Pub Date : 2026-01-27DOI: 10.1016/j.nanoen.2026.111758
Zeqing Hu , Minwen Yang , Wenjie Li , Jiahao Jiang , Jing Shuai
Diamond-like CuInTe2 is a promising candidate for mid-temperature thermoelectrics, yet its performance is severely bottlenecked by the intrinsic trade-off between a low carrier concentration and a high lattice thermal conductivity. Herein, we demonstrate a stepwise decoupling strategy that orchestrates electronic and thermal transport via In-vacancy engineering and isoelectronic Ag alloying. First, the introduction of In vacancies drives the Fermi level deep into the valence band while inducing valence band flattening at the M and R points. This modification significantly enhances the density-of-states effective mass and hole concentration, yielding a superior power factor. Subsequently, Ag alloying drastically suppresses the lattice thermal conductivity through a synergistic combination of strain/mass field fluctuations, reduced Debye frequency, and, critically, strong coupling between low-frequency optical and acoustic phonons. Validated by comprehensive experimental characterization and density functional theory calculations, this approach achieves a peak figure-of-merit of ∼1.12 at 820 K in Cu0.85Ag0.15In0.96Te2, representing a ∼143 % enhancement over pristine CuInTe2. This work establishes a precise paradigm for manipulating band structure and phonon anharmonicity to unlock the full potential of diamond-like thermoelectric materials.
{"title":"Orchestrating valence band flattening and phonon coupling for high-performance CuInTe2 thermoelectrics","authors":"Zeqing Hu , Minwen Yang , Wenjie Li , Jiahao Jiang , Jing Shuai","doi":"10.1016/j.nanoen.2026.111758","DOIUrl":"10.1016/j.nanoen.2026.111758","url":null,"abstract":"<div><div>Diamond-like CuInTe<sub>2</sub> is a promising candidate for mid-temperature thermoelectrics, yet its performance is severely bottlenecked by the intrinsic trade-off between a low carrier concentration and a high lattice thermal conductivity. Herein, we demonstrate a stepwise decoupling strategy that orchestrates electronic and thermal transport via In-vacancy engineering and isoelectronic Ag alloying. First, the introduction of In vacancies drives the Fermi level deep into the valence band while inducing valence band flattening at the <em>M</em> and <em>R</em> points. This modification significantly enhances the density-of-states effective mass and hole concentration, yielding a superior power factor. Subsequently, Ag alloying drastically suppresses the lattice thermal conductivity through a synergistic combination of strain/mass field fluctuations, reduced Debye frequency, and, critically, strong coupling between low-frequency optical and acoustic phonons. Validated by comprehensive experimental characterization and density functional theory calculations, this approach achieves a peak figure-of-merit of ∼1.12 at 820 K in Cu<sub>0.85</sub>Ag<sub>0.15</sub>In<sub>0.96</sub>Te<sub>2</sub>, representing a ∼143 % enhancement over pristine CuInTe<sub>2</sub>. This work establishes a precise paradigm for manipulating band structure and phonon anharmonicity to unlock the full potential of diamond-like thermoelectric materials.</div></div>","PeriodicalId":394,"journal":{"name":"Nano Energy","volume":"150 ","pages":"Article 111758"},"PeriodicalIF":17.1,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076531","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}
Pub Date : 2026-01-26DOI: 10.1016/j.nanoen.2026.111753
Meng Tian , Hui Zhang , Mingyu Ma , Gang Ye , Jian Liu , Shuyan Shao , Zhen Li
Side-chain engineering of n-type polymers has received much less attention than backbone manipulation. This study demonstrates unique advantages of fluoroalkyl hybrid glycol ether side chains of naphthalene diimide (NDI)-based electron transport layers (ETLs) compared to their counterpart (P3O) without fluoroalkyl terminals. First, the fluoroalkyl hybrid glycol ether side chains shift the polymer chain orientation from edge-on in P3O to face-on in P3F, P5F, and P7F, thereby accelerating charge transport. Second, they introduce interfacial dipoles that passivate defects at the perovskite surface, generating an additional electric field that improves electron transfer efficiency. Third, they remarkably enhance the moisture resistance of ETLs and the ambient stability of Dion-Jacobson hybrid perovskite solar cells (DJHPSCs). Consequently, NDI-polymers with fluoroalkyl hybrid glycol ether side chains remarkably improved the power conversion efficiency (PCE) and lifetime of the DJHPSCs compared to the counterpart using P3O. For instance, P3F as ETL yields a power conversion efficiency (PCE) of 14.21 % and allows the device to retain 80.2 % of its initial PCE after 2077 h of air exposure. This represents a remarkable improvement in both PCE and lifetime compared to the device using P3O as ETL, which delivers a low PCE of 11.14 %, and retains 48 % of its initial value after 1740 h of air exposure.
{"title":"Revealing the role of the fluoroalkyl hybrid glycol ether side chains of n-type polymers in the performance of Dion-Jacobson perovskite solar cells","authors":"Meng Tian , Hui Zhang , Mingyu Ma , Gang Ye , Jian Liu , Shuyan Shao , Zhen Li","doi":"10.1016/j.nanoen.2026.111753","DOIUrl":"10.1016/j.nanoen.2026.111753","url":null,"abstract":"<div><div>Side-chain engineering of n-type polymers has received much less attention than backbone manipulation. This study demonstrates unique advantages of fluoroalkyl hybrid glycol ether side chains of naphthalene diimide (NDI)-based electron transport layers (ETLs) compared to their counterpart (P3O) without fluoroalkyl terminals. First, the fluoroalkyl hybrid glycol ether side chains shift the polymer chain orientation from edge-on in P3O to face-on in P3F, P5F, and P7F, thereby accelerating charge transport. Second, they introduce interfacial dipoles that passivate defects at the perovskite surface, generating an additional electric field that improves electron transfer efficiency. Third, they remarkably enhance the moisture resistance of ETLs and the ambient stability of Dion-Jacobson hybrid perovskite solar cells (DJHPSCs). Consequently, NDI-polymers with fluoroalkyl hybrid glycol ether side chains remarkably improved the power conversion efficiency (PCE) and lifetime of the DJHPSCs compared to the counterpart using P3O. For instance, P3F as ETL yields a power conversion efficiency (PCE) of 14.21 % and allows the device to retain 80.2 % of its initial PCE after 2077 h of air exposure. This represents a remarkable improvement in both PCE and lifetime compared to the device using P3O as ETL, which delivers a low PCE of 11.14 %, and retains 48 % of its initial value after 1740 h of air exposure.</div></div>","PeriodicalId":394,"journal":{"name":"Nano Energy","volume":"150 ","pages":"Article 111753"},"PeriodicalIF":17.1,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146047820","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}
Pub Date : 2026-01-26DOI: 10.1016/j.nanoen.2026.111754
Xuejie Wang , Lugang Ma , Wenxue Yan , Xue Zhang , Jinbao Han , Weilai Yu , Tao Liu
Polyanion Na3V2(PO4)3 (NVP) is a promising cathode for sodium-ion batteries due to its robust NASICON framework and excellent thermal stability, yet its practical utility remains constrained by low electronic conductivity, sluggish Na⁺ transport, and capacity degradation at high rates. Here, we present a scalable Mo6 + -doping strategy enabled by an integrated solid-phase nanomanufacturing route—combining sand milling, spray drying, and deposition of a uniform ∼3 nm carbon shell—to achieve homogeneous dopant distribution and optimized particle architecture. Mechanistically, Mo6+ serves as both an electronic enhancer and local structural regulator. Strengthened Mo–O bonding and subtle lattice perturbations—shortened Mo–O, slightly elongated adjacent V–O, and increased Mo–Na distances—expand Na⁺ diffusion channels. Concurrently, Mo 3d–derived defect states near the Fermi level narrow the bandgap and enrich frontier-state density. DFT calculations and spectroscopic analyses confirm strong Mo–O hybridization, charge redistribution, and significantly reduced Na⁺ migration barriers. During cycling, a reversible Na2V1.96Mo0.04(PO4)3 intermediate forms, alleviating lattice mismatch and enabling rapid phase transitions. Consequently, Na3V1.96Mo0.04(PO4)3/C delivers ≈ 112 mAh g−1 at 0.1 C, 83.2 mAh g−1 at 20 C, and maintains 69 mAh g−1 after 6000 cycles at 20 C. Overall, this work demonstrates that precise high-valence dopant engineering, coupled with nanoscale carbon architectures, offers a practical and generalizable strategy for developing high-rate, long-life NASICON-type cathodes.
聚阴离子Na3V2(PO4)3 （NVP）是一种很有前途的钠离子电池阴极，由于其强大的NASICON框架和优异的热稳定性，但其实际应用仍然受到低电子导电性、Na⁺传输缓慢和高速率容量退化的限制。在这里，我们提出了一种可扩展的Mo6 +掺杂策略，该策略通过集成的固相纳米制造路线-结合砂磨，喷雾干燥和均匀的~ 3 nm碳壳沉积-实现均匀的掺杂分布和优化的颗粒结构。从机理上讲，Mo6+同时起到电子增强剂和局部结构调节器的作用。增强的Mo-O键和细微的晶格微扰-缩短了Mo-O，略微拉长了相邻的V-O，增加了Mo-Na的距离-扩展了Na⁺的扩散通道。同时，Mo在费米能级附近的三维缺陷态缩小了带隙，丰富了边界态密度。DFT计算和光谱分析证实了很强的Mo-O杂化、电荷再分配和Na⁺迁移障碍的显著降低。在循环过程中，形成可逆的Na2V1.96Mo0.04(PO4)3中间体，减轻了晶格失配并实现了快速相变。因此，Na3V1.96Mo0.04(PO4)3/C在0.1 C时输出≈ 112 mAh g−1，在20 C时输出83.2 mAh g−1，在20 C下循环6000次后保持69 mAh g−1。总的来说，这项工作表明，精确的高价掺杂工程，加上纳米级碳结构，为开发高速率、长寿命的nasicon型阴极提供了一种实用的、可推广的策略。
{"title":"High-valence Mo doping enables phase-stable, fast-transport Na3V2(PO4)3 cathodes for high-performance sodium-ion batteries","authors":"Xuejie Wang , Lugang Ma , Wenxue Yan , Xue Zhang , Jinbao Han , Weilai Yu , Tao Liu","doi":"10.1016/j.nanoen.2026.111754","DOIUrl":"10.1016/j.nanoen.2026.111754","url":null,"abstract":"<div><div>Polyanion Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (NVP) is a promising cathode for sodium-ion batteries due to its robust NASICON framework and excellent thermal stability, yet its practical utility remains constrained by low electronic conductivity, sluggish Na⁺ transport, and capacity degradation at high rates. Here, we present a scalable Mo<sup>6 +</sup> -doping strategy enabled by an integrated solid-phase nanomanufacturing route—combining sand milling, spray drying, and deposition of a uniform ∼3 nm carbon shell—to achieve homogeneous dopant distribution and optimized particle architecture. Mechanistically, Mo<sup>6+</sup> serves as both an electronic enhancer and local structural regulator. Strengthened Mo–O bonding and subtle lattice perturbations—shortened Mo–O, slightly elongated adjacent V–O, and increased Mo–Na distances—expand Na⁺ diffusion channels. Concurrently, Mo 3d–derived defect states near the Fermi level narrow the bandgap and enrich frontier-state density. DFT calculations and spectroscopic analyses confirm strong Mo–O hybridization, charge redistribution, and significantly reduced Na⁺ migration barriers. During cycling, a reversible Na<sub>2</sub>V<sub>1.96</sub>Mo<sub>0.04</sub>(PO<sub>4</sub>)<sub>3</sub> intermediate forms, alleviating lattice mismatch and enabling rapid phase transitions. Consequently, Na<sub>3</sub>V<sub>1.96</sub>Mo<sub>0.04</sub>(PO<sub>4</sub>)<sub>3</sub>/C delivers ≈ 112 mAh g<sup>−1</sup> at 0.1 C, 83.2 mAh g<sup>−1</sup> at 20 C, and maintains 69 mAh g<sup>−1</sup> after 6000 cycles at 20 C. Overall, this work demonstrates that precise high-valence dopant engineering, coupled with nanoscale carbon architectures, offers a practical and generalizable strategy for developing high-rate, long-life NASICON-type cathodes.</div></div>","PeriodicalId":394,"journal":{"name":"Nano Energy","volume":"150 ","pages":"Article 111754"},"PeriodicalIF":17.1,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146045218","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}
Pub Date : 2026-01-23DOI: 10.1016/j.nanoen.2026.111751
Amit Bhowmick , Bo Rui , Shuguo Sun , Xijun Tan , Bingqing Wei , Youngwon Hahn , Sandeep Kulathu , Victor Oancea , Wenquan Lu , Jun Xu
Understanding and mitigating lithium plating remains one of the most pressing challenges in advancing the safety and longevity of lithium-ion batteries (LIBs). Here, we present a novel integrative framework that combines in-operando swelling force measurements with a physics-based electro-chemo-mechanical model to uncover previously inaccessible insights into lithium plating dynamics under mechanical constraints. Unlike existing approaches that focus primarily on electrochemical signatures, our approach captures the coupled mechanical responses of commercial pouch cells during cycling, revealing how mechanical constraints fundamentally alter degradation pathways. We demonstrate that the use of a moderate stacking pressure suppresses lithium plating and enhances lithium stripping. This mechanically driven structural effect, coupled with the electrochemical process, significantly extends the linear aging regime in LIBs. Intriguingly, intermittent capacity recovery events that were observed during the battery cycling suggest dynamic lithium reactivation, a phenomenon rarely captured in real-time. This study pioneers a stress-aware methodology for diagnosing and managing lithium plating, establishing a new paradigm for real-time battery health monitoring. The findings offer transformative implications for the design of durable, high-performance LIB systems, opening new avenues for intelligent control strategies in battery management systems.
{"title":"Electrochemo-mechanics unlocks hidden dynamics of lithium plating under stacking pressure","authors":"Amit Bhowmick , Bo Rui , Shuguo Sun , Xijun Tan , Bingqing Wei , Youngwon Hahn , Sandeep Kulathu , Victor Oancea , Wenquan Lu , Jun Xu","doi":"10.1016/j.nanoen.2026.111751","DOIUrl":"10.1016/j.nanoen.2026.111751","url":null,"abstract":"<div><div>Understanding and mitigating lithium plating remains one of the most pressing challenges in advancing the safety and longevity of lithium-ion batteries (LIBs). Here, we present a novel integrative framework that combines in-operando swelling force measurements with a physics-based electro-chemo-mechanical model to uncover previously inaccessible insights into lithium plating dynamics under mechanical constraints. Unlike existing approaches that focus primarily on electrochemical signatures, our approach captures the coupled mechanical responses of commercial pouch cells during cycling, revealing how mechanical constraints fundamentally alter degradation pathways. We demonstrate that the use of a moderate stacking pressure suppresses lithium plating and enhances lithium stripping. This mechanically driven structural effect, coupled with the electrochemical process, significantly extends the linear aging regime in LIBs. Intriguingly, intermittent capacity recovery events that were observed during the battery cycling suggest dynamic lithium reactivation, a phenomenon rarely captured in real-time. This study pioneers a stress-aware methodology for diagnosing and managing lithium plating, establishing a new paradigm for real-time battery health monitoring. The findings offer transformative implications for the design of durable, high-performance LIB systems, opening new avenues for intelligent control strategies in battery management systems.</div></div>","PeriodicalId":394,"journal":{"name":"Nano Energy","volume":"150 ","pages":"Article 111751"},"PeriodicalIF":17.1,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033820","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}
Pub Date : 2026-01-23DOI: 10.1016/j.nanoen.2026.111750
Yunfeng Wang , Haibao Mu , Huanmin Yao , Shasha He , Shuai Wang , Yiyun Yang , Yaxin Chen , Xinran Chen , Guanjun Zhang
Triboelectric flexible wearable sensors provide a new momentum for the intelligent and digital development of rehabilitation medicine, and effectively address the key challenges of sensor power supply, sensitivity, and comfort. However, the lack of reliable control methods for material doping makes it difficult to further enhance the sensitivity of triboelectric sensors. Inspired by the efficient water transport mechanism in plants, this study employed an AC electric field-assisted method to fabricate MXene/Ecoflex composite films (ACC films) with an oriented structure. The influence of the electric field on MXene orientation behavior and its formation mechanism were systematically investigated. Experimental results demonstrate that the oriented MXene filler effectively enhances the film's charge storage capacity and reduces charge dissipation, thus significantly improving the output performance of the triboelectric nanogenerator (TENG). The open-circuit voltage, short-circuit current, and charge density of ACC-TENG prepared under a 600 V/mm electric field increased by 25.2 %, 34 %, and 31 %, respectively, comparing to the film without an applied electric field. Ultimately, the constructed ACC-TENG was applied as a flexible sensor for human motion monitoring and rehabilitation assessment, achieving highly sensitive detection of subtle motion features such as joint flexion duration, flexion angle, and finger tremors during gripping (with conventional gripping signals reaching 20 V output). This provides innovative material design concepts and technical pathways for the advancement of intelligent rehabilitation medicine.
{"title":"Electric field-assisted construction of bionic directional channels enhances charge storage in MXene/Ecoflex triboelectric nanogenerators for self-powered sensing","authors":"Yunfeng Wang , Haibao Mu , Huanmin Yao , Shasha He , Shuai Wang , Yiyun Yang , Yaxin Chen , Xinran Chen , Guanjun Zhang","doi":"10.1016/j.nanoen.2026.111750","DOIUrl":"10.1016/j.nanoen.2026.111750","url":null,"abstract":"<div><div>Triboelectric flexible wearable sensors provide a new momentum for the intelligent and digital development of rehabilitation medicine, and effectively address the key challenges of sensor power supply, sensitivity, and comfort. However, the lack of reliable control methods for material doping makes it difficult to further enhance the sensitivity of triboelectric sensors. Inspired by the efficient water transport mechanism in plants, this study employed an AC electric field-assisted method to fabricate MXene/Ecoflex composite films (ACC films) with an oriented structure. The influence of the electric field on MXene orientation behavior and its formation mechanism were systematically investigated. Experimental results demonstrate that the oriented MXene filler effectively enhances the film's charge storage capacity and reduces charge dissipation, thus significantly improving the output performance of the triboelectric nanogenerator (TENG). The open-circuit voltage, short-circuit current, and charge density of ACC-TENG prepared under a 600 V/mm electric field increased by 25.2 %, 34 %, and 31 %, respectively, comparing to the film without an applied electric field. Ultimately, the constructed ACC-TENG was applied as a flexible sensor for human motion monitoring and rehabilitation assessment, achieving highly sensitive detection of subtle motion features such as joint flexion duration, flexion angle, and finger tremors during gripping (with conventional gripping signals reaching 20 V output). This provides innovative material design concepts and technical pathways for the advancement of intelligent rehabilitation medicine.</div></div>","PeriodicalId":394,"journal":{"name":"Nano Energy","volume":"150 ","pages":"Article 111750"},"PeriodicalIF":17.1,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033823","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}
Pub Date : 2026-01-23DOI: 10.1016/j.nanoen.2026.111752
Yuhan Liu , Xueyan Kang , Qianxun Li , Wanran Lin , Ruohong Bian , Peiyuan Ye , Jiongjiong Li , Jiannan Pei , Feng Jiang , Hao Yang , Zhouguang Lu , Zhenghe Xu
In contrast to the widely investigated biomass-derived systems, petroleum-pitch-based hard carbons face persistent challenges in balancing plateau capacity of closed pores and reversible storage efficiency of Na⁺. The difficulty originates from uncontrolled oxygen distribution and nonuniform crosslinking during preoxidation, which lead to undesired coking and limited pore confinement after carbonization. Herein, we introduce a sequential air-acid-air (AAA) pulsed strategy that programs oxygen flux to achieve homogeneous crosslinking in low-softening-point petroleum pitch before carbonization. Short liquid-oxidation pulses with intermediate drying suppress surface densification and guide the controlled uptake and staged removal of oxygenated groups. The resulting microstructure features confined voids and interlocking edge defects with tuned interlayer spacing, enabling fast Na+ transport and plateau storage. Combining high capacity and durability, the optimized AAA-PHC-1400 achieves a Na+ storage capacity of 392.9 mAh g−1 with an 87.4 % initial Coulombic efficiency (ICE) and retains 89.0 % of its original capacity after 2900 cycles, while Na3V2(PO4)2F3 (NVPF)|AAA-PHC-1400 full cells maintain 86.6 % of its original capacity after 100 cycles. By varying the liquid oxidant chemistry and concentration, terminal pre-oxidation temperature and carbonization temperature, we mapped out a practical process window of linking sequence parameters with pore architecture and electrochemical metrics. Mechanistic evidence from in-situ Raman tracking of band shifts during sodiation, together with EPR and XPS signatures of paramagnetic species at low potentials, corroborates a plateau storage pathway arising from confined pores and tuned interlayer spacing. This work elevates pitch pre-oxidation from empirical practice to a sequence-encoded design principle, providing a scalable route of manufacturing high-performance hard carbon anode materials.
与广泛研究的生物质衍生体系相比，石油沥青基硬碳在平衡封闭孔隙的平台容量和Na⁺的可逆存储效率方面面临着持续的挑战。预氧化的难点在于预氧化过程中氧分布不控制和交联不均匀，导致不期望的焦化和碳化后有限的孔隙约束。本文介绍了一种顺序空气-酸-空气（AAA）脉冲策略，通过对氧通量进行编程，在低软化点石油沥青中实现炭化前的均匀交联。短的液体氧化脉冲与中间干燥抑制表面致密化，引导控制摄取和含氧基团的分阶段去除。得到的微观结构具有狭窄的空隙和互锁的边缘缺陷，层间距可调，可实现快速Na+传输和平台存储。优化后的AAA-PHC-1400电池容量为392.9 mAh g-1，初始库仑效率（ICE）为87.4%，循环2900次后仍保持89.0%的原始容量，而Na3V2(PO4)2F3 (NVPF)|AAA-PHC-1400电池在循环100次后仍保持86.6%的原始容量。通过改变液体氧化剂的化学性质和浓度、终端预氧化温度和碳化温度，我们绘制了一个实用的过程窗口，将序列参数与孔隙结构和电化学指标联系起来。来自于原位拉曼光谱对碱化过程中带移的跟踪，以及顺磁物质在低电位下的EPR和XPS特征的机理证据，证实了由受限孔隙和调整层间距引起的平台储存途径。这项工作将沥青预氧化从经验实践提升到序列编码设计原则，为制造高性能硬碳阳极材料提供了可扩展的途径。
{"title":"Controllable homogeneous oxygen crosslinking in pitch for high-performance sodium-ion batteries by sequential air-acid-air oxidation","authors":"Yuhan Liu , Xueyan Kang , Qianxun Li , Wanran Lin , Ruohong Bian , Peiyuan Ye , Jiongjiong Li , Jiannan Pei , Feng Jiang , Hao Yang , Zhouguang Lu , Zhenghe Xu","doi":"10.1016/j.nanoen.2026.111752","DOIUrl":"10.1016/j.nanoen.2026.111752","url":null,"abstract":"<div><div>In contrast to the widely investigated biomass-derived systems, petroleum-pitch-based hard carbons face persistent challenges in balancing plateau capacity of closed pores and reversible storage efficiency of Na⁺. The difficulty originates from uncontrolled oxygen distribution and nonuniform crosslinking during preoxidation, which lead to undesired coking and limited pore confinement after carbonization. Herein, we introduce a sequential air-acid-air (AAA) pulsed strategy that programs oxygen flux to achieve homogeneous crosslinking in low-softening-point petroleum pitch before carbonization. Short liquid-oxidation pulses with intermediate drying suppress surface densification and guide the controlled uptake and staged removal of oxygenated groups. The resulting microstructure features confined voids and interlocking edge defects with tuned interlayer spacing, enabling fast Na<sup>+</sup> transport and plateau storage. Combining high capacity and durability, the optimized AAA-PHC-1400 achieves a Na<sup>+</sup> storage capacity of 392.9 mAh g<sup>−1</sup> with an 87.4 % initial Coulombic efficiency (ICE) and retains 89.0 % of its original capacity after 2900 cycles, while Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub>F<sub>3</sub> (NVPF)|AAA-PHC-1400 full cells maintain 86.6 % of its original capacity after 100 cycles. By varying the liquid oxidant chemistry and concentration, terminal pre-oxidation temperature and carbonization temperature, we mapped out a practical process window of linking sequence parameters with pore architecture and electrochemical metrics. Mechanistic evidence from <em>in-situ</em> Raman tracking of band shifts during sodiation, together with EPR and XPS signatures of paramagnetic species at low potentials, corroborates a plateau storage pathway arising from confined pores and tuned interlayer spacing. This work elevates pitch pre-oxidation from empirical practice to a sequence-encoded design principle, providing a scalable route of manufacturing high-performance hard carbon anode materials.</div></div>","PeriodicalId":394,"journal":{"name":"Nano Energy","volume":"150 ","pages":"Article 111752"},"PeriodicalIF":17.1,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146047867","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}
Growing concerns regarding environmental and energy challenges have substantially contributed in the development of efficient and sustainable PWS (photocatalytic water splitting) techniques has been greatly aided by. Beyond enormous photocatalytic materials, CPs (coordination polymers), which are made from metal nodes and organic linkers, have demonstrated extensive potential because of their structural tunability, suitable Eg (energy bandgap) energies, and ability to enable efficient charge separation. High surface areas, dual active sites, a variety of pore architectures and tunable functionalities are some of the distinctive structural features of CPs that cooperatively enhance light harvesting, enable photoinduced charge carrier separation and transport, and promote efficient interaction between catalytic sites and water molecules. These characteristics play a major role in upgrading the overall functioning of PWS systems. In this review, we first examine the detailed molecular structure of CPs using a computational approach. Following this, the classification of CPs is presented, with a particular emphasis on different metal-centered frameworks, dimensionality, and porosity, along with modification strategies. These metals are of particular interest due to favourable redox properties, variable coordination geometries, and strong light absorption capabilities. Moreover, the role of different ligands and heterojunction in CPs have been explored. The construction of heterostructures based on these metals facilitates efficient charge separation, which is critical for effective photocatalytic applications. Additionally, the mechanism of photocatalytic OWS (overall water splitting) has been discussed, with an emphasis on the fundamental processes of light absorption, photocarriers separation, and surface redox reactions involved in H2 and O2 evolution. Besides this, we also provided a brief overview of the role of interfacial defects, active sites, and co-catalysts, as well as the unique advantages of CPs in photocatalysis. In addition, recent applications of CP-based photocatalysts for PWS are highlighted, with particular attention to mechanistic insights and performance. Finally, the review summarised by outlining the key disputes and future research directions for advancing CP-based photocatalysts in OWS applications.
{"title":"Emerging coordination polymer photocatalysts for water splitting: From mechanistic insights and design strategies to application roadmap","authors":"Akanksha Chauhan , Rohit Kumar , Pankaj Raizada , Khoa Dang Dang , Quyet Van Le , Aftab Aslam Parwaz Khan , Pardeep Singh , Van-Huy Nguyen , Anita Sudhaik","doi":"10.1016/j.nanoen.2026.111749","DOIUrl":"10.1016/j.nanoen.2026.111749","url":null,"abstract":"<div><div>Growing concerns regarding environmental and energy challenges have substantially contributed in the development of efficient and sustainable PWS (photocatalytic water splitting) techniques has been greatly aided by. Beyond enormous photocatalytic materials, CPs (coordination polymers), which are made from metal nodes and organic linkers, have demonstrated extensive potential because of their structural tunability, suitable E<sub>g</sub> (energy bandgap) energies, and ability to enable efficient charge separation. High surface areas, dual active sites, a variety of pore architectures and tunable functionalities are some of the distinctive structural features of CPs that cooperatively enhance light harvesting, enable photoinduced charge carrier separation and transport, and promote efficient interaction between catalytic sites and water molecules. These characteristics play a major role in upgrading the overall functioning of PWS systems. In this review, we first examine the detailed molecular structure of CPs using a computational approach. Following this, the classification of CPs is presented, with a particular emphasis on different metal-centered frameworks, dimensionality, and porosity, along with modification strategies. These metals are of particular interest due to favourable redox properties, variable coordination geometries, and strong light absorption capabilities. Moreover, the role of different ligands and heterojunction in CPs have been explored. The construction of heterostructures based on these metals facilitates efficient charge separation, which is critical for effective photocatalytic applications. Additionally, the mechanism of photocatalytic OWS (overall water splitting) has been discussed, with an emphasis on the fundamental processes of light absorption, photocarriers separation, and surface redox reactions involved in H<sub>2</sub> and O<sub>2</sub> evolution. Besides this, we also provided a brief overview of the role of interfacial defects, active sites, and co-catalysts, as well as the unique advantages of CPs in photocatalysis. In addition, recent applications of CP-based photocatalysts for PWS are highlighted, with particular attention to mechanistic insights and performance. Finally, the review summarised by outlining the key disputes and future research directions for advancing CP-based photocatalysts in OWS applications.</div></div>","PeriodicalId":394,"journal":{"name":"Nano Energy","volume":"149 ","pages":"Article 111749"},"PeriodicalIF":17.1,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033821","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}
Pub Date : 2026-01-21DOI: 10.1016/j.nanoen.2026.111725
Mengyao Li , Xifei Li , Jun Li , Ruixian Duan , Xuexia Song , Guiqiang Cao , Junqian Liu , Jingjing Wang , Wenbin Li
Lithium/carbon fluoride (Li/CFx) primary batteries suffer from severe voltage hysteresis and rapid capacity degradation at high current densities, presenting significant challenges for achieving superior rate performance. This work proposes a modification strategy for fabricating an amorphous MnO2-anchored CF composite cathode via rapid in-situ reduction. The amorphous MnO2 provides abundant active sites and diffusion channels on the CF substrate surface, thereby improving the utilization efficiency of the conversion reaction. Compared with CF and c-MnO2@CF, a-MnO2@CF-2 exhibits enhanced electrical conductivity, effectively mitigating voltage hysteresis and delivering superior electrochemical performance under high-rate discharge conditions. Experimental results demonstrate that a-MnO2@CF-2 achieves a maximum energy density of 2.05 × 103 Wh kg−1 at 0.1 C. Compared with pristine CF, the discharge rate performance improves from 2 C to 15 C, while the power density increases from 3.11 kW kg−1 to 27.9 kW kg−1. Ex situ XPS and XRD analyses reveal an “in situ electrochemical activation” mechanism: a-MnO2 preferentially undergoes lithiation at 2.5 V to form highly conductive LiXMnO2 networks, which reduce interfacial resistance and activate CF discharge at elevated potentials (>2.5 V). DRT analysis reveals that the abundant surface defects of amorphous MnO2 facilitate the Li+ transport pathways. Additionally, theoretical calculations reveal that, compared with c-MnO2@CF, the d orbital of Mn in a-MnO2@CF is closer to the Fermi level. This shift leads to greater electron transfer from MnO2, to CF, and consequently reduces the overlap between C and F p-orbitals in the CF component of the composite. This reduction in orbital overlap weakens C-F p-p orbital hybridization, thereby enhancing the semi-ionic character of the C-F bonds. This work demonstrates a highly feasible chemical modification strategy for constructing composite cathodes, enabling significant performance improvements in Li/CFX primary batteries.
{"title":"Engineering d-band center of MnO2 to promote semi-ionic C-F bonding for high-rate Li-CFx batteries","authors":"Mengyao Li , Xifei Li , Jun Li , Ruixian Duan , Xuexia Song , Guiqiang Cao , Junqian Liu , Jingjing Wang , Wenbin Li","doi":"10.1016/j.nanoen.2026.111725","DOIUrl":"10.1016/j.nanoen.2026.111725","url":null,"abstract":"<div><div>Lithium/carbon fluoride (Li/CF<sub>x</sub>) primary batteries suffer from severe voltage hysteresis and rapid capacity degradation at high current densities, presenting significant challenges for achieving superior rate performance. This work proposes a modification strategy for fabricating an amorphous MnO<sub>2</sub>-anchored CF composite cathode via rapid in-situ reduction. The amorphous MnO<sub>2</sub> provides abundant active sites and diffusion channels on the CF substrate surface, thereby improving the utilization efficiency of the conversion reaction. Compared with CF and c-MnO<sub>2</sub>@CF, a-MnO<sub>2</sub>@CF-2 exhibits enhanced electrical conductivity, effectively mitigating voltage hysteresis and delivering superior electrochemical performance under high-rate discharge conditions. Experimental results demonstrate that a-MnO<sub>2</sub>@CF-2 achieves a maximum energy density of 2.05 × 10<sup>3</sup> Wh kg<sup>−1</sup> at 0.1 C. Compared with pristine CF, the discharge rate performance improves from 2 C to 15 C, while the power density increases from 3.11 kW kg<sup>−1</sup> to 27.9 kW kg<sup>−1</sup>. Ex situ XPS and XRD analyses reveal an “in situ electrochemical activation” mechanism: a-MnO<sub>2</sub> preferentially undergoes lithiation at 2.5 V to form highly conductive Li<sub>X</sub>MnO<sub>2</sub> networks, which reduce interfacial resistance and activate CF discharge at elevated potentials (>2.5 V). DRT analysis reveals that the abundant surface defects of amorphous MnO<sub>2</sub> facilitate the Li<sup>+</sup> transport pathways. Additionally, theoretical calculations reveal that, compared with c-MnO<sub>2</sub>@CF, the d orbital of Mn in a-MnO<sub>2</sub>@CF is closer to the Fermi level. This shift leads to greater electron transfer from MnO<sub>2</sub>, to CF, and consequently reduces the overlap between C and F <em>p</em>-orbitals in the CF component of the composite. This reduction in orbital overlap weakens C-F <em>p-p</em> orbital hybridization, thereby enhancing the semi-ionic character of the C-F bonds. This work demonstrates a highly feasible chemical modification strategy for constructing composite cathodes, enabling significant performance improvements in Li/CF<sub>X</sub> primary batteries.</div></div>","PeriodicalId":394,"journal":{"name":"Nano Energy","volume":"149 ","pages":"Article 111725"},"PeriodicalIF":17.1,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014772","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}
Pub Date : 2026-01-20DOI: 10.1016/j.nanoen.2026.111746
SeungJe Lee , Sangwon Nam , Jin Il Jang , Yuna Kwon , Huiyeong Kang , Yong Jae Lee , Keyong Nam Lee , Gang Yeol Yoo , Changwook Kim , Hyun Min Cho , Hyung Min Kim , Heesun Yang , Jae Kyu Song , Young Rag Do
High costs and efficiency degradation from surface defects in small-chip top-down fabrication impede micro-light-emitting diodes commercialization. To address this, we introduce Ultraviolet-irradiated moisture adsorption as a novel top-down approach, integrated with defect-reducing etching, to enhance ultra-small micro-light-emitting diodes. Ultraviolet-irradiated moisture adsorption is crucial: it effectively reduces surface strain caused by dangling and oxidized bonds through moisture adsorption, thereby facilitating significant delayed luminescence via detrapping from shallow trap states. This mechanism profoundly improves the internal quantum efficiency of ultra- micro-light-emitting diodes and the external quantum efficiency of light-emitting diode devices. Our approach, including defect-removal and strain-alleviation, yielded highly promising results for sub-5 μm fin- light-emitting diodes, achieving an internal quantum efficiency of 70.9 % and an external quantum efficiency of 16.5 %. By actively leveraging delayed luminescence through Ultraviolet-irradiated moisture adsorption, these methods offer a cost-effective and highly efficient solution, holding great potential for future micro-light-emitting diodes display commercialization.
{"title":"Delayed luminescence in sub-5 μm InGaN/GaN fin-LEDs with efficiency enhancement by UV-induced moisture adsorption","authors":"SeungJe Lee , Sangwon Nam , Jin Il Jang , Yuna Kwon , Huiyeong Kang , Yong Jae Lee , Keyong Nam Lee , Gang Yeol Yoo , Changwook Kim , Hyun Min Cho , Hyung Min Kim , Heesun Yang , Jae Kyu Song , Young Rag Do","doi":"10.1016/j.nanoen.2026.111746","DOIUrl":"10.1016/j.nanoen.2026.111746","url":null,"abstract":"<div><div>High costs and efficiency degradation from surface defects in small-chip top-down fabrication impede micro-light-emitting diodes commercialization. To address this, we introduce Ultraviolet-irradiated moisture adsorption as a novel top-down approach, integrated with defect-reducing etching, to enhance ultra-small micro-light-emitting diodes. Ultraviolet-irradiated moisture adsorption is crucial: it effectively reduces surface strain caused by dangling and oxidized bonds through moisture adsorption, thereby facilitating significant delayed luminescence <em>via</em> detrapping from shallow trap states. This mechanism profoundly improves the internal quantum efficiency of ultra- micro-light-emitting diodes and the external quantum efficiency of light-emitting diode devices. Our approach, including defect-removal and strain-alleviation, yielded highly promising results for sub-5 μm fin- light-emitting diodes, achieving an internal quantum efficiency of 70.9 % and an external quantum efficiency of 16.5 %. By actively leveraging delayed luminescence through Ultraviolet-irradiated moisture adsorption, these methods offer a cost-effective and highly efficient solution, holding great potential for future micro-light-emitting diodes display commercialization.</div></div>","PeriodicalId":394,"journal":{"name":"Nano Energy","volume":"149 ","pages":"Article 111746"},"PeriodicalIF":17.1,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014738","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}
Pub Date : 2026-01-20DOI: 10.1016/j.nanoen.2026.111747
Ruiwen Xie , Maximilian Mellin , Wolfram Jaegermann , Jan P. Hofmann , Frank M.F. de Groot , Hongbin Zhang
Understanding the evolution of the physicochemical bulk properties during the Li deintercalation process is critical for optimizing battery cathode materials. In this study, we combine X-ray photoelectron spectroscopy (XPS), density functional theory plus dynamical mean-field theory (DFT+DMFT), and charge transfer multiplet (CTM) model to investigate how hybridization between transition metal (TM) 3 and oxygen 2 orbitals evolves upon Li deintercalation. Based on the presented approach combining theoretical calculations and experimental studies of pristine and deintercalated cathodes, two key aspects of ion batteries are examined: i) the detailed electronic structure and involved changes with deintercalation associated with the charge compensation mechanism, and ii) the precise experimental analysis of XPS data which are dominated by charge transfer coupled to final-state effects affecting the satellite structure. As main result for the investigated Li–TM oxides, the results indicate that the electron transfer coupled to the Li-ion migration does not follow a rigid band model but is influenced by changes in TM 3 and O 2 states hybridization. This integrated approach suggests that 2 XPS satellite peak intensity of TM is sensitive to changes in redox chemistry, providing an indirect experimental descriptor of cathode redox behavior and guiding the design of more efficient battery materials.
{"title":"Redox chemistry of LiCoO2, LiNiO2, and LiNi1/3Mn1/3Co1/3O2 cathodes: Deduced via XPS, DFT+DMFT, and charge transfer multiplet simulations","authors":"Ruiwen Xie , Maximilian Mellin , Wolfram Jaegermann , Jan P. Hofmann , Frank M.F. de Groot , Hongbin Zhang","doi":"10.1016/j.nanoen.2026.111747","DOIUrl":"10.1016/j.nanoen.2026.111747","url":null,"abstract":"<div><div>Understanding the evolution of the physicochemical bulk properties during the Li deintercalation process is critical for optimizing battery cathode materials. In this study, we combine X-ray photoelectron spectroscopy (XPS), density functional theory plus dynamical mean-field theory (DFT+DMFT), and charge transfer multiplet (CTM) model to investigate how hybridization between transition metal (TM) 3<span><math><mi>d</mi></math></span> and oxygen 2<span><math><mi>p</mi></math></span> orbitals evolves upon Li deintercalation. Based on the presented approach combining theoretical calculations and experimental studies of pristine and deintercalated cathodes, two key aspects of ion batteries are examined: i) the detailed electronic structure and involved changes with deintercalation associated with the charge compensation mechanism, and ii) the precise experimental analysis of XPS data which are dominated by charge transfer coupled to final-state effects affecting the satellite structure. As main result for the investigated Li–TM oxides, the results indicate that the electron transfer coupled to the Li<span><math><msup><mrow></mrow><mrow><mo>+</mo></mrow></msup></math></span>-ion migration does not follow a rigid band model but is influenced by changes in TM 3<span><math><mi>d</mi></math></span> and O 2<span><math><mi>p</mi></math></span> states hybridization. This integrated approach suggests that 2<span><math><mi>p</mi></math></span> XPS satellite peak intensity of TM is sensitive to changes in redox chemistry, providing an indirect experimental descriptor of cathode redox behavior and guiding the design of more efficient battery materials.</div></div>","PeriodicalId":394,"journal":{"name":"Nano Energy","volume":"149 ","pages":"Article 111747"},"PeriodicalIF":17.1,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014737","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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