate flame-retardant polymer membranes with locking-desolvating kinetics for safe LMBs. The prepared electrode/electrolyte interface demonstrates electrolyte-locking capability and facilitates lithium ion desolvation, contributing to inhibiting the decomposition of electrolyte and improving the efficiency of lithium ion transport. Symmetrical cells and full cells exhibit superior cycling stability and specific discharge capacity, attributed to the polymer membranes that can effectively suppress lithium dendrite formation and minimize dead lithium accumulation. Notably, the incorporation of flame-retardant molecules within the polymer matrix significantly enhances the thermal stability of composite anodes and promotes the safety of LMBs. The methodology can be extended to explore other safe and cost-effective polymers, advancing LMBs towards practical energy storage applications.
{"title":"Manipulation of electrolyte locking-desolvating kinetics enabling scalable flame-retardant polymer protector for thermally safe lithium metal batteries","authors":"Liu Yang , Yisha Wang , Haoteng Sun , Mingtong Zhang , Tianxiang Yang , Hanqi Zhang , Jixin Zhu","doi":"10.1016/j.jechem.2025.11.014","DOIUrl":"10.1016/j.jechem.2025.11.014","url":null,"abstract":"<div><div>Lithium metal batteries (LMBs) offer remarkable energy density and theoretical capacity, positioning them as critical enablers for next-generation electric vehicles and high-power devices. However, persistent commercialization hurdles arise from uncontrolled lithium nucleation dynamics that trigger dendritic architectures and interfacial incompatibility, which degrade cycling performance and escalate safety risks. Here, an electrospinning method was proposed to fabricate flame-retardant polymer membranes with locking-desolvating kinetics for safe LMBs. The prepared electrode/electrolyte interface demonstrates electrolyte-locking capability and facilitates lithium ion desolvation, contributing to inhibiting the decomposition of electrolyte and improving the efficiency of lithium ion transport. Symmetrical cells and full cells exhibit superior cycling stability and specific discharge capacity, attributed to the polymer membranes that can effectively suppress lithium dendrite formation and minimize dead lithium accumulation. Notably, the incorporation of flame-retardant molecules within the polymer matrix significantly enhances the thermal stability of composite anodes and promotes the safety of LMBs. The methodology can be extended to explore other safe and cost-effective polymers, advancing LMBs towards practical energy storage applications.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 15-24"},"PeriodicalIF":14.9,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692965","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-17DOI: 10.1016/j.jechem.2025.11.009
Sangyeon Won , Junhyuk Ji , Gwan Hyeon Park , Subin Kim , Song Kyu Kang , Minho Kim , Junbeom Maeng , Won Bae Kim
Practical application of lithium-sulfur (Li-S) batteries is hindered by the migration of lithium polysulfides (LiPSs), sluggish conversion kinetics, and anode instability. In these regards, with a novel strategy focusing on the selective elevation of d-orbitals, Mn/Fe dual-atom catalysts (MnFe DACs) embedded in N-doped carbon frameworks are designed. Theoretical calculations reveal that energy levels of dz2, dzx, and dyz orbitals participating in d-p hybridization are elevated closer to the Fermi level at both Mn and Fe sites, thereby reducing orbital occupancy in antibonding states. Consequently, these electronic features via the selective d-orbital elevation enable enhanced adsorption strength toward intermediate LiPSs and accelerate redox reaction during cell operation. Also, the MnFe DAC improves anode stability by regulating Li-ion flux with its lithiophilic active sites. Specifically, the cell equipped with MnFe DAC-modified separator maintains a capacity of 758.4 mAh g−1 after 400 cycles at 0.5 C. Notably, the cell demonstrates a high initial capacity of 822.7 mAh g−1 with only 0.047% decay rate over 1000 cycles at 1 C. Even under high sulfur-loading (5.0 mg cm−2) and low electrolyte-to-sulfur (E/S) ratio (6 μL mg−1), a high initial areal capacity of 4.94 mAh cm−2 with 92.5% retention after 50 cycles at 0.1 C is achieved. This study provides guidelines on selective modulation of d-orbitals in DACs for high-performance Li-S batteries.
锂硫（Li-S）电池的实际应用受到锂多硫化物（LiPSs）迁移、转化动力学缓慢和阳极不稳定的阻碍。在这方面，采用一种新的策略，重点关注d轨道的选择性提升，设计了嵌入n掺杂碳框架的Mn/Fe双原子催化剂（MnFe DACs）。理论计算表明，参与d-p杂化的dz2、dzx和dyz轨道在Mn和Fe位置的能级都提高到接近费米能级，从而减少了反键态的轨道占用。因此，通过选择性的d轨道提升，这些电子特征增强了对中间LiPSs的吸附强度，并加速了细胞运行过程中的氧化还原反应。此外，MnFe DAC通过其亲锂活性位点调节锂离子通量来提高阳极稳定性。具体来说,细胞配备MnFe DAC-modified分离器维护一个容量为758.4 mAh g−1 400年以后周期在0.5 C。值得注意的是,细胞表明高初始容量的822.7 mAh克−1只有0.047%的衰变率超过1000周期在1 C,即使在高sulfur-loading(5.0毫克厘米−2)和低electrolyte-to-sulfur (E / S)比率(6μL mg−1),高初始区域容量的4.94 mAh厘米−2 92.5%保留后50周期在0.1摄氏度。本研究为高性能锂硫电池dac中d轨道的选择性调制提供了指导。
{"title":"Selective elevation of d-orbital energies by Mn/Fe dual-atom catalyst accelerating sulfur redox kinetics in lithium-sulfur batteries","authors":"Sangyeon Won , Junhyuk Ji , Gwan Hyeon Park , Subin Kim , Song Kyu Kang , Minho Kim , Junbeom Maeng , Won Bae Kim","doi":"10.1016/j.jechem.2025.11.009","DOIUrl":"10.1016/j.jechem.2025.11.009","url":null,"abstract":"<div><div>Practical application of lithium-sulfur (Li-S) batteries is hindered by the migration of lithium polysulfides (LiPSs), sluggish conversion kinetics, and anode instability. In these regards, with a novel strategy focusing on the selective elevation of <em>d</em>-orbitals, Mn/Fe dual-atom catalysts (MnFe DACs) embedded in N-doped carbon frameworks are designed. Theoretical calculations reveal that energy levels of <em>d</em><sub>z</sub><sub>2</sub>, <em>d</em><sub>zx</sub>, and <em>d</em><sub>yz</sub> orbitals participating in <em>d</em>-<em>p</em> hybridization are elevated closer to the Fermi level at both Mn and Fe sites, thereby reducing orbital occupancy in antibonding states. Consequently, these electronic features via the selective <em>d</em>-orbital elevation enable enhanced adsorption strength toward intermediate LiPSs and accelerate redox reaction during cell operation. Also, the MnFe DAC improves anode stability by regulating Li-ion flux with its lithiophilic active sites. Specifically, the cell equipped with MnFe DAC-modified separator maintains a capacity of 758.4 mAh g<sup>−1</sup> after 400 cycles at 0.5 C. Notably, the cell demonstrates a high initial capacity of 822.7 mAh g<sup>−1</sup> with only 0.047% decay rate over 1000 cycles at 1 C. Even under high sulfur-loading (5.0 mg cm<sup>−2</sup>) and low electrolyte-to-sulfur (E/S) ratio (6 μL mg<sup>−1</sup>), a high initial areal capacity of 4.94 mAh cm<sup>−2</sup> with 92.5% retention after 50 cycles at 0.1 C is achieved. This study provides guidelines on selective modulation of <em>d</em>-orbitals in DACs for high-performance Li-S batteries.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"114 ","pages":"Pages 906-918"},"PeriodicalIF":14.9,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-17DOI: 10.1016/j.jechem.2025.10.060
Kun Liu , Rui Wang , Zhengjun Tu , Liang Zhao , Fengnian Wang , Yinshi Li
Forced convection between the reactants and the catalyst in solar-driven hydrogen production systems increases heat loss, thereby constraining the hydrogen evolution rate. To address these challenges, we proposed a multi-interface-induced radiant heat activation strategy that utilizes photothermally generated radiant heat to pre-activate reactants. This process enables the rapid interfacial vaporization of reactants and significantly enhances mass transfer. The resulting multi-interface heating system (MIH) developed achieves gradient heat utilization, combining broadband solar absorption with low thermal emittance, while ensuring precise spatiotemporal coordination between reactant supply and catalytic activity. As a result, a high hydrogen evolution rate of 242 mmol g−1 h−1 is achieved under 1 sun illumination at room temperature, using formic acid (HCOOH) as a liquid hydrogen carrier. This work demonstrates an efficient, low-energy pathway for hydrogen generation and offers a promising platform for practical solar-to-hydrogen conversion under ambient conditions.
{"title":"Multi-interface-induced radiant heat activation strategy: achieving solar-driven hydrogen production from formic acid","authors":"Kun Liu , Rui Wang , Zhengjun Tu , Liang Zhao , Fengnian Wang , Yinshi Li","doi":"10.1016/j.jechem.2025.10.060","DOIUrl":"10.1016/j.jechem.2025.10.060","url":null,"abstract":"<div><div>Forced convection between the reactants and the catalyst in solar-driven hydrogen production systems increases heat loss, thereby constraining the hydrogen evolution rate. To address these challenges, we proposed a multi-interface-induced radiant heat activation strategy that utilizes photothermally generated radiant heat to pre-activate reactants. This process enables the rapid interfacial vaporization of reactants and significantly enhances mass transfer. The resulting multi-interface heating system (MIH) developed achieves gradient heat utilization, combining broadband solar absorption with low thermal emittance, while ensuring precise spatiotemporal coordination between reactant supply and catalytic activity. As a result, a high hydrogen evolution rate of 242 mmol g<sup>−1</sup> h<sup>−1</sup> is achieved under 1 sun illumination at room temperature, using formic acid (HCOOH) as a liquid hydrogen carrier. This work demonstrates an efficient, low-energy pathway for hydrogen generation and offers a promising platform for practical solar-to-hydrogen conversion under ambient conditions.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 76-84"},"PeriodicalIF":14.9,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692961","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-17DOI: 10.1016/j.jechem.2025.10.061
Tianshuang Qi , Kai Xiong , Xiong Zhang , Honggang Ding , Haiping Yang
To address the challenges of weak cycling stability and low capacity in hard carbon (HC), elucidating the structure-performance relationship between their microstructure and potassium-ion battery (PIB) performance is crucial. To this end, this study developed an interpretable machine learning workflow that identified optimal machine learning models for six key electrochemical performance metrics, including cycling performance, through multi-model comparison. All performance prediction models demonstrated excellent generalization capability, with the AdaBoost model achieving the highest test set coefficient of determination (R2) of 0.819 for the cyclic factor, while all models maintain root mean square error (RMSE) below 8 %. By integrating advanced interpretable ML methods such as Shapley additive explanations (SHAP) and accumulated local effects (ALE), the study systematically identified critical thresholds and synergistic interaction ranges where key structural features exert positive effects. Taking the cyclic factor as an example, the results reveal that optimal synergistic enhancement of cycling performance is achieved when degree of graphitization ranges between 100 % and 200 %, S content exceeds 7 at%, and the number of graphene layers exceeds 3. The data-driven paradigm of “structural features-performance output-synergistic thresholds” established in this work provides a reliable theoretical foundation and experimentally verifiable optimization pathway for the targeted design of high-performance HC anodes.
{"title":"Machine learning predicts microstructure impact on discharge performance in hard carbon anodes for K-ion batteries","authors":"Tianshuang Qi , Kai Xiong , Xiong Zhang , Honggang Ding , Haiping Yang","doi":"10.1016/j.jechem.2025.10.061","DOIUrl":"10.1016/j.jechem.2025.10.061","url":null,"abstract":"<div><div>To address the challenges of weak cycling stability and low capacity in hard carbon (HC), elucidating the structure-performance relationship between their microstructure and potassium-ion battery (PIB) performance is crucial. To this end, this study developed an interpretable machine learning workflow that identified optimal machine learning models for six key electrochemical performance metrics, including cycling performance, through multi-model comparison. All performance prediction models demonstrated excellent generalization capability, with the AdaBoost model achieving the highest test set coefficient of determination (R<sup>2</sup>) of 0.819 for the cyclic factor, while all models maintain root mean square error (RMSE) below 8 %. By integrating advanced interpretable ML methods such as Shapley additive explanations (SHAP) and accumulated local effects (ALE), the study systematically identified critical thresholds and synergistic interaction ranges where key structural features exert positive effects. Taking the cyclic factor as an example, the results reveal that optimal synergistic enhancement of cycling performance is achieved when degree of graphitization ranges between 100 % and 200 %, S content exceeds 7 at%, and the number of graphene layers exceeds 3. The data-driven paradigm of “structural features-performance output-synergistic thresholds” established in this work provides a reliable theoretical foundation and experimentally verifiable optimization pathway for the targeted design of high-performance HC anodes.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 282-297"},"PeriodicalIF":14.9,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145798330","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-17DOI: 10.1016/j.jechem.2025.11.010
Jiyu Cai , Zhenzhen Yang , Yingying Xie , Matthew Li , Guanyi Wang , Wenquan Lu , Yuzi Liu , Xiangbo Meng , Gabriel M. Veith , Hao Jia , Wu Xu , Guiliang Xu , Zonghai Chen
Silicon (Si) is a promising high-capacity anode in lithium-ion batteries but suffers from chronic chemical degradation and capacity fading during calendar aging, greatly hindering its automobile applications. Electrolyte engineering currently relies on conventional evaluation criteria of reducing coulombic consumption, which implicitly presume its equivalence to irreversible capacity loss and complicates battery development. We introduce the detrimental ratio ρ to quantify the fraction of parasitic species that permanently degrades active material. This metric is independent and crucially complements total coulombic consumption for accurate performance evaluation. We systematically investigate multiple electrolyte formulations using high-precision leakage current measurements, open-circuit-voltage experiments, and post-mortem characterizations. Although some electrolytes exhibit similarly low coulombic consumption, they diverge significantly in capacity retention and ρ. Especially, dimethyl-carbonate-based localized-high concentration electrolyte can synergically achieve low coulombic consumption and detrimental ratio ρ during calendar aging, owing to its chemically inert and structurally resilient solid-electrolyte interface with minimal isolated Si material. By contrast, increasing fluoroethylene carbonate (FEC) additive content suppresses electrolyte breakdown but suffers aggravated chemical degradation of more LixSi isolation for irreversible capacity loss with a rising ρ. This study critically reveals that the chemistry-characteristic detrimental ratio ρ establishes physically informed performance evaluation to pave the way for accelerating battery development.
{"title":"The detrimental ratio (ρ): A critical metric complementing coulombic loss for long calendar-life silicon-based lithium-ion batteries","authors":"Jiyu Cai , Zhenzhen Yang , Yingying Xie , Matthew Li , Guanyi Wang , Wenquan Lu , Yuzi Liu , Xiangbo Meng , Gabriel M. Veith , Hao Jia , Wu Xu , Guiliang Xu , Zonghai Chen","doi":"10.1016/j.jechem.2025.11.010","DOIUrl":"10.1016/j.jechem.2025.11.010","url":null,"abstract":"<div><div>Silicon (Si) is a promising high-capacity anode in lithium-ion batteries but suffers from chronic chemical degradation and capacity fading during calendar aging, greatly hindering its automobile applications. Electrolyte engineering currently relies on conventional evaluation criteria of reducing coulombic consumption, which implicitly presume its equivalence to irreversible capacity loss and complicates battery development. We introduce the detrimental ratio <em>ρ</em> to quantify the fraction of parasitic species that permanently degrades active material. This metric is independent and crucially complements total coulombic consumption for accurate performance evaluation. We systematically investigate multiple electrolyte formulations using high-precision leakage current measurements, open-circuit-voltage experiments, and post-mortem characterizations. Although some electrolytes exhibit similarly low coulombic consumption, they diverge significantly in capacity retention and <em>ρ</em>. Especially, dimethyl-carbonate-based localized-high concentration electrolyte can synergically achieve low coulombic consumption and detrimental ratio <em>ρ</em> during calendar aging, owing to its chemically inert and structurally resilient solid-electrolyte interface with minimal isolated Si material. By contrast, increasing fluoroethylene carbonate (FEC) additive content suppresses electrolyte breakdown but suffers aggravated chemical degradation of more Li<em><sub>x</sub></em>Si isolation for irreversible capacity loss with a rising <em>ρ</em>. This study critically reveals that the chemistry-characteristic detrimental ratio <em>ρ</em> establishes physically informed performance evaluation to pave the way for accelerating battery development.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"114 ","pages":"Pages 955-963"},"PeriodicalIF":14.9,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786722","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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