Pub Date : 2026-01-13DOI: 10.1016/j.electacta.2026.148203
Neuryelen dos Santos Bandeira, Lucas Moreira Silva, William Reis de Araujo, João Paulo Vita Damasceno
{"title":"Fullerenol as electrode modifier for improving proton transfer and mitigating byproducts in the electrochemical detection of hydroquinone","authors":"Neuryelen dos Santos Bandeira, Lucas Moreira Silva, William Reis de Araujo, João Paulo Vita Damasceno","doi":"10.1016/j.electacta.2026.148203","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148203","url":null,"abstract":"","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"30 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962735","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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 : 2026-01-13DOI: 10.1016/j.electacta.2026.148190
Jia-Shiun Tu, Chun-Pei Cho
This study systematically investigates the effect of nitrogen plasma modification on the electrochemical performance of multilayer Ti3C2Tx in an aqueous l-cysteine containing electrolyte. By varying the plasma duration from 0 min to 20 min, the 10 min condition yielded the best overall response among the tested durations, where an optimal degree of near-surface activation (electrochemically accessible sites/defects) was introduced without substantial disruption of the Ti–C–Ti conductive framework. This balanced interfacial state enhanced pseudocapacitance and ion accessibility to near-surface sites, resulting in the highest specific capacitance (∼67 F·g⁻1 at 2 mV·s⁻1) and a b value of 0.67, consistent with mixed charge-storage kinetics featuring a predominantly surface-controlled contribution with partial diffusion/transport limitation. The electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy results supported this interpretation, showing more favorable interfacial impedance/charge-transfer characteristics, a reduction of loosely bound/unstable fluorine species, and moderate surface-chemistry evolution after the 10-min treatment, whereas prolonged plasma exposure (20 min) induced over-etching/over-oxidation, structural degradation, and increased transport limitations. Therefore, careful control of plasma activation duration is crucial for achieving an optimal balance between surface activity and ion transport, providing an experimentally grounded basis for tuning MXene-electrolyte interfaces in aqueous supercapacitor systems.
{"title":"Enhanced electrochemical energy storage performance of multilayer Ti3C2Tx electrodes via nitrogen plasma modification in l-cysteine electrolyte","authors":"Jia-Shiun Tu, Chun-Pei Cho","doi":"10.1016/j.electacta.2026.148190","DOIUrl":"10.1016/j.electacta.2026.148190","url":null,"abstract":"<div><div>This study systematically investigates the effect of nitrogen plasma modification on the electrochemical performance of multilayer Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> in an aqueous <span>l</span>-cysteine containing electrolyte. By varying the plasma duration from 0 min to 20 min, the 10 min condition yielded the best overall response among the tested durations, where an optimal degree of near-surface activation (electrochemically accessible sites/defects) was introduced without substantial disruption of the Ti–C–Ti conductive framework. This balanced interfacial state enhanced pseudocapacitance and ion accessibility to near-surface sites, resulting in the highest specific capacitance (∼67 F·g⁻<sup>1</sup> at 2 mV·s⁻<sup>1</sup>) and a b value of 0.67, consistent with mixed charge-storage kinetics featuring a predominantly surface-controlled contribution with partial diffusion/transport limitation. The electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy results supported this interpretation, showing more favorable interfacial impedance/charge-transfer characteristics, a reduction of loosely bound<strong>/</strong>unstable fluorine species, and moderate surface-chemistry evolution after the 10-min treatment, whereas prolonged plasma exposure (20 min) induced over-etching/over-oxidation, structural degradation, and increased transport limitations. Therefore, careful control of plasma activation duration is crucial for achieving an optimal balance between surface activity and ion transport, providing an experimentally grounded basis for tuning MXene-electrolyte interfaces in aqueous supercapacitor systems.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"551 ","pages":"Article 148190"},"PeriodicalIF":5.6,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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 : 2026-01-13DOI: 10.1016/j.electacta.2026.148196
Bhakti G. Thali, Dhiraj S. Agrahari, Rajesh M. Kamble
In this research, a novel material is presented that combines glucose sensing with capacitive functionalities, offering a promising solution to the challenges posed by glucose monitoring in medical technologies. Additionally, it addresses the urgent requirement for innovative energy storage devices needed to support the growing demands of modern medical systems. Researchers are intrigued by hybrid nanocomposite (NC) materials due to their high conductivity, large surface area, and stability. In this study, a simple and facile ultrasound method was used to incorporate Barium strontium titanate (BSTO) into the graphene nanosheets (GNS) matrix. The fabricated sensor is sensitive to glucose concentrations ranging from 0.5 to 14 mM with limit of detection of 0.35 mM, emphasizing robust stability. Furthermore, the BSTO/GNS delivered specific capacitance (Cs) of 803.20 F/g and specific capacity (Csp) of 156.85 mAh/g at 1 A/g employing three electrode configuration. In tests conducted with a two electrode system, the BSTO/GNS//AC device is found to deliver a Cs of 172.89 F/g at an applied current of 1 A/g. Additionally, after 10,000 cycles, the device maintained 83.26% of its original capacitance and showed coulombic retention of 93.15% for charge transfer efficiency, demonstrating robust performance during extended operation. At a current density of 1 A/g, the device demonstrated a power density (P) reaching 850.00 W/kg alongside an energy density (E) of 69.39 Wh/kg. This indicates its capability to deliver significant power output while storing a substantial amount of energy within the given operating conditions. The BSTO/GNS electrode could be used for dual purpose in glucose sensing and supercapacitors (SCs), making it a versatile material with applications in medical, food, electronics, transportation, and energy.
在这项研究中，提出了一种结合了葡萄糖传感和电容功能的新型材料，为医疗技术中葡萄糖监测带来的挑战提供了一个有希望的解决方案。此外，它还解决了支持现代医疗系统日益增长的需求所需的创新能量存储设备的迫切需求。混合纳米复合材料（NC）由于其高导电性、大表面积和稳定性而引起了研究人员的兴趣。在这项研究中，采用一种简单易行的超声方法将钛酸锶钡（BSTO）掺入石墨烯纳米片（GNS）基质中。该传感器对0.5 ~ 14 mM的葡萄糖浓度敏感，检测限为0.35 mM，具有很强的稳定性。此外，采用三电极配置，BSTO/GNS在1 A/g时的比电容（Cs）为803.20 F/g，比容量（Csp）为156.85 mAh/g。在用双电极系统进行的测试中，发现BSTO/GNS/ AC装置在施加电流为1 a /g时提供了172.89 F/g的Cs。此外，经过10,000次循环后，器件保持了原始电容的83.26%，电荷转移效率的库仑保留率为93.15%，在长时间运行中表现出稳健的性能。在电流密度为1 a /g时，该器件的功率密度(P)达到850.00 W/kg，能量密度(E)达到69.39 Wh/kg。这表明它的能力提供显著的功率输出，同时在给定的操作条件下存储大量的能量。BSTO/GNS电极可用于葡萄糖传感和超级电容器（SCs）的双重用途，使其成为一种多功能材料，可用于医疗，食品，电子，运输和能源。
{"title":"Fabrication of barium strontium titanate encapsulated with graphene nanosheets for bifunctional sensor and energy storage application","authors":"Bhakti G. Thali, Dhiraj S. Agrahari, Rajesh M. Kamble","doi":"10.1016/j.electacta.2026.148196","DOIUrl":"10.1016/j.electacta.2026.148196","url":null,"abstract":"<div><div>In this research, a novel material is presented that combines glucose sensing with capacitive functionalities, offering a promising solution to the challenges posed by glucose monitoring in medical technologies. Additionally, it addresses the urgent requirement for innovative energy storage devices needed to support the growing demands of modern medical systems. Researchers are intrigued by hybrid nanocomposite (NC) materials due to their high conductivity, large surface area, and stability. In this study, a simple and facile ultrasound method was used to incorporate Barium strontium titanate (BSTO) into the graphene nanosheets (GNS) matrix. The fabricated sensor is sensitive to glucose concentrations ranging from 0.5 to 14 mM with limit of detection of 0.35 mM, emphasizing robust stability. Furthermore, the BSTO/GNS delivered specific capacitance (C<sub>s</sub>) of 803.20 F/g and specific capacity (C<sub>sp</sub>) of 156.85 mAh/g at 1 A/g employing three electrode configuration. In tests conducted with a two electrode system, the BSTO/GNS//AC device is found to deliver a C<sub>s</sub> of 172.89 F/g at an applied current of 1 A/g. Additionally, after 10,000 cycles, the device maintained 83.26% of its original capacitance and showed coulombic retention of 93.15% for charge transfer efficiency, demonstrating robust performance during extended operation. At a current density of 1 A/g, the device demonstrated a power density (P) reaching 850.00 W/kg alongside an energy density (E) of 69.39 Wh/kg. This indicates its capability to deliver significant power output while storing a substantial amount of energy within the given operating conditions. The BSTO/GNS electrode could be used for dual purpose in glucose sensing and supercapacitors (SCs), making it a versatile material with applications in medical, food, electronics, transportation, and energy.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"551 ","pages":"Article 148196"},"PeriodicalIF":5.6,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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 : 2026-01-13DOI: 10.1016/j.electacta.2026.148207
Luyao Zhang, Shengyue Zhang, Hongjiao Chen, Xiangyu Wang, Bin Hui
The sluggish oxygen reduction reaction (ORR) kinetics severely restricts the performance and commercialization of Zn-air batteries (ZABs). Herein, a facile and scalable approach is proposed to synthesize a powerful N, B co-doped carbon electrocatalyst (NBCW-900) from paulownia wood (PW) biomass. The delignified treatment of natural wood optimized pores structures and made full exposure of hydroxyl sites, achieving a high-loading level of N and B heteroatoms (N: 10.3 at. % and B: 10.6 at. %). The high-density active sites with N-B coordination, pyridinic N, and graphitic N contributed to high ORR activity and selectivity. The NBCW-900 sample showed a high onset potential of 0.970 V and high half-wave potential of 0.849 V, and had a low Tafel slope of 92.57 mV dec−1. The liquid ZABs achieved an open-circuit voltage of 1.478 V and a high peak power density of 188.82 mW cm−2. The assembled flexible ZABs delivered a voltage of 1.410 V, operated stably for 10 h, and endured over 40 h cycling under various bending angles ranged from 0° to 180°. This work offers a feasible strategy for developing wood-derived metal-free carbon electrocatalysts, promoting the commercialization progress of sustainable ZABs.
{"title":"Design on high-content N and B heteroatoms embedded in wood-derived carbon for boosting the performances of liquid and flexible Zn-air batteries","authors":"Luyao Zhang, Shengyue Zhang, Hongjiao Chen, Xiangyu Wang, Bin Hui","doi":"10.1016/j.electacta.2026.148207","DOIUrl":"10.1016/j.electacta.2026.148207","url":null,"abstract":"<div><div>The sluggish oxygen reduction reaction (ORR) kinetics severely restricts the performance and commercialization of Zn-air batteries (ZABs). Herein, a facile and scalable approach is proposed to synthesize a powerful N, B co-doped carbon electrocatalyst (NBCW-900) from paulownia wood (PW) biomass. The delignified treatment of natural wood optimized pores structures and made full exposure of hydroxyl sites, achieving a high-loading level of N and B heteroatoms (N: 10.3 at. % and B: 10.6 at. %). The high-density active sites with N-B coordination, pyridinic N, and graphitic N contributed to high ORR activity and selectivity. The NBCW-900 sample showed a high onset potential of 0.970 V and high half-wave potential of 0.849 V, and had a low Tafel slope of 92.57 mV dec<sup>−1</sup>. The liquid ZABs achieved an open-circuit voltage of 1.478 V and a high peak power density of 188.82 mW cm<sup>−2</sup>. The assembled flexible ZABs delivered a voltage of 1.410 V, operated stably for 10 h, and endured over 40 h cycling under various bending angles ranged from 0° to 180°. This work offers a feasible strategy for developing wood-derived metal-free carbon electrocatalysts, promoting the commercialization progress of sustainable ZABs.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"551 ","pages":"Article 148207"},"PeriodicalIF":5.6,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962107","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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 : 2026-01-12DOI: 10.1016/j.electacta.2026.148182
Yihang Song, HanYu Zhou, Weijia Wang, Lijun Yang, Xiaoze Du
All-solid-state sodium batteries are considered a promising technology for large-scale energy storage owing to their intrinsic safety and the natural abundance of sodium resources. Although high ionic conductivity is exhibited by sulfide-based systems such as Na3SbS4, challenges in achieving a balance between ionic transport and electrochemical stability remain. In this study, a synergistic cation-anion co-doping strategy is proposed to overcome the intrinsic trade-off of single-element doping. By using first-principles density functional theory combined with ab initio molecular dynamics, the structural, ionic, and electronic properties of Na3SbS4 co-doped with M6+ (M = W, Mo) and X− (X = F, Cl, Br, I) are systematically investigated. Based on comprehensive analysis, the WCl and WBr co-doped systems are found to exhibit the most balanced performance among all candidates. In these systems, wide electronic band gaps are maintained, ensuring excellent electronic insulation. Simultaneously, competitive room-temperature ionic conductivities, associated with low activation energies, are also achieved. This optimal balance is attributed to co-doping–induced lattice distortions. Through these distortions Na+ migration pathways are reconstructed into highly connected diffusion networks, while structural integrity and electronic stability are preserved. In addition to bulk transport properties, first-principles interface calculations reveal favorable interfacial compatibility between Na metal and WCl/WBr-co-doped Na3SbS4, characterized by stable interfacial adhesion and localized charge redistribution, highlighting their practical applicability in all-solid-state sodium batteries. In contrast, Mo-based and F/I-containing systems are characterized by either narrower band gaps or excessive migration barriers at the current 6% doping concentration. However, improved performance may be exhibited at lower concentrations, which can be attributed to reduced defect interaction and impurity-derived states overlap. Overall, the intrinsic structure–property relationships among lattice distortion, migration dimensionality, and electronic structure in co-doped Na3SbS4 are elucidated in this work. It is demonstrated that synergistic anion–cation co-doping is an effective strategy to achieve concurrent enhancement of ionic conductivity and electrochemical stability. Through these findings, theoretical guidance is provided for the rational design of next-generation high-performance sulfide solid-state electrolytes.
{"title":"A Mechanistic Study of Cation-Anion Co-doped Sulfide Solid-State Electrolytes for Sodium-ion Batteries","authors":"Yihang Song, HanYu Zhou, Weijia Wang, Lijun Yang, Xiaoze Du","doi":"10.1016/j.electacta.2026.148182","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148182","url":null,"abstract":"All-solid-state sodium batteries are considered a promising technology for large-scale energy storage owing to their intrinsic safety and the natural abundance of sodium resources. Although high ionic conductivity is exhibited by sulfide-based systems such as Na<ce:inf loc=\"post\">3</ce:inf>SbS<ce:inf loc=\"post\">4</ce:inf>, challenges in achieving a balance between ionic transport and electrochemical stability remain. In this study, a synergistic cation-anion co-doping strategy is proposed to overcome the intrinsic trade-off of single-element doping. By using first-principles density functional theory combined with ab initio molecular dynamics, the structural, ionic, and electronic properties of Na<ce:inf loc=\"post\">3</ce:inf>SbS<ce:inf loc=\"post\">4</ce:inf> co-doped with M<ce:sup loc=\"post\">6+</ce:sup> (M = W, Mo) and X<ce:sup loc=\"post\">−</ce:sup> (X = F, Cl, Br, I) are systematically investigated. Based on comprehensive analysis, the WCl and WBr co-doped systems are found to exhibit the most balanced performance among all candidates. In these systems, wide electronic band gaps are maintained, ensuring excellent electronic insulation. Simultaneously, competitive room-temperature ionic conductivities, associated with low activation energies, are also achieved. This optimal balance is attributed to co-doping–induced lattice distortions. Through these distortions Na<ce:sup loc=\"post\">+</ce:sup> migration pathways are reconstructed into highly connected diffusion networks, while structural integrity and electronic stability are preserved. In addition to bulk transport properties, first-principles interface calculations reveal favorable interfacial compatibility between Na metal and WCl/WBr-co-doped Na<ce:inf loc=\"post\">3</ce:inf>SbS<ce:inf loc=\"post\">4</ce:inf>, characterized by stable interfacial adhesion and localized charge redistribution, highlighting their practical applicability in all-solid-state sodium batteries. In contrast, Mo-based and F/I-containing systems are characterized by either narrower band gaps or excessive migration barriers at the current 6% doping concentration. However, improved performance may be exhibited at lower concentrations, which can be attributed to reduced defect interaction and impurity-derived states overlap. Overall, the intrinsic structure–property relationships among lattice distortion, migration dimensionality, and electronic structure in co-doped Na<ce:inf loc=\"post\">3</ce:inf>SbS<ce:inf loc=\"post\">4</ce:inf> are elucidated in this work. It is demonstrated that synergistic anion–cation co-doping is an effective strategy to achieve concurrent enhancement of ionic conductivity and electrochemical stability. Through these findings, theoretical guidance is provided for the rational design of next-generation high-performance sulfide solid-state electrolytes.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"40 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956707","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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 : 2026-01-12DOI: 10.1016/j.electacta.2026.148178
Wei Chen , Shiyu Fu , Di Wu , Zhengchun Liu
Clostridium difficile infection (CDI) has become a pressing global health challenge, with increasing incidence, recurrence, and mortality in both healthcare and community settings. The pathogen's escalating virulence and antimicrobial resistance underscore the urgent need for rapid, accurate diagnostics to guide treatment and prevent spread. In this paper, we developed an ultrasensitive electrochemical aptasensor based on DNA walker and redox capacitor (catechol (Cat)-chitosan (Chi)-dual redox mediator (1,1′-ferrocene dimethanol (Fc)-hexaammineruthenium (Ⅲ) chloride (Ru3+)) signal amplification strategy for the detection of CD toxin B (TcdB). By optimizing the biotinylated walking strand(WS):the blocking strand(BS) hybridization ratio (1:2), the DNA walker (the magnetic bead(MB)@the double stranded (DS)@the biotinylated hairpin-structured (HP)) was successfully assembled, and its assembly was verified using UV–Vis absorption spectroscopy, Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), dynamic light scattering (DLS), and zeta potential analysis. The proposed electrochemical aptasensor exhibited an ultralow detection limit of 0.43 pg/mL for TcdB, with a linear range of 1∼243 pg/mL (R²=0.996), along with excellent selectivity, satisfactory stability and reliable regeneration. The proposed electrochemical aptasensor can be used to detect stool samples (the spiked recovery rate was 95.33%∼105.48%) due to the use of MB for separation, thus avoiding the influence of complex components in the stool samples and laying the foundation for its clinical application.
{"title":"Construction of an electrochemical aptasensor based on DNA walker and redox capacitor for ultrasensitive detection of Clostridium difficile toxin B","authors":"Wei Chen , Shiyu Fu , Di Wu , Zhengchun Liu","doi":"10.1016/j.electacta.2026.148178","DOIUrl":"10.1016/j.electacta.2026.148178","url":null,"abstract":"<div><div><em>Clostridium difficile</em> infection (CDI) has become a pressing global health challenge, with increasing incidence, recurrence, and mortality in both healthcare and community settings. The pathogen's escalating virulence and antimicrobial resistance underscore the urgent need for rapid, accurate diagnostics to guide treatment and prevent spread. In this paper, we developed an ultrasensitive electrochemical aptasensor based on DNA walker and redox capacitor (catechol (Cat)-chitosan (Chi)-dual redox mediator (1,1′-ferrocene dimethanol (Fc)-hexaammineruthenium (Ⅲ) chloride (Ru<sup>3+</sup>)) signal amplification strategy for the detection of CD toxin B (TcdB). By optimizing the biotinylated walking strand(WS):the blocking strand(BS) hybridization ratio (1:2), the DNA walker (the magnetic bead(MB)@the double stranded (DS)@the biotinylated hairpin-structured (HP)) was successfully assembled, and its assembly was verified using UV–Vis absorption spectroscopy, Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), dynamic light scattering (DLS), and zeta potential analysis. The proposed electrochemical aptasensor exhibited an ultralow detection limit of 0.43 pg/mL for TcdB, with a linear range of 1∼243 pg/mL (R²=0.996), along with excellent selectivity, satisfactory stability and reliable regeneration. The proposed electrochemical aptasensor can be used to detect stool samples (the spiked recovery rate was 95.33%∼105.48%) due to the use of MB for separation, thus avoiding the influence of complex components in the stool samples and laying the foundation for its clinical application.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"551 ","pages":"Article 148178"},"PeriodicalIF":5.6,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956231","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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 : 2026-01-12DOI: 10.1016/j.electacta.2026.148187
Rui Huang , Rongjin Lin , Aoyu Ren , Funing Zhao , Changyong Zhao , Runcang Sun , Xiaofei Yang , Xuejie Gao
Solid-state electrolytes (SSEs) are promising for high-energy-density lithium metal batteries (LMBs), yet they typically suffer from low ionic conductivity and unstable electrode interfaces. To tackle these issues concurrently, here, we designed a cyclodextrin-incorporated PVDF hybrid electrolyte (CD@PVDF). Its superior performance originates from a synergistic mechanism that integrates dynamic hydrogen-bonding networks with effective anion confinement. Specifically, the abundant hydroxyl groups of CD form strong OH···F hydrogen bonds with PVDF, facilitating a phase transition from α- to β-phase and establishing a dynamically cross-linked polymer framework. The framework greatly improves the mobility of polymer segments and facilitates fast Li+ transport along the chains. Meanwhile, the hydrophobic cavities of CD immobilize TFSI- anions via host-guest interactions, generating localized high-concentration Li+ domains that optimize the ion transport pathway and lower the activation barrier for migration. As a result, the CD@PVDF electrolyte achieves a high ionic conductivity of 1.93 × 10–4 S cm-1, a low activation energy of 0.35 eV, and a Li+ transference number of 0.91. The Li-Li symmetric cells employing CD@PVDF demonstrate ultrastable cycling exceeding 4000 h with a low overpotential of 84 mV at 1 mA cm-2 and 1 mAh cm-2. Moreover, Li-LFP full cells delivered an excellent capacity retention with the capacity retention of 98.5 % over 3000 cycles at 5 C. This work highlighted a synergistic design strategy that combined hydrogen-bonding engineering with anion confinement, offering valuable insights into the development of safe and high-performance SPEs for next-generation LMBs.
固态电解质（sse）在高能量密度锂金属电池（lmb）中很有前景，但它们通常存在离子电导率低和电极界面不稳定的问题。为了同时解决这些问题，我们设计了一种含环糊精的PVDF混合电解质（CD@PVDF）。其优越的性能源于一种将动态氢键网络与有效的阴离子约束相结合的协同机制。具体来说，CD丰富的羟基与PVDF形成强的O-H··F氢键，促进了从α-相到β-相的转变，建立了动态交联的聚合物框架。该框架极大地提高了聚合物段的迁移率，促进了Li+沿链的快速迁移。同时，CD的疏水空腔通过主-客体相互作用固定TFSI-阴离子，产生局部高浓度Li+结构域，优化离子传输途径，降低迁移的激活屏障。结果表明，CD@PVDF电解质具有1.93 × 10-4 S cm-1的高离子电导率、0.35 eV的低活化能和0.91的Li+转移数。采用CD@PVDF的锂离子对称电池在1ma cm-2和1mah cm-2下具有84 mV的低过电位，可实现超过4000 h的超稳定循环。此外，Li-LFP全电池在5℃下3000次循环时的容量保持率为98.5%。这项工作强调了氢键工程与阴离子约束相结合的协同设计策略，为下一代lmb安全和高性能spe的开发提供了有价值的见解。
{"title":"Solid-state electrolytes with synergistic hydrogen-bonding and anion-confinement for stable lithium metal batteries","authors":"Rui Huang , Rongjin Lin , Aoyu Ren , Funing Zhao , Changyong Zhao , Runcang Sun , Xiaofei Yang , Xuejie Gao","doi":"10.1016/j.electacta.2026.148187","DOIUrl":"10.1016/j.electacta.2026.148187","url":null,"abstract":"<div><div>Solid-state electrolytes (SSEs) are promising for high-energy-density lithium metal batteries (LMBs), yet they typically suffer from low ionic conductivity and unstable electrode interfaces. To tackle these issues concurrently, here, we designed a cyclodextrin-incorporated PVDF hybrid electrolyte (CD@PVDF). Its superior performance originates from a synergistic mechanism that integrates dynamic hydrogen-bonding networks with effective anion confinement. Specifically, the abundant hydroxyl groups of CD form strong O<img>H···F hydrogen bonds with PVDF, facilitating a phase transition from <em>α</em>- to <em>β</em>-phase and establishing a dynamically cross-linked polymer framework. The framework greatly improves the mobility of polymer segments and facilitates fast Li<sup>+</sup> transport along the chains. Meanwhile, the hydrophobic cavities of CD immobilize TFSI<sup>-</sup> anions via host-guest interactions, generating localized high-concentration Li<sup>+</sup> domains that optimize the ion transport pathway and lower the activation barrier for migration. As a result, the CD@PVDF electrolyte achieves a high ionic conductivity of 1.93 × 10<sup>–4</sup> S cm<sup>-1</sup>, a low activation energy of 0.35 eV, and a Li<sup>+</sup> transference number of 0.91. The Li-Li symmetric cells employing CD@PVDF demonstrate ultrastable cycling exceeding 4000 h with a low overpotential of 84 mV at 1 mA cm<sup>-2</sup> and 1 mAh cm<sup>-2</sup>. Moreover, Li-LFP full cells delivered an excellent capacity retention with the capacity retention of 98.5 % over 3000 cycles at 5 C. This work highlighted a synergistic design strategy that combined hydrogen-bonding engineering with anion confinement, offering valuable insights into the development of safe and high-performance SPEs for next-generation LMBs.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"551 ","pages":"Article 148187"},"PeriodicalIF":5.6,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949920","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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 : 2026-01-12DOI: 10.1016/j.electacta.2026.148129
Ho-Jin Lee , Alfi Rodiansyah , Hyunmin Na , Jeong-Ho Park , Ilgyu Kim , Ki Ro Yoon , Changwook Dong , Seoyoon Kweon , Joonwon Lim , Ji-Won Jung
Nitrogen-related catalytic sites of carbon nanotubes (CNTs) are regarded as an active site for formation of discharge product (Li2O2) in nonaqueous lithium-oxygen batteries. Although tremendous efforts have been devoted to increasing N-doping sites on CNTs, seeking a potent way to enrich N-sites has been fraught with challenges. Herein, the outer walls of one-dimensional multi-walled CNTs (N-u-CNTs) were successfully unzipped and N-doped by electrochemical methods, providing unzipped graphene nanoribbons with a large number of N-sites. In particular, a unique pyrazole-group – including -N-N-H – generated by unzipping can effectively draw electrons from oxygen, which plays a critical role in the adsorption of O2– and nucleation/growth of Li2O2. The high-density N-sites of N-u-CNTs promote film-like Li2O2 deposition, delivering a high discharging capacity of Li-O2 cells. By combining the N-u-CNTs with MnOx catalyst for a reversible charging process, the Li-O2 cells could last over 100 cycles with a limited capacity of 0.5 mAh cm–2. We elucidate the underlying mechanism of nucleation and growth of Li2O2 on N-u-CNTs and offer insights that help utilize viable N-u-CNTs for primary and secondary Li-air batteries.
碳纳米管（CNTs）的氮相关催化位点被认为是非水锂氧电池中形成放电产物（Li2O2）的活性位点。尽管人们在增加碳纳米管上的n掺杂位点方面做出了巨大的努力，但寻找一种富集n掺杂位点的有效方法却充满了挑战。本文通过电化学方法对一维多壁碳纳米管（N-u-CNTs）的外壁进行了成功的解压缩和n掺杂，提供了具有大量n位的解压缩石墨烯纳米带。特别是通过解压缩生成的独特的吡唑基团-包括- n - n - h -，可以有效地从氧中吸收电子，这对O2 -的吸附和Li2O2的成核/生长起着关键作用。N-u-CNTs的高密度n位促进了薄膜状Li2O2沉积，从而提供了高放电容量的Li-O2电池。通过将N-u-CNTs与MnOx催化剂结合进行可逆充电过程，Li-O2电池可以以0.5 mAh cm-2的有限容量持续100多次循环。我们阐明了Li2O2在N-u-CNTs上成核和生长的潜在机制，并提供了有助于将可行的N-u-CNTs用于一次和二次锂空气电池的见解。
{"title":"Achieving high discharge capacity of nonaqueous Li-O2 batteries using graphene nanoribbons synthesized via unzipping carbon nanotubes","authors":"Ho-Jin Lee , Alfi Rodiansyah , Hyunmin Na , Jeong-Ho Park , Ilgyu Kim , Ki Ro Yoon , Changwook Dong , Seoyoon Kweon , Joonwon Lim , Ji-Won Jung","doi":"10.1016/j.electacta.2026.148129","DOIUrl":"10.1016/j.electacta.2026.148129","url":null,"abstract":"<div><div>Nitrogen-related catalytic sites of carbon nanotubes (CNTs) are regarded as an active site for formation of discharge product (Li<sub>2</sub>O<sub>2</sub>) in nonaqueous lithium-oxygen batteries. Although tremendous efforts have been devoted to increasing N-doping sites on CNTs, seeking a potent way to enrich N-sites has been fraught with challenges. Herein, the outer walls of one-dimensional multi-walled CNTs (N-u-CNTs) were successfully unzipped and N-doped by electrochemical methods, providing unzipped graphene nanoribbons with a large number of N-sites. In particular, a unique pyrazole-group – including -N-N-H – generated by unzipping can effectively draw electrons from oxygen, which plays a critical role in the adsorption of O<sub>2</sub>– and nucleation/growth of Li<sub>2</sub>O<sub>2</sub>. The high-density N-sites of N-u-CNTs promote film-like Li<sub>2</sub>O<sub>2</sub> deposition, delivering a high discharging capacity of Li-O<sub>2</sub> cells. By combining the N-u-CNTs with MnO<sub>x</sub> catalyst for a reversible charging process, the Li-O<sub>2</sub> cells could last over 100 cycles with a limited capacity of 0.5 mAh cm<sup>–2</sup>. We elucidate the underlying mechanism of nucleation and growth of Li<sub>2</sub>O<sub>2</sub> on N-u-CNTs and offer insights that help utilize viable N-u-CNTs for primary and secondary Li-air batteries.</div></div>","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"550 ","pages":"Article 148129"},"PeriodicalIF":5.6,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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 : 2026-01-12DOI: 10.1016/j.electacta.2026.148181
Abhishek Paudel, Ying Wang
Total metal-free batteries are emerging as a sustainable alternative to traditional metal-based systems, offering eco-friendliness, biocompatibility, and cost-effectiveness by eliminating critical and toxic metals from both electrodes and electrolytes. Among them, ammonium-ion batteries (AIBs) have attracted significant attention due to the abundant availability of NH₄⁺ ions, their favorable transport kinetics, and compatibility with organic electrode materials. The nonmetal charge carriers also open the door to the development of total metal-free batteries by coupling with organic electrodes. This review presents a comprehensive overview of recent developments in total metal-free AIBs, focusing on the design and electrochemical behaviors of organic anodes and cathodes, such as polyimide, PANI, PTMA, and perylene derivatives. We summarize full-cell configurations employing aqueous, organic, and quasi-solid-state electrolytes, and highlight their voltage windows, capacities, rate capabilities, and cycling performance. Emphasis is placed on understanding the NH₄⁺ storage mechanisms, including hydrogen-bond-driven adsorption and reversible redox reactions. The influence of solvation structure and electrolyte engineering, such as utilizing antisolvents or hydrogel-based media, is also discussed. Despite encouraging results, challenges remain for these total metal-free batteries, including limited capacity, narrow voltage windows, and dissolution of organic materials. We identify key scientific and engineering obstacles and suggest future directions to guide the rational development of high-performance, flexible, and environmentally benign energy storage systems based on total metal-free chemistry.
{"title":"Recent Progress in Total Metal-Free Batteries: Materials, Mechanisms, and Challenges","authors":"Abhishek Paudel, Ying Wang","doi":"10.1016/j.electacta.2026.148181","DOIUrl":"https://doi.org/10.1016/j.electacta.2026.148181","url":null,"abstract":"Total metal-free batteries are emerging as a sustainable alternative to traditional metal-based systems, offering eco-friendliness, biocompatibility, and cost-effectiveness by eliminating critical and toxic metals from both electrodes and electrolytes. Among them, ammonium-ion batteries (AIBs) have attracted significant attention due to the abundant availability of NH₄⁺ ions, their favorable transport kinetics, and compatibility with organic electrode materials. The nonmetal charge carriers also open the door to the development of total metal-free batteries by coupling with organic electrodes. This review presents a comprehensive overview of recent developments in total metal-free AIBs, focusing on the design and electrochemical behaviors of organic anodes and cathodes, such as polyimide, PANI, PTMA, and perylene derivatives. We summarize full-cell configurations employing aqueous, organic, and quasi-solid-state electrolytes, and highlight their voltage windows, capacities, rate capabilities, and cycling performance. Emphasis is placed on understanding the NH₄⁺ storage mechanisms, including hydrogen-bond-driven adsorption and reversible redox reactions. The influence of solvation structure and electrolyte engineering, such as utilizing antisolvents or hydrogel-based media, is also discussed. Despite encouraging results, challenges remain for these total metal-free batteries, including limited capacity, narrow voltage windows, and dissolution of organic materials. We identify key scientific and engineering obstacles and suggest future directions to guide the rational development of high-performance, flexible, and environmentally benign energy storage systems based on total metal-free chemistry.","PeriodicalId":305,"journal":{"name":"Electrochimica Acta","volume":"3 1","pages":""},"PeriodicalIF":6.6,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949919","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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