Jangwhan Seok, Chanyou Chung, Hyunbeom Lee, Subin Ahn, Seongeun Lee, Sangbin Park, Sunhyun Hwang, Jaeyoung Kim, Jeonghyun Seo, Sungwoo Noh, Juyeong Seong, Sangheon Lee, Won‐Sub Yoon
All‐solid‐state batteries (ASSBs) promise safer energy storage and the potential to outperform current lithium‐ion batteries. Ni‐rich cathodes deliver high energy density, whereas sulfide solid electrolytes offer exceptional Li + conductivity and inherent mechanical compliance, making their combination particularly attractive. Yet their capacity fades rapidly because (electro)chemical and mechanical degradation occur concurrently within the cathode. Here, we propose an approach to decouple these two factors in LiNi 0.8 Co 0.1 Mn 0.1 O 2 |Li 6 PS 5 Cl 0.5 Br 0.5 |Li metal cells by monitoring the state‐of‐charge window. Uncoated cathodes experience capacity fading primarily due to (electro)chemical degradation: interfacial reactions form resistive interphases consisting of NiO‐like rock salt, SO x , PO x , and related species that hinder Li + extraction, resulting in pronounced charge fading. A conformal LiNbO 3 coating on the cathode surface suppresses interfacial reactions, significantly mitigating charge fading but revealing dominant discharge fading arising from mechanical degradation, such as particle cracking and interfacial delamination. While the protective coating stabilizes the interface and improves initial performance, the increased capacity intensifies electrode volume changes, underscoring the need for integrated electro‐chemo‐mechanical design strategies. Evaluating charge and discharge fading outlines the interplay between (electro)chemical and mechanical degradation and offers a new diagnostic framework to guide the development of more durable, high‐energy‐density ASSBs.
{"title":"Decoupling Chemical and Mechanical Contributions to Capacity Fading in Ni‐Rich Cathodes for Sulfide‐Based All‐Solid‐State Batteries","authors":"Jangwhan Seok, Chanyou Chung, Hyunbeom Lee, Subin Ahn, Seongeun Lee, Sangbin Park, Sunhyun Hwang, Jaeyoung Kim, Jeonghyun Seo, Sungwoo Noh, Juyeong Seong, Sangheon Lee, Won‐Sub Yoon","doi":"10.1002/aenm.202506351","DOIUrl":"https://doi.org/10.1002/aenm.202506351","url":null,"abstract":"All‐solid‐state batteries (ASSBs) promise safer energy storage and the potential to outperform current lithium‐ion batteries. Ni‐rich cathodes deliver high energy density, whereas sulfide solid electrolytes offer exceptional Li <jats:sup>+</jats:sup> conductivity and inherent mechanical compliance, making their combination particularly attractive. Yet their capacity fades rapidly because (electro)chemical and mechanical degradation occur concurrently within the cathode. Here, we propose an approach to decouple these two factors in LiNi <jats:sub>0.8</jats:sub> Co <jats:sub>0.1</jats:sub> Mn <jats:sub>0.1</jats:sub> O <jats:sub>2</jats:sub> |Li <jats:sub>6</jats:sub> PS <jats:sub>5</jats:sub> Cl <jats:sub>0.5</jats:sub> Br <jats:sub>0.5</jats:sub> |Li metal cells by monitoring the state‐of‐charge window. Uncoated cathodes experience capacity fading primarily due to (electro)chemical degradation: interfacial reactions form resistive interphases consisting of NiO‐like rock salt, SO <jats:italic> <jats:sub>x</jats:sub> </jats:italic> , PO <jats:italic> <jats:sub>x</jats:sub> </jats:italic> , and related species that hinder Li <jats:sup>+</jats:sup> extraction, resulting in pronounced charge fading. A conformal LiNbO <jats:sub>3</jats:sub> coating on the cathode surface suppresses interfacial reactions, significantly mitigating charge fading but revealing dominant discharge fading arising from mechanical degradation, such as particle cracking and interfacial delamination. While the protective coating stabilizes the interface and improves initial performance, the increased capacity intensifies electrode volume changes, underscoring the need for integrated electro‐chemo‐mechanical design strategies. Evaluating charge and discharge fading outlines the interplay between (electro)chemical and mechanical degradation and offers a new diagnostic framework to guide the development of more durable, high‐energy‐density ASSBs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"30 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056007","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}
Jin-Hao Zhang, Yu Zhang, Zhi-Yuan Gu, Jin-Xiu Chen, Chen-Hao Yu, Ayaulym Belgibayeva, Gulnur Kalimuldina, Xin-Bing Cheng, Long Kong
Sluggish lithium (Li) de-coordination kinetics on the interface hinder the development of high-energy and low-temperature Li-metal batteries (LMBs). In principle, weakly coordinated solvents and anions contribute to improved low-temperature battery performances due to low Li de-solvation and de-anion energy barrier on the anode interface. However, extensive works employ strategies that go against the above-mentioned principle, commonly using strong coordination strength solvents and anions to facilitate rate and cyclic performances. The in-depth understanding of this refined Li coordination structure that accelerates Li redox kinetics remains rather elusive. To bridge such gap between theoretical implication and realistic practice of solvent and salt selection, this work examines a model electrolyte involving the strong coordination strength salt (lithium nitrate, LiNO3) and solvent (triethyl phosphate, TEP) to decipher how electron transfer occurred in the cluster solvation impacts Li charge density and dictates Li transport kinetics. One of the critical interpretations is that the electron-donating nature of LiNO3 reduces the positive charge of Li+, which dampens the interaction between Li+ and TEP ligands. Another key finding is that clustering [LiNO3–Li+–TEP] intensifies the interfacial charge exchange to hasten Li transport kinetics, since anion-participated cluster solvates exhibit high effective charges than that of anion-lean Li solvates. This work updates the understanding of why the cluster solvates benefits Li de-coordination kinetics and hopes to finger out new principles to select Li salts and solvents for better low-temperature Li metal batteries.
{"title":"Dampening Lithium Charge Density by Clustering Solvents and Anions to Tame Lithium De-Coordination Energy for Low-Temperature Lithium-Metal Batteries","authors":"Jin-Hao Zhang, Yu Zhang, Zhi-Yuan Gu, Jin-Xiu Chen, Chen-Hao Yu, Ayaulym Belgibayeva, Gulnur Kalimuldina, Xin-Bing Cheng, Long Kong","doi":"10.1002/aenm.202505551","DOIUrl":"https://doi.org/10.1002/aenm.202505551","url":null,"abstract":"Sluggish lithium (Li) de-coordination kinetics on the interface hinder the development of high-energy and low-temperature Li-metal batteries (LMBs). In principle, weakly coordinated solvents and anions contribute to improved low-temperature battery performances due to low Li de-solvation and de-anion energy barrier on the anode interface. However, extensive works employ strategies that go against the above-mentioned principle, commonly using strong coordination strength solvents and anions to facilitate rate and cyclic performances. The in-depth understanding of this refined Li coordination structure that accelerates Li redox kinetics remains rather elusive. To bridge such gap between theoretical implication and realistic practice of solvent and salt selection, this work examines a model electrolyte involving the strong coordination strength salt (lithium nitrate, LiNO<sub>3</sub>) and solvent (triethyl phosphate, TEP) to decipher how electron transfer occurred in the cluster solvation impacts Li charge density and dictates Li transport kinetics. One of the critical interpretations is that the electron-donating nature of LiNO<sub>3</sub> reduces the positive charge of Li<sup>+</sup>, which dampens the interaction between Li<sup>+</sup> and TEP ligands. Another key finding is that clustering [LiNO<sub>3</sub>–Li<sup>+</sup>–TEP] intensifies the interfacial charge exchange to hasten Li transport kinetics, since anion-participated cluster solvates exhibit high effective charges than that of anion-lean Li solvates. This work updates the understanding of why the cluster solvates benefits Li de-coordination kinetics and hopes to finger out new principles to select Li salts and solvents for better low-temperature Li metal batteries.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"41 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048864","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}
Franz Jacobi, Rudolf Frank Baumgart, Robert Leiter, Marius Hermesdorf, Sri Rezeki, Alexander Kemmesies, Christof Neumann, Andrey Turchanin, Christopher Schlesiger, Simon Fleischmann, Desirée Leistenschneider
Alkaline zinc‐air batteries (ZABs) have attracted interest in recent years for their high theoretical energy density and use of low‐cost, abundant zinc metal as the anode. In order to overcome the activation energy barrier of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), noble metals are commonly used. Within this work, transition metal‐functionalized Poly(heptazine imide)s (PHIs) are studied as an alternative and more abundant electrocatalyst, as they offer the homogenous immobilization of metals within their ordered structure. Introducing Fe and Ni into the PHI network enables the formation of single and mixed transition metal PHIs, which show reduced overpotentials for ORR and OER. The formation of Ni single atoms even induces outstanding catalytic activity for the OER during charging of ZAB full cells with performance comparable to that of RuO 2 . Furthermore, full cell tests show excellent stability over the course of 250 discharge‐charge cycles, making it a promising system for sustainable energy storage. This work paves the way for the molecular design of a novel material class as an electrocatalyst for ZAB.
{"title":"Influence of Metal Species and Content of Fe‐Ni‐Poly(heptazine imides) on their Properties as Electrocatalysts for Zinc‐Air Batteries","authors":"Franz Jacobi, Rudolf Frank Baumgart, Robert Leiter, Marius Hermesdorf, Sri Rezeki, Alexander Kemmesies, Christof Neumann, Andrey Turchanin, Christopher Schlesiger, Simon Fleischmann, Desirée Leistenschneider","doi":"10.1002/aenm.202506308","DOIUrl":"https://doi.org/10.1002/aenm.202506308","url":null,"abstract":"Alkaline zinc‐air batteries (ZABs) have attracted interest in recent years for their high theoretical energy density and use of low‐cost, abundant zinc metal as the anode. In order to overcome the activation energy barrier of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), noble metals are commonly used. Within this work, transition metal‐functionalized Poly(heptazine imide)s (PHIs) are studied as an alternative and more abundant electrocatalyst, as they offer the homogenous immobilization of metals within their ordered structure. Introducing Fe and Ni into the PHI network enables the formation of single and mixed transition metal PHIs, which show reduced overpotentials for ORR and OER. The formation of Ni single atoms even induces outstanding catalytic activity for the OER during charging of ZAB full cells with performance comparable to that of RuO <jats:sub>2</jats:sub> . Furthermore, full cell tests show excellent stability over the course of 250 discharge‐charge cycles, making it a promising system for sustainable energy storage. This work paves the way for the molecular design of a novel material class as an electrocatalyst for ZAB.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"17 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043001","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}
Sodium-ion batteries with abundant resources and cost-effectiveness are promising candidates for energy storage. However, their insufficient energy density impedes deployment in energy-intensive applications. Anode-free configurations maximize energy density by eliminating the initial anode host, while facing critical challenges of irreversible sodium plating/stripping. Here, we present double-coordination electrolyte additives-benzimidazole (BZ) and zinc trifluoromethanesulfonate (ZF) to address these intrinsic limitations. The highly polar ZF pulls out the solvents in the primary solvation sheath for Na+ diffusivity improving. Simultaneously, the ZF-BZ complexes preferentially adsorb and decompose on the Cu foil surface, in situ forming a high-entropy solid electrolyte interphase (ZnF2, NaF, Na2O, Na2CO3, and Na3N). This ultrathin interphase (3.7 nm) features superior mechanical toughness and a lowered nucleation barrier, thereby facilitating rapid, uniform, and highly reversible sodium plating/stripping. Consequently, the Na||Cu cell using 1 m NaPF6–diethylene glycol dimethyl–BZ/ZF electrolyte achieved an average Coulombic efficiency of 99.58% for 432 cycles at 3 mA cm−2/3 mAh cm−2 and stable cycling stability for 800 h in Na||Na cell. The assembled anode-less cell delivers a high energy-density of 327.54 Wh kg−1.
钠离子电池具有丰富的资源和成本效益，是一种很有前途的储能材料。然而，它们的能量密度不足阻碍了在能源密集型应用中的部署。无阳极配置通过消除初始阳极宿主来最大化能量密度，同时面临不可逆镀钠/剥离的关键挑战。在这里，我们提出了双配位电解质添加剂-苯并咪唑（BZ）和三氟甲磺酸锌（ZF）来解决这些固有的局限性。高极性的ZF将主溶剂鞘中的溶剂拉出，提高Na+的扩散率。同时，ZF-BZ配合物在Cu箔表面优先吸附分解，在原位形成高熵固体电解质界面（ZnF2、NaF、Na2O、Na2CO3和Na3N）。这种超薄间相（3.7 nm）具有优异的机械韧性和较低的成核屏障，从而促进快速、均匀和高度可逆的镀钠/剥离。结果表明，使用1 m napf6 -二甘醇二甲基- bz /ZF电解质的Na||Cu电池在3ma cm - 2/ 3mah cm - 2下循环432次，平均库仑效率达到99.58%，在Na||Na电池中稳定循环800 h。组装的无阳极电池提供327.54 Wh kg−1的高能量密度。
{"title":"Double-Coordination Additives Induced High-Entropy SEI for Stable Anode-Less Sodium Metal Batteries","authors":"Zhengda Lv, Xindan Li, Wenbin Li, Jun Luo, Yunhua Ling, Yue Sun, Xiujuan Lu, Shuai Guo, Shaohua Ge, Enhui Wang, Mingrui Yang, Weihua Chen","doi":"10.1002/aenm.202506756","DOIUrl":"https://doi.org/10.1002/aenm.202506756","url":null,"abstract":"Sodium-ion batteries with abundant resources and cost-effectiveness are promising candidates for energy storage. However, their insufficient energy density impedes deployment in energy-intensive applications. Anode-free configurations maximize energy density by eliminating the initial anode host, while facing critical challenges of irreversible sodium plating/stripping. Here, we present double-coordination electrolyte additives-benzimidazole (BZ) and zinc trifluoromethanesulfonate (ZF) to address these intrinsic limitations. The highly polar ZF pulls out the solvents in the primary solvation sheath for Na<sup>+</sup> diffusivity improving. Simultaneously, the ZF-BZ complexes preferentially adsorb and decompose on the Cu foil surface, in situ forming a high-entropy solid electrolyte interphase (ZnF<sub>2,</sub> NaF, Na<sub>2</sub>O, Na<sub>2</sub>CO<sub>3,</sub> and Na<sub>3</sub>N). This ultrathin interphase (3.7 nm) features superior mechanical toughness and a lowered nucleation barrier, thereby facilitating rapid, uniform, and highly reversible sodium plating/stripping. Consequently, the Na||Cu cell using 1 <span>m</span> NaPF<sub>6–</sub>diethylene glycol dimethyl–BZ/ZF electrolyte achieved an average Coulombic efficiency of 99.58% for 432 cycles at 3 mA cm<sup>−2</sup>/3 mAh cm<sup>−2</sup> and stable cycling stability for 800 h in Na||Na cell. The assembled anode-less cell delivers a high energy-density of 327.54 Wh kg<sup>−1</sup>.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"274 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146042996","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}
Bonyoung Ku, Lahyeon Jang, Hyunji Kweon, Jinho Ahn, Sunha Hwang, Jihoe Lee, Myungeun Choi, Sunyoung Yoo, Kwangho Yoo, Kyu-young Park, Jongsoon Kim
Mn-rich Li[Mn1-xFex]PO4 (LMFP) cathodes are promising candidates for next-generation lithium-ion batteries due to their structural stability and cost-effectiveness. However, under industrially relevant high-mass-loading conditions, they still suffer from severe performance degradation, particularly during fast charging. In this study, we systematically demonstrate that charge-transfer resistance, rather than bulk Li+ diffusivity, governs the kinetic limitations of LMFP electrodes with an areal capacity of ∼3.5 mAh cm−2 (∼23 mg cm−2 mass loading). Surface analyses reveal that the buildup of electronically and ionically insulating LiF at the cathode–electrolyte interphase (CEI) is the primary cause of sluggish charge transfer, highlighting a previously overlooked detrimental role of LiF. Guided by this insight, we implement an interfacial engineering strategy that suppresses LiF formation at the CEI. Remarkably, the resulting high-mass-loading LMFP cathodes deliver a 1.6-fold increase in capacity at 5C and retain ∼87% of their initial capacity after 100 cycles at 2C. Moreover, operando structural analysis reveals that electrodes with LiF-suppressed CEI maintain a robust single-phase transition during fast cycling, directly linking interfacial LiF suppression to significantly enhanced charge-transfer kinetics. This work highlights the critical importance of CEI engineering in enabling fast-charging Mn-rich olivine cathodes under practical, high-mass-loading conditions.
富锰Li[Mn1-xFex]PO4 （LMFP）阴极由于其结构稳定性和成本效益而成为下一代锂离子电池的有希望的候选者。然而，在工业相关的高质量负载条件下，它们仍然遭受严重的性能下降，特别是在快速充电时。在这项研究中，我们系统地证明了电荷转移电阻，而不是体积Li+扩散率，决定了面积容量为~ 3.5 mAh cm - 2 （~ 23 mg cm - 2质量负载）的LMFP电极的动力学限制。表面分析表明，阴极-电解质界面（CEI）的电子和离子绝缘LiF的积累是电荷转移缓慢的主要原因，突出了先前被忽视的LiF的有害作用。在这种见解的指导下，我们实施了一种界面工程策略，以抑制CEI处的生命形成。值得注意的是，由此产生的高质量负载LMFP阴极在5C下的容量增加了1.6倍，并且在2C下循环100次后保持了初始容量的约87%。此外，operando结构分析表明，具有liff抑制的CEI的电极在快速循环过程中保持了强大的单相转变，直接将界面liff抑制与显著增强的电荷转移动力学联系起来。这项工作强调了CEI工程在实际高质量负载条件下实现富锰橄榄石阴极快速充电的关键重要性。
{"title":"Enhanced Fast-Charging Performance of High-Mass-Loading Mn-Rich Li[Mn1-xFex]PO4 Cathodes via LiF-Less Cathode–Electrolyte Interphase","authors":"Bonyoung Ku, Lahyeon Jang, Hyunji Kweon, Jinho Ahn, Sunha Hwang, Jihoe Lee, Myungeun Choi, Sunyoung Yoo, Kwangho Yoo, Kyu-young Park, Jongsoon Kim","doi":"10.1002/aenm.202506130","DOIUrl":"https://doi.org/10.1002/aenm.202506130","url":null,"abstract":"Mn-rich Li[Mn<sub>1-</sub><i><sub>x</sub></i>Fe<i><sub>x</sub></i>]PO<sub>4</sub> (LMFP) cathodes are promising candidates for next-generation lithium-ion batteries due to their structural stability and cost-effectiveness. However, under industrially relevant high-mass-loading conditions, they still suffer from severe performance degradation, particularly during fast charging. In this study, we systematically demonstrate that charge-transfer resistance, rather than bulk Li<sup>+</sup> diffusivity, governs the kinetic limitations of LMFP electrodes with an areal capacity of ∼3.5 mAh cm<sup>−2</sup> (∼23 mg cm<sup>−2</sup> mass loading). Surface analyses reveal that the buildup of electronically and ionically insulating LiF at the cathode–electrolyte interphase (CEI) is the primary cause of sluggish charge transfer, highlighting a previously overlooked detrimental role of LiF. Guided by this insight, we implement an interfacial engineering strategy that suppresses LiF formation at the CEI. Remarkably, the resulting high-mass-loading LMFP cathodes deliver a 1.6-fold increase in capacity at 5C and retain ∼87% of their initial capacity after 100 cycles at 2C. Moreover, <i>operando</i> structural analysis reveals that electrodes with LiF-suppressed CEI maintain a robust single-phase transition during fast cycling, directly linking interfacial LiF suppression to significantly enhanced charge-transfer kinetics. This work highlights the critical importance of CEI engineering in enabling fast-charging Mn-rich olivine cathodes under practical, high-mass-loading conditions.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"43 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043000","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}
Yingjie He, Yao Tan, Qiuwen Liu, Bojing Sun, Qin Chen, Baixiong Liu, Kang Liu, Min Liu
Electrochemical CO reduction to ethanol offers a sustainable route for carbon utilization, but the uncontrollable hydrogenation pathway in post C─C coupling limits its selectivity. Herein, we introduced Pb doping to modulate the carbophobicity of Cu catalyst, thereby directing hydrogenation toward the β-C of the key *CH2CHO intermediate and boosting ethanol production. Density functional theory calculations revealed that Pb incorporation reduced electron transfer from Cu to *CH2CHO, weakening the Cu─C bond and favoring the β-C hydrogenation over the ethylene pathway. In situ X-ray absorption spectroscopy confirmed that Pb doping lowered the electron density at Cu sites, resulting in weakened CO adsorption, consistent with a carbophobic catalyst surface. In situ attenuated total reflectance Fourier transform infrared spectroscopy further revealed suppressed CO coverage and enhanced accumulation of ethanol-pathway intermediates (*OC2H5) on the Pb-doped Cu. As a result, the optimized PbCu catalyst achieved an ethanol Faradaic efficiency of 55.2% with a partial current density of ∼500 mA cm−2, outperforming most reported CO reduction catalysts. This work highlights carbophobicity engineering as a powerful strategy to fine-tune intermediate binding and selectively drive ethanol production in CO/CO2 electroreduction.
电化学CO还原为乙醇提供了一种可持续的碳利用途径，但后C─C偶联过程中不可控的加氢途径限制了其选择性。在此，我们引入铅掺杂来调节Cu催化剂的疏碳性，从而将氢化作用引向关键*CH2CHO中间体的β-C，从而提高乙醇的产量。密度泛函理论计算表明，Pb的加入减少了Cu到*CH2CHO的电子转移，削弱了Cu─C键，有利于β-C在乙烯途径中的加氢。原位x射线吸收光谱证实，Pb掺杂降低了Cu位点的电子密度，导致CO吸附减弱，与催化剂表面的疏碳性一致。原位衰减全反射傅立叶变换红外光谱进一步揭示了铅掺杂Cu上CO覆盖被抑制和乙醇途径中间体（*OC2H5）积累增强。结果表明，优化后的PbCu催化剂的乙醇法拉第效率为55.2%，偏电流密度为~ 500 mA cm−2，优于大多数报道的CO还原催化剂。这项工作强调了在CO/CO2电还原中，疏碳工程是一种微调中间结合和选择性驱动乙醇生产的有力策略。
{"title":"Manipulating Cu Surface Carbophobicity with Pb for Efficient CO-to-Ethanol Electroconversion","authors":"Yingjie He, Yao Tan, Qiuwen Liu, Bojing Sun, Qin Chen, Baixiong Liu, Kang Liu, Min Liu","doi":"10.1002/aenm.202506794","DOIUrl":"https://doi.org/10.1002/aenm.202506794","url":null,"abstract":"Electrochemical CO reduction to ethanol offers a sustainable route for carbon utilization, but the uncontrollable hydrogenation pathway in post C─C coupling limits its selectivity. Herein, we introduced Pb doping to modulate the carbophobicity of Cu catalyst, thereby directing hydrogenation toward the β-C of the key <sup>*</sup>CH<sub>2</sub>CHO intermediate and boosting ethanol production. Density functional theory calculations revealed that Pb incorporation reduced electron transfer from Cu to <sup>*</sup>CH<sub>2</sub>CHO, weakening the Cu─C bond and favoring the β-C hydrogenation over the ethylene pathway. In situ X-ray absorption spectroscopy confirmed that Pb doping lowered the electron density at Cu sites, resulting in weakened CO adsorption, consistent with a carbophobic catalyst surface. In situ attenuated total reflectance Fourier transform infrared spectroscopy further revealed suppressed CO coverage and enhanced accumulation of ethanol-pathway intermediates (<sup>*</sup>OC<sub>2</sub>H<sub>5</sub>) on the Pb-doped Cu. As a result, the optimized PbCu catalyst achieved an ethanol Faradaic efficiency of 55.2% with a partial current density of ∼500 mA cm<sup>−2</sup>, outperforming most reported CO reduction catalysts. This work highlights carbophobicity engineering as a powerful strategy to fine-tune intermediate binding and selectively drive ethanol production in CO/CO<sub>2</sub> electroreduction.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"31 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034209","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}
Combining the high ionic conductivity of inorganic filler with the robust strength of organic matrix is a valid strategy to boost the ion transport and interface stability of composite solid electrolyte, which effectively inhibits dendrite growth of zinc anode and active material dissolution of cathode for zinc metal batteries (ZMBs). Herein, DLM@SA@Zn quasi-solid-state electrolytes (QSSEs) are constructed by sodium alginate (SA) and dolomite (DLM) through self-assembly film technology, and delivers wide operating voltage window (3.08 V), high ionic conductivity (2.22 mS cm−1), and high Zn2+ transference number (0.84). For the Zn//AC@I2 cells in DLM@SA@Zn electrolyte, a high-capacity retention ratio of 82.48% is achieved after 22 000 cycles at 1 A g−1, and a high reversible capacity of 162.7 mAh g−1 is maintained after 250 cycles at 0.5 A g−1 under high temperature of 60°C. These outstanding performances can be attributed to the low zinc diffusion energy barriers, superior structural stability, and strong polyiodide adsorption capability, consequently guaranteeing uniform Zn deposition, ignorable iodine dissolution, and polyiodide shuttle-free behavior. Furthermore, Zn//NH4V4O10 cells also exhibit a high-capacity retention ratio of 81% after 200 cycles at 0.5 A g−1 in DLM@SA@Zn electrolyte, highlighting its promising application potential in ZMBs, and providing new insights for the rational design of QSSEs.
将无机填料的高离子电导率与有机基体的强强度相结合，是提高复合固体电解质离子传输和界面稳定性的有效策略，可有效抑制锌金属电池锌阳极枝晶生长和阴极活性物质溶解。本文采用海藻酸钠（SA）和白云石（DLM）通过自组装膜技术构建了DLM@SA@Zn准固态电解质（qsse），具有宽工作电压窗（3.08 V）、高离子电导率（2.22 mS cm−1）和高Zn2+转移数（0.84）的特点。在DLM@SA@Zn电解液中，锌//AC@I2电池在1 a g−1下循环22000次后容量保持率达到82.48%，在0.5 a g−1下高温60℃下循环250次后容量保持162.7 mAh g−1的高可逆容量。这些优异的性能可归因于低锌扩散能垒、优异的结构稳定性和较强的聚碘吸附能力，从而保证了均匀的锌沉积、忽略碘的溶解和聚碘的无梭行为。此外，在DLM@SA@Zn电解液中，在0.5 a g−1下循环200次后，Zn//NH4V4O10电池的容量保持率高达81%，突出了其在zmb中的应用潜力，并为qss的合理设计提供了新的见解。
{"title":"A Mineral-Biopolymer Synergistic Quasi-Solid-State Electrolyte for Long-Lasting Zinc Metal Batteries","authors":"Chi Chen, Fulong Li, Yating Gao, Gai Li, Lutong Shan, Yicai Pan, Yongqiang Yang, Wen Chen, Xiaoxiao Liang, Jing Li, Zhenyue Xing, Peng Rao, Zhenye Kang, Yingjie Hua, Xiaodong Shi, Xinlong Tian","doi":"10.1002/aenm.202505241","DOIUrl":"https://doi.org/10.1002/aenm.202505241","url":null,"abstract":"Combining the high ionic conductivity of inorganic filler with the robust strength of organic matrix is a valid strategy to boost the ion transport and interface stability of composite solid electrolyte, which effectively inhibits dendrite growth of zinc anode and active material dissolution of cathode for zinc metal batteries (ZMBs). Herein, DLM@SA@Zn quasi-solid-state electrolytes (QSSEs) are constructed by sodium alginate (SA) and dolomite (DLM) through self-assembly film technology, and delivers wide operating voltage window (3.08 V), high ionic conductivity (2.22 mS cm<sup>−1</sup>), and high Zn<sup>2+</sup> transference number (0.84). For the Zn//AC@I<sub>2</sub> cells in DLM@SA@Zn electrolyte, a high-capacity retention ratio of 82.48% is achieved after 22 000 cycles at 1 A g<sup>−1</sup>, and a high reversible capacity of 162.7 mAh g<sup>−1</sup> is maintained after 250 cycles at 0.5 A g<sup>−1</sup> under high temperature of 60°C. These outstanding performances can be attributed to the low zinc diffusion energy barriers, superior structural stability, and strong polyiodide adsorption capability, consequently guaranteeing uniform Zn deposition, ignorable iodine dissolution, and polyiodide shuttle-free behavior. Furthermore, Zn//NH<sub>4</sub>V<sub>4</sub>O<sub>10</sub> cells also exhibit a high-capacity retention ratio of 81% after 200 cycles at 0.5 A g<sup>−1</sup> in DLM@SA@Zn electrolyte, highlighting its promising application potential in ZMBs, and providing new insights for the rational design of QSSEs.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"3 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034210","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}
Hard carbon anodes for sodium-ion batteries rely on Na+ insertion into graphite-like layers below 0.1 V, where closed-pore structures are critical for high energy density. However, controlling hard carbon microstructures remains challenging. Here, the industrial lignin precursor was simply pre-pyrolyzed and carbonized to synthesize high-performance hard carbon with curved graphite-like layers forming topological cavities. Through GITT and in situ TEM, we visualized Na+ (de)intercalation and demonstrated that closed pores (∼1 nm) enhance sodium storage. Even the FFT transform revealed the appearance of a new material lattice (C32Na). This work provides insights for tuning hard carbon microstructures and biomass bulk processing and value-added utilization.
{"title":"In Situ TEM Reveals the Hard Carbon Sodium Storage Mechanism and Discovers the Sodium Carbide","authors":"Huimin Cao, Yizhao Zhao, Zhiyi Huang, Xingxiang Ji, Shoujuan Wang, Wanqi Duan, Yuebin Xi, Yuanwei Sun, Fangong Kong, Yu Liu, Huan Wang","doi":"10.1002/aenm.202505191","DOIUrl":"https://doi.org/10.1002/aenm.202505191","url":null,"abstract":"Hard carbon anodes for sodium-ion batteries rely on Na<sup>+</sup> insertion into graphite-like layers below 0.1 V, where closed-pore structures are critical for high energy density. However, controlling hard carbon microstructures remains challenging. Here, the industrial lignin precursor was simply pre-pyrolyzed and carbonized to synthesize high-performance hard carbon with curved graphite-like layers forming topological cavities. Through GITT and in situ TEM, we visualized Na<sup>+</sup> (de)intercalation and demonstrated that closed pores (∼1 nm) enhance sodium storage. Even the FFT transform revealed the appearance of a new material lattice (C<sub>32</sub>Na). This work provides insights for tuning hard carbon microstructures and biomass bulk processing and value-added utilization.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"287 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146042997","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}
Organosulfur polymers, valued for their structural tunability and environmental friendliness as cathode materials for lithium-sulfur (Li-S) batteries, face challenges in practical applications due to inadequate cycling stability and rate performance. Herein, we report the rational design and green synthesis of a heterocycle-bridged short sulfur-chain polymer, namely poly(pyrazine tetrasulfide) (PPZTS), with a sulfur-rich atomic chain structure as a high-performance cathode material for lithium-organosulfide batteries. The pyrazine-bridged short sulfur-chain structure in PPZTS prevents the formation and shuttling of long-chain polysulfides, and the electronegative π-conjugated pyrazine rings facilitate uniform Li+ diffusion, leading to significant improvements in both cycling stability and rate performance. The PPZTS cathode achieves a high capacity of 1250 mAh g−1 at 0.1 A g−1 and 660 mAh g−1 at 5.0 A g−1. When cycled at 1.0 A g−1, the PPZTS cathode demonstrates an initial capacity of 850.9 mAh g−1 and retaining 630.4 mAh g−1 after 400 cycles. The PPZTS cathode also demonstrates robust performance across a wide temperature range from −20 to 80°C, and the deployment in soft-packed batteries further suggests its potential practicability. This work underscores the intriguing potential of heterocycle-linked short sulfur-chain polymers as cathode materials for alkali metal-organosulfide batteries, addressing key challenges in organosulfur polymer applications for advanced energy storage devices.
有机硫聚合物作为锂硫电池的正极材料，具有结构可调节性和环境友好性，但由于循环稳定性和倍率性能不足，在实际应用中面临挑战。本文报道了一种具有富硫原子链结构的杂环桥接短硫链聚合物聚吡嗪四硫醚（PPZTS）的合理设计和绿色合成，作为锂有机硫化电池的高性能正极材料。PPZTS中吡嗪桥接的短硫链结构阻止了长链多硫化物的形成和穿梭，电负性π共轭吡嗪环促进Li+均匀扩散，循环稳定性和速率性能均有显著提高。PPZTS阴极在0.1 a g−1和5.0 a g−1时的高容量分别为1250 mAh g−1和660 mAh g−1。当在1.0 A g−1下循环时，PPZTS阴极的初始容量为850.9 mAh g−1，在400次循环后保持630.4 mAh g−1。PPZTS阴极在- 20至80°C的宽温度范围内也表现出稳健的性能，并且在软包装电池中的部署进一步表明了其潜在的实用性。这项工作强调了杂环连接的短硫链聚合物作为碱金属-有机硫化物电池正极材料的有趣潜力，解决了有机硫聚合物在先进储能设备应用中的关键挑战。
{"title":"Heterocycle-Bridged Short Sulfur-Chain Polymers for Polysulfide-Suppressing Cathodes in Lithium-Organosulfide Batteries","authors":"Xingkai Ma, Huan Li, Junchuan Liang, Yaoda Wang, Tianyu Shen, Xinmei Song, Zuoao Wu, Huaizhu Wang, Lina Qin, Tianchen Yu, Zuoxiu Tie, Zhong Jin","doi":"10.1002/aenm.202506388","DOIUrl":"https://doi.org/10.1002/aenm.202506388","url":null,"abstract":"Organosulfur polymers, valued for their structural tunability and environmental friendliness as cathode materials for lithium-sulfur (Li-S) batteries, face challenges in practical applications due to inadequate cycling stability and rate performance. Herein, we report the rational design and green synthesis of a heterocycle-bridged short sulfur-chain polymer, namely poly(pyrazine tetrasulfide) (PPZTS), with a sulfur-rich atomic chain structure as a high-performance cathode material for lithium-organosulfide batteries. The pyrazine-bridged short sulfur-chain structure in PPZTS prevents the formation and shuttling of long-chain polysulfides, and the electronegative π-conjugated pyrazine rings facilitate uniform Li<sup>+</sup> diffusion, leading to significant improvements in both cycling stability and rate performance. The PPZTS cathode achieves a high capacity of 1250 mAh g<sup>−1</sup> at 0.1 A g<sup>−1</sup> and 660 mAh g<sup>−1</sup> at 5.0 A g<sup>−1</sup>. When cycled at 1.0 A g<sup>−1</sup>, the PPZTS cathode demonstrates an initial capacity of 850.9 mAh g<sup>−1</sup> and retaining 630.4 mAh g<sup>−1</sup> after 400 cycles. The PPZTS cathode also demonstrates robust performance across a wide temperature range from −20 to 80°C, and the deployment in soft-packed batteries further suggests its potential practicability. This work underscores the intriguing potential of heterocycle-linked short sulfur-chain polymers as cathode materials for alkali metal-organosulfide batteries, addressing key challenges in organosulfur polymer applications for advanced energy storage devices.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"59 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034208","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}
Potassium-ion batteries (KIBs) are gaining attention as a sustainable alternative to lithium- and sodium-based systems, benefiting from the abundance of potassium, low-cost salts, and the potential use of biomass-derived carbons. Their favorable redox potential, compatibility with aluminum current collectors, and stable SEI formation provide unique advantages, though the large ionic radius of K+ poses challenges for designing stable and high-capacity anodes. This review categorizes KIB anodes into five classes—alloy-based, intercalation-type, conversion-type, conversion–intercalation hybrids, and organic systems—and critically evaluates their redox mechanisms, electrochemical performance, and structural evolution. Beyond the active materials, we highlight the often-overlooked but crucial influence of electrolyte formulations (e.g., potassium hexafluorophosphate (KPF6), potassium bis(fluorosulfonyl)imide (KFSI), or concentrated electrolytes) and binder chemistries in governing solid electrolyte interface (SEI) stability, ion transport, and electrode durability. We also discuss recent commercialization efforts, including Natron Energy's Prussian blue–based systems, and outline a forward-looking roadmap that integrates materials innovation with electrode–electrolyte engineering and sustainability principles. By bridging mechanistic understanding with industrial perspectives, this review provides guidance for advancing KIBs toward practical, environmentally responsible energy storage solutions.
{"title":"Potassium-Ion Battery Anodes: Mechanistic Frameworks, Electrolyte/Binder Integration, and Roadmap Toward Commercialization","authors":"Manab Kundu, Rajashree Konar, Sandipan Maiti","doi":"10.1002/aenm.202505727","DOIUrl":"https://doi.org/10.1002/aenm.202505727","url":null,"abstract":"Potassium-ion batteries (KIBs) are gaining attention as a sustainable alternative to lithium- and sodium-based systems, benefiting from the abundance of potassium, low-cost salts, and the potential use of biomass-derived carbons. Their favorable redox potential, compatibility with aluminum current collectors, and stable SEI formation provide unique advantages, though the large ionic radius of K<sup>+</sup> poses challenges for designing stable and high-capacity anodes. This review categorizes KIB anodes into five classes—alloy-based, intercalation-type, conversion-type, conversion–intercalation hybrids, and organic systems—and critically evaluates their redox mechanisms, electrochemical performance, and structural evolution. Beyond the active materials, we highlight the often-overlooked but crucial influence of electrolyte formulations (e.g., potassium hexafluorophosphate (KPF<sub>6</sub>), potassium bis(fluorosulfonyl)imide (KFSI), or concentrated electrolytes) and binder chemistries in governing solid electrolyte interface (SEI) stability, ion transport, and electrode durability. We also discuss recent commercialization efforts, including Natron Energy's Prussian blue–based systems, and outline a forward-looking roadmap that integrates materials innovation with electrode–electrolyte engineering and sustainability principles. By bridging mechanistic understanding with industrial perspectives, this review provides guidance for advancing KIBs toward practical, environmentally responsible energy storage solutions.","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"56 1","pages":""},"PeriodicalIF":27.8,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146042998","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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