Pub Date : 2026-08-06DOI: 10.1016/j.ensm.2026.105445
Zheng Hu, Yuxin Ran, Junpeng Xie, Xusheng Wang, Jianqiu Zhu, Yao Liu, Liang Ma, Wenjie Mai, Jinliang Li
As a representative NASICON-type cathode, Na3V2(PO4)3 (NVP) is hindered by intrinsically sluggish electron transport within the V-O framework, which induces severe polarization and rapid capacity decay under high-rate operation. In this work, we propose crystal structure modulation enabled by the introduction of trace amounts of Cu to overcome the electronic and structural limitations of NVP. Replacing V3+ with trace amounts of Cu2+ alters the local energy landscape, thereby improving local structural symmetry and stability over extended cycling. Furthermore, extending along the c‑axis directly enlarges the Na‑ion migration pathways, resulting in a 2.7-fold increase in ionic conductance. This behavior simplifies the two-phase reaction mechanism and leads to improved cycling performance over a wide temperature range. Benefiting from this modification, the optimized NVP delivers 112.3 mAh g-1 at 0.2 C and retains an 86% capacity retention after 10,000 cycles at 50 C. Remarkably, high stability is maintained from -20°C (97.3 mAh g-1 at 0.2 C) to 60°C (92.3 mAh g-1 at 20 C), outperforming all previously reported works. We believe that our trace copper-mediated crystal structure of NASICON-type cathodes offers a guiding pathway for developing next-generation, highly stable cathode materials.
Na3V2(PO4)3 （NVP）作为一种典型的nasicon型阴极，在V-O框架内受到固有的缓慢电子传递的阻碍，在高速率运行时导致严重的极化和快速的容量衰减。在这项工作中，我们提出通过引入微量Cu来实现晶体结构调制，以克服NVP的电子和结构限制。用微量Cu2+代替V3+改变了局部的能量格局，从而提高了局部结构的对称性和稳定性。此外，沿着c轴的延伸直接扩大了Na离子的迁移路径，导致离子电导增加2.7倍。这种行为简化了两相反应机理，并在较宽的温度范围内改善了循环性能。得益于这一改进，优化后的NVP在0.2℃下可提供112.3 mAh g-1，在50℃下进行10,000次循环后仍能保持86%的容量。值得注意的是，在-20℃（0.2℃时97.3 mAh g-1）至60℃（20℃时92.3 mAh g-1）期间保持了高稳定性，优于之前报道的所有工作。我们相信，我们的微量铜介导的nasicon型阴极晶体结构为开发下一代高稳定的阴极材料提供了指导途径。
{"title":"Trace Copper-Mediated Crystal Structure Modulation Enables Superior Stable Sodium Storage in NASICON Cathodes","authors":"Zheng Hu, Yuxin Ran, Junpeng Xie, Xusheng Wang, Jianqiu Zhu, Yao Liu, Liang Ma, Wenjie Mai, Jinliang Li","doi":"10.1016/j.ensm.2026.105445","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105445","url":null,"abstract":"As a representative NASICON-type cathode, Na<ce:inf loc=\"post\">3</ce:inf>V<ce:inf loc=\"post\">2</ce:inf>(PO<ce:inf loc=\"post\">4</ce:inf>)<ce:inf loc=\"post\">3</ce:inf> (NVP) is hindered by intrinsically sluggish electron transport within the V-O framework, which induces severe polarization and rapid capacity decay under high-rate operation. In this work, we propose crystal structure modulation enabled by the introduction of trace amounts of Cu to overcome the electronic and structural limitations of NVP. Replacing V3+ with trace amounts of Cu<ce:sup loc=\"post\">2+</ce:sup> alters the local energy landscape, thereby improving local structural symmetry and stability over extended cycling. Furthermore, extending along the c‑axis directly enlarges the Na‑ion migration pathways, resulting in a 2.7-fold increase in ionic conductance. This behavior simplifies the two-phase reaction mechanism and leads to improved cycling performance over a wide temperature range. Benefiting from this modification, the optimized NVP delivers 112.3 mAh g<ce:sup loc=\"post\">-1</ce:sup> at 0.2 C and retains an 86% capacity retention after 10,000 cycles at 50 C. Remarkably, high stability is maintained from -20°C (97.3 mAh g<ce:sup loc=\"post\">-1</ce:sup> at 0.2 C) to 60°C (92.3 mAh g<ce:sup loc=\"post\">-1</ce:sup> at 20 C), outperforming all previously reported works. We believe that our trace copper-mediated crystal structure of NASICON-type cathodes offers a guiding pathway for developing next-generation, highly stable cathode materials.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"159 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148717432","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}
Developing hydrogel electrolytes with both high ionic conductivity and mechanical robustness remains a core challenge for structural batteries. Inspired by scorpion slit sensilla, we propose a stretch-induced topological reconfiguration strategy to achieve a highly uniaxial synergistic orientation of silver nanowires and Ti3C2Tx MXene within a polyacrylamide hydrogel (S-OAMP), building ordered 1D confined nanochannels. Within this confined framework, a confined competitive ligand-exchange hopping (CCLEH) mechanism is revealed. This mechanism thermodynamically disrupts the conventional hydration steady state by generating a binding energy of ΔG=-5.8 kJ mol-1, driving a transition of Zn2+ from 3D random diffusion to 1D directional transport featuring a low energy barrier of Ea=29.8 kJ mol-1. The S-OAMP electrolyte delivers a superior ionic conductivity of 52.9 mS cm-1 and a high Zn2+ transference number of 0.89. Compounded with carbon fibers, under varying tensile loads, the transverse contraction of S-OAMP driven by the anisotropic Poisson effect radially compresses the 1D channels, achieving a remarkable discharge capacity recovery of nearly two-thirds and further validating the applicability of the CCLEH mechanism. Structural batteries retain 81.9% capacity over 1400 cycles, and Zn||Zn symmetric cells endure prolonged cycling exceeding 2600 h. The CCLEH mechanism provides a new paradigm for designing high-load-bearing, long-lifespan solid-state energy materials.
开发既具有高离子电导率又具有机械稳健性的水凝胶电解质仍然是结构电池的核心挑战。受蝎子狭缝感受器的启发，我们提出了一种拉伸诱导的拓扑重构策略，以实现银纳米线和Ti3C2Tx MXene在聚丙烯酰胺水凝胶（S-OAMP）中的高度单轴协同取向，构建有序的一维受限纳米通道。在这个有限的框架内，揭示了一个有限竞争配体交换跳变（CCLEH）机制。这一热力学机制通过产生ΔG=-5.8 kJ mol-1的结合能，打破了传统的水合稳定状态，驱动Zn2+从3D随机扩散向具有Ea=29.8 kJ mol-1的低能垒的一维定向输运转变。S-OAMP电解质具有52.9 mS cm-1的优异离子电导率和0.89的高Zn2+转移数。与碳纤维复合，在不同拉伸载荷下，各向异性泊松效应驱动的S-OAMP横向收缩径向压缩一维通道，实现了近三分之二的放电容量恢复，进一步验证了CCLEH机制的适用性。结构电池在1400次循环中仍能保持81.9%的容量，而锌对称电池的循环时间超过2600小时。CCLEH机制为设计高承载、长寿命的固态能源材料提供了新的范式。
{"title":"Bionic topology reconstruction drives confined competitive ligand-exchange hopping dynamics in hydrogel electrolytes to achieve high-performance structural Zn-Ion batteries","authors":"Junhang Xu, Zhongyuan Shi, Yifei Liu, Qigang Han, Shuqing Kou","doi":"10.1016/j.ensm.2026.105446","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105446","url":null,"abstract":"Developing hydrogel electrolytes with both high ionic conductivity and mechanical robustness remains a core challenge for structural batteries. Inspired by scorpion slit sensilla, we propose a stretch-induced topological reconfiguration strategy to achieve a highly uniaxial synergistic orientation of silver nanowires and Ti<ce:inf loc=\"post\">3</ce:inf>C<ce:inf loc=\"post\">2</ce:inf>T<ce:inf loc=\"post\">x</ce:inf> MXene within a polyacrylamide hydrogel (S-OAMP), building ordered 1D confined nanochannels. Within this confined framework, a confined competitive ligand-exchange hopping (C<ce:glyph name=\"sbnd\"></ce:glyph>CLEH) mechanism is revealed. This mechanism thermodynamically disrupts the conventional hydration steady state by generating a binding energy of ΔG=-5.8 kJ mol<ce:sup loc=\"post\">-1</ce:sup>, driving a transition of Zn<ce:sup loc=\"post\">2+</ce:sup> from 3D random diffusion to 1D directional transport featuring a low energy barrier of Ea=29.8 kJ mol<ce:sup loc=\"post\">-1</ce:sup>. The S-OAMP electrolyte delivers a superior ionic conductivity of 52.9 mS cm<ce:sup loc=\"post\">-1</ce:sup> and a high Zn<ce:sup loc=\"post\">2+</ce:sup> transference number of 0.89. Compounded with carbon fibers, under varying tensile loads, the transverse contraction of S-OAMP driven by the anisotropic Poisson effect radially compresses the 1D channels, achieving a remarkable discharge capacity recovery of nearly two-thirds and further validating the applicability of the C<ce:glyph name=\"sbnd\"></ce:glyph>CLEH mechanism. Structural batteries retain 81.9% capacity over 1400 cycles, and Zn||Zn symmetric cells endure prolonged cycling exceeding 2600 h. The C<ce:glyph name=\"sbnd\"></ce:glyph>CLEH mechanism provides a new paradigm for designing high-load-bearing, long-lifespan solid-state energy materials.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"67 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148717434","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}
Catalytic strategies currently provide an effective way to tackle the shuttle effect and sluggish reaction kinetics in lithium-sulfur batteries. While elemental doping has been employed to tailor the electronic structure of catalysts, the concerted manipulation of spin states at active centers via cation-anion co-doping remains incompletely explored. Here, we devise an Fe and P co-doping strategy to forge a spin-polarized CoSe2 catalyst through a hydrothermal route followed by gas-phase phosphorization. Density functional theory calculations, substantiated by experimental evidence, reveal that P doping first induces adjacent Co atoms to adopt a high-spin configuration. On this basis, the implanted Fe centers further trigger 3d electron spin flipping on additional vicinal Co atoms across asymmetric Fe-Se-Co bridges, elevating them from a low-spin (t2g6eg1) to a high-spin (t2g5eg2) state. This sequential synergy significantly amplifies the overall spin polarization, refines orbital hybridization between metal sites and polysulfides, diminishes antibonding electron occupation, and enhances adsorption bond orders, thereby substantially boosting sulfur conversion kinetics. Li-S batteries incorporating this catalyst attain a stellar reversible capacity of 622.7 mAh g⁻1 at 4 C and stable 2000-cycle longevity at 4 C, with a capacity decay rate of merely 0.033% per cycle. This work charts a new avenue for elevating lithium-sulfur battery efficacy through spin-state engineering powered by cation-anion co-doping.
催化策略是目前解决锂硫电池穿梭效应和反应动力学缓慢的有效途径。虽然元素掺杂已被用于调整催化剂的电子结构，但通过阳离子-阴离子共掺杂对活性中心自旋态的协同操纵仍未完全探索。在这里，我们设计了一种铁和磷共掺杂策略，通过水热途径形成自旋极化的CoSe2催化剂，然后进行气相磷酸化。密度泛函理论计算和实验证据表明，P掺杂首先诱导相邻的Co原子采用高自旋构型。在此基础上，植入的Fe中心进一步触发相邻Co原子在不对称Fe- se -Co桥上的三维电子自旋翻转，使它们从低自旋（t2g6eg1）状态提升到高自旋（t2g5eg2）状态。这种顺序的协同作用显著地放大了整体的自旋极化，精炼了金属位点和多硫化物之间的轨道杂化，减少了反键电子占据，增强了吸附键的顺序，从而大大提高了硫转化动力学。含有这种催化剂的锂- s电池在4℃时的可逆容量为622.7 mAh g - 1，在4℃时的稳定2000循环寿命，每个循环的容量衰减率仅为0.033%。这项工作为通过正阴离子共掺杂驱动的自旋态工程提高锂硫电池的效率开辟了一条新的途径。
{"title":"Engineering high-spin cobalt centers via cation-anion co-doping to boost polysulfide conversion in lithium-sulfur batteries","authors":"Fen Li, Guo Liu, Qi Zeng, Xiaoxiang Sun, Jiayou Tao, Chang Li, Zhenxing Zhang, Jijun Zhao","doi":"10.1016/j.ensm.2026.105447","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105447","url":null,"abstract":"Catalytic strategies currently provide an effective way to tackle the shuttle effect and sluggish reaction kinetics in lithium-sulfur batteries. While elemental doping has been employed to tailor the electronic structure of catalysts, the concerted manipulation of spin states at active centers via cation-anion co-doping remains incompletely explored. Here, we devise an Fe and P co-doping strategy to forge a spin-polarized CoSe<ce:inf loc=\"post\">2</ce:inf> catalyst through a hydrothermal route followed by gas-phase phosphorization. Density functional theory calculations, substantiated by experimental evidence, reveal that P doping first induces adjacent Co atoms to adopt a high-spin configuration. On this basis, the implanted Fe centers further trigger 3d electron spin flipping on additional vicinal Co atoms across asymmetric Fe-Se-Co bridges, elevating them from a low-spin (t<ce:inf loc=\"post\">2g</ce:inf><ce:sup loc=\"post\">6</ce:sup>e<ce:inf loc=\"post\">g</ce:inf><ce:sup loc=\"post\">1</ce:sup>) to a high-spin (t<ce:inf loc=\"post\">2g</ce:inf><ce:sup loc=\"post\">5</ce:sup>e<ce:inf loc=\"post\">g</ce:inf><ce:sup loc=\"post\">2</ce:sup>) state. This sequential synergy significantly amplifies the overall spin polarization, refines orbital hybridization between metal sites and polysulfides, diminishes antibonding electron occupation, and enhances adsorption bond orders, thereby substantially boosting sulfur conversion kinetics. Li-S batteries incorporating this catalyst attain a stellar reversible capacity of 622.7 mAh g⁻<ce:sup loc=\"post\">1</ce:sup> at 4 C and stable 2000-cycle longevity at 4 C, with a capacity decay rate of merely 0.033% per cycle. This work charts a new avenue for elevating lithium-sulfur battery efficacy through spin-state engineering powered by cation-anion co-doping.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"15 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148717433","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 : 2026-08-06DOI: 10.1016/j.ensm.2026.105428
Kurt R. Hebert
Liquid cell batteries with lithium metal anodes may exhibit degraded Coulombic efficiency due to plating of porous, filamentary deposits. Experiments suggest that filament growth is controlled by lithium diffusion-induced compressive stress. In situ wafer curvature measurements can reveal the dynamic stress response of lithium deposits during cycling, but the interpretation of these experiments is complicated by the unknown and changing deposit morphology. Here, a new modeling approach is introduced that avoids this difficulty by focusing on the curvature response in open-circuit intervals during cycling. We demonstrate fitting of experimental curvature transients to characterize evolution of deposit morphology, metal-phase diffusion and mechanical deformation in cycling experiments. The model is based on metal-phase diffusion accommodated by elastic deformation and power-law creep, and is validated by comparison of the fit creep parameters with independent nanoindentation experiments. The results provide evidence for the presence of diffusion-induced compressive stress in plating periods. Lithium stripping is shown to generate tensile stress in lithium in a micron-thick surface-adjacent layer, consistent with experimental observations of submicron near-surface voids.
{"title":"Analysis of stress evolution in lithium metal anodes during plating and stripping cycles","authors":"Kurt R. Hebert","doi":"10.1016/j.ensm.2026.105428","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105428","url":null,"abstract":"Liquid cell batteries with lithium metal anodes may exhibit degraded Coulombic efficiency due to plating of porous, filamentary deposits. Experiments suggest that filament growth is controlled by lithium diffusion-induced compressive stress. In situ wafer curvature measurements can reveal the dynamic stress response of lithium deposits during cycling, but the interpretation of these experiments is complicated by the unknown and changing deposit morphology. Here, a new modeling approach is introduced that avoids this difficulty by focusing on the curvature response in open-circuit intervals during cycling. We demonstrate fitting of experimental curvature transients to characterize evolution of deposit morphology, metal-phase diffusion and mechanical deformation in cycling experiments. The model is based on metal-phase diffusion accommodated by elastic deformation and power-law creep, and is validated by comparison of the fit creep parameters with independent nanoindentation experiments. The results provide evidence for the presence of diffusion-induced compressive stress in plating periods. Lithium stripping is shown to generate tensile stress in lithium in a micron-thick surface-adjacent layer, consistent with experimental observations of submicron near-surface voids.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"61 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148717544","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}
The realization of Zn-air batteries (ZABs) for electric vehicles and portable devices critically depends on high-performance air electrodes capable of fast mass transport, efficient catalysis for the oxygen reduction/evolution reactions (ORR/OER) and desirable oxidation resistance, but the actual assembly is still a great challenge. In this work, a single-walled carbon nanotube (SWCNT) multifunctional film is proposed directly as binder-free air electrode to overcome the dilemma. Specifically, FeNi₃ nanoparticles are anchored on SWCNTs during the film synthesis, whereas the Fe-N4 moieties are introduced via a post-treatment process involving sublimation of iron phthalocyanine. Thereinto, high-quality SWCNT units ensure excellent stability of the resulting electrode due to the intrinsic property of high oxidation resistance and three-dimensional interwoven SWCNT bundles without any binder are qualified for fast O2 diffusion to active sites. Furthermore, combined experimental results and theoretical calculations reveal that FeNi nanoparticles and Fe-N4 moieties anchored on the curved nanotube walls interact synergistically to boost catalytic activities. As a result, the film electrode exhibits a low overall overpotential of 0.63 V (EOER/10-EORR/half), better than the precious metal-based catalysts (Pt/C-Ir/C: 0.72V). When directly assembled into binder-free air electrodes for ZABs, ultrahigh output performance (peak power density: 251 mW cm-2) and ultralong-life charge-discharge cycling stability (1600 h) are realized.
用于电动汽车和便携式设备的锌空气电池（ZABs）的实现关键取决于能够快速传输质量、高效催化氧还原/演化反应（ORR/OER）和理想的抗氧化性的高性能空气电极，但实际组装仍然是一个巨大的挑战。在这项工作中，提出了一种单壁碳纳米管（SWCNT）多功能薄膜直接作为无粘结剂的空气电极来克服这一困境。具体来说，FeNi₃纳米颗粒在薄膜合成过程中被固定在SWCNTs上，而Fe-N4部分是通过涉及酞菁铁升华的后处理过程引入的。其中，高质量的swcnts单元由于其固有的高抗氧化性和无粘结剂的三维交织swcnts束的特性，确保了所得到电极的优异稳定性，可以快速将O2扩散到活性位点。此外，结合实验结果和理论计算表明，FeNi纳米颗粒和固定在弯曲纳米管壁上的Fe-N4基团相互作用，提高了催化活性。结果表明，薄膜电极整体过电位较低，为0.63 V （EOER/10-EORR/一半），优于贵金属基催化剂（Pt/C- ir /C: 0.72V）。当直接组装成无粘结剂的ZABs空气电极时，实现了超高的输出性能（峰值功率密度：251 mW cm-2）和超长寿命的充放电循环稳定性（1600 h）。
{"title":"Single-walled carbon nanotube film based self-adhesive air electrode featuring interaction-enhanced dual sites for high-performance Zn-Air batteries","authors":"Yu Meng, Zhong-Qiang Ni, Rui-Hong Xie, Mengke Zou, Hao Yang, Yi-Long Chen, Pengfei Xie, Jin-Cheng Li, Peng-Xiang Hou, Chang Liu","doi":"10.1016/j.ensm.2026.105441","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105441","url":null,"abstract":"The realization of Zn-air batteries (ZABs) for electric vehicles and portable devices critically depends on high-performance air electrodes capable of fast mass transport, efficient catalysis for the oxygen reduction/evolution reactions (ORR/OER) and desirable oxidation resistance, but the actual assembly is still a great challenge. In this work, a single-walled carbon nanotube (SWCNT) multifunctional film is proposed directly as binder-free air electrode to overcome the dilemma. Specifically, FeNi₃ nanoparticles are anchored on SWCNTs during the film synthesis, whereas the Fe-N<ce:inf loc=\"post\">4</ce:inf> moieties are introduced via a post-treatment process involving sublimation of iron phthalocyanine. Thereinto, high-quality SWCNT units ensure excellent stability of the resulting electrode due to the intrinsic property of high oxidation resistance and three-dimensional interwoven SWCNT bundles without any binder are qualified for fast O<ce:inf loc=\"post\">2</ce:inf> diffusion to active sites. Furthermore, combined experimental results and theoretical calculations reveal that FeNi nanoparticles and Fe-N<ce:inf loc=\"post\">4</ce:inf> moieties anchored on the curved nanotube walls interact synergistically to boost catalytic activities. As a result, the film electrode exhibits a low overall overpotential of 0.63 V (E<ce:inf loc=\"post\">OER/10</ce:inf>-E<ce:inf loc=\"post\">ORR/half</ce:inf>), better than the precious metal-based catalysts (Pt/C-Ir/C: 0.72V). When directly assembled into binder-free air electrodes for ZABs, ultrahigh output performance (peak power density: 251 mW cm<ce:sup loc=\"post\">-2</ce:sup>) and ultralong-life charge-discharge cycling stability (1600 h) are realized.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"26 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148692350","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}
Ni-rich LiNi0.8Co0.1Mn0.1O2 (NCM811) is a promising high-voltage cathode material for high-energy-density lithium-ion batteries (LIBs). However, its practical application is hindered by the instability of the cathode–electrolyte interface under high-voltage and elevated-temperature operating conditions. Herein, 6-fluoro-3-cyanopyridine (FCP) is introduced as a multifunctional film-forming electrolyte additive to stabilize the NCM811 cathode, enabling synergistic improvements in high-voltage stability (4.5 V) and thermal stability under elevated-temperature conditions (55°C). Density functional theory calculations and electrochemical characterizations reveal that FCP preferentially undergoes oxidative decomposition, forming a LiF/-C=N-C-enriched cathode-electrolyte interphase (CEI) on the NCM811 surface. The resulting CEI effectively enhances the structural stability of the NCM811 cathode, suppressing irreversible surface phase reconstruction and transition-metal dissolution during high-voltage cycling while facilitating Li+ transport kinetics. Consequently, NCM811/Li half-cells with 2.0 wt.% FCP exhibit much higher capacity retentions of 63.9% after 600 cycles at 25°C and 74.2% after 200 cycles at 55°C within 3.0∼4.5 V, significantly outperforming those with the Base electrolyte (32.1% and 59.9%, respectively). The practicality of the FCP additive is further demonstrated in NCM811/graphite full-cells, which deliver superior capacity retentions of 80.0% after 500 cycles at 25°C and 70.6% after 200 cycles at 55°C, compared with 57.8% and 32.8%, respectively, for the Base electrolyte. This work provides valuable insights into the design of multifunctional electrolyte additives by integrating complementary functional groups into a single molecular framework, offering an effective strategy for stabilizing high-voltage NCM811 cathodes and advancing high-energy-density LIBs with enhanced high-temperature durability.
富镍LiNi0.8Co0.1Mn0.1O2 （NCM811）是一种很有前途的高能密度锂离子电池（LIBs）高压正极材料。然而，在高压和高温条件下，阴极-电解质界面的不稳定性阻碍了其实际应用。本文引入6-氟-3-氰吡啶（FCP）作为多功能成膜电解质添加剂，以稳定NCM811阴极，从而协同提高高压稳定性（4.5 V）和高温条件下（55°C）的热稳定性。密度泛函理论计算和电化学表征表明，FCP优先进行氧化分解，在NCM811表面形成LiF/ c = n -C富集的阴极-电解质界面（CEI）。由此产生的CEI有效地增强了NCM811阴极的结构稳定性，抑制了高压循环过程中不可逆的表面相重构和过渡金属的溶解，同时促进了Li+的传输动力学。因此，2.0 wt.% FCP的NCM811/Li半电池在25°C下循环600次后的容量保留率为63.9%，在3.0 ~ 4.5 V下在55°C下循环200次后的容量保留率为74.2%，显著优于使用碱性电解质的电池（分别为32.1%和59.9%）。FCP添加剂的实用性在NCM811/石墨全电池中得到进一步验证，在25°C下循环500次和55°C下循环200次后，FCP添加剂的容量保留率分别为80.0%和70.6%，而碱性电解质的容量保留率分别为57.8%和32.8%。本研究通过将互补的官能团整合到单个分子框架中，为多功能电解质添加剂的设计提供了有价值的见解，为稳定高压NCM811阴极和提高高温耐久性的高能量密度lib提供了有效的策略。
{"title":"Synergistic Interphase and Electrolyte Stabilization through Integrating Complementary Functional Groups into a Single Molecular Framework for High-Voltage NCM811 Cathodes with High-Temperature Adaptability","authors":"Mingjun Ma, Haolei Chen, Haonan Huang, Yijie Lin, Yuling Fu, Shuai Chen, Huahua Chen, Xinqi Chen, Jiarong He, Lidan Xing, Weishan Li","doi":"10.1016/j.ensm.2026.105439","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105439","url":null,"abstract":"Ni-rich LiNi<ce:inf loc=\"post\">0.8</ce:inf>Co<ce:inf loc=\"post\">0.1</ce:inf>Mn<ce:inf loc=\"post\">0.1</ce:inf>O<ce:inf loc=\"post\">2</ce:inf> (NCM811) is a promising high-voltage cathode material for high-energy-density lithium-ion batteries (LIBs). However, its practical application is hindered by the instability of the cathode–electrolyte interface under high-voltage and elevated-temperature operating conditions. Herein, 6-fluoro-3-cyanopyridine (FCP) is introduced as a multifunctional film-forming electrolyte additive to stabilize the NCM811 cathode, enabling synergistic improvements in high-voltage stability (4.5 V) and thermal stability under elevated-temperature conditions (55°C). Density functional theory calculations and electrochemical characterizations reveal that FCP preferentially undergoes oxidative decomposition, forming a LiF/-C=N-C-enriched cathode-electrolyte interphase (CEI) on the NCM811 surface. The resulting CEI effectively enhances the structural stability of the NCM811 cathode, suppressing irreversible surface phase reconstruction and transition-metal dissolution during high-voltage cycling while facilitating Li<ce:sup loc=\"post\">+</ce:sup> transport kinetics. Consequently, NCM811/Li half-cells with 2.0 wt.% FCP exhibit much higher capacity retentions of 63.9% after 600 cycles at 25°C and 74.2% after 200 cycles at 55°C within 3.0∼4.5 V, significantly outperforming those with the Base electrolyte (32.1% and 59.9%, respectively). The practicality of the FCP additive is further demonstrated in NCM811/graphite full-cells, which deliver superior capacity retentions of 80.0% after 500 cycles at 25°C and 70.6% after 200 cycles at 55°C, compared with 57.8% and 32.8%, respectively, for the Base electrolyte. This work provides valuable insights into the design of multifunctional electrolyte additives by integrating complementary functional groups into a single molecular framework, offering an effective strategy for stabilizing high-voltage NCM811 cathodes and advancing high-energy-density LIBs with enhanced high-temperature durability.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"14 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148692126","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}
The practical application of high-loading silicon-carbon (Si/C) anodes is hindered by sluggish and non-uniform prelithiation, stemming from inadequate lithium-ion (Li+) transport and large volume changes. To address this, we have designed a three-dimensional (3D) networked ion-conductive binder, which leverages abundant sulfonate (-SO3−) groups as Li+ hopping sites, thus synergizing with dynamic hydrogen bonds to construct a continuous 3D Li+ transport network. This network not only accommodates volume changes but also enables rapid and homogeneous Li+ migration. By combining ex/in-situ characterization with theoretical simulations, we reveal that the -SO3− groups facilitate Li+ desolvation and promote the formation of a robust, LiF-rich solid electrolyte interphase (SEI). As a result, the modified Si/C electrode achieves an exceptional initial Coulombic efficiency (ICE) of 102.7% and a high areal capacity of 4.63 mAh cm−2 after ∼3 minutes of prelithiation at 5 mg cm−2. When paired with an NCM85 cathode, the full-cell delivers an ICE of 89.36% and retains an energy density of 484 Wh kg−1 after 50 cycles. This work elucidates the pivotal roles between prelithiation kinetics and interfacial stability, which establishes a functional-binder design strategy for overcoming the critical bottlenecks in high-capacity Si-based lithium-ion batteries.
由于锂离子（Li+）输运不足和体积变化大，高负载硅碳（Si/C）阳极的预锂化缓慢且不均匀，阻碍了其实际应用。为了解决这个问题，我们设计了一种三维（3D）网络离子导电粘合剂，它利用丰富的磺酸盐（-SO3−）基团作为Li+跳跃位点，从而与动态氢键协同构建连续的3D Li+传输网络。该网络不仅可以适应体积变化，还可以实现快速均匀的Li+迁移。通过将ex/原位表征与理论模拟相结合，我们发现-SO3−基团促进Li+的脱溶，并促进形成坚固的、富含Li - f的固体电解质界面相（SEI）。结果表明，在5 mg cm - 2下预锂化约3分钟后，改性的Si/C电极获得了102.7%的初始库仑效率（ICE）和4.63 mAh cm - 2的高面容量。当与NCM85阴极配对时，完整的电池提供89.36%的ICE，并在50次循环后保持484 Wh kg−1的能量密度。这项工作阐明了预锂化动力学和界面稳定性之间的关键作用，为克服高容量硅基锂离子电池的关键瓶颈建立了一种功能粘合剂设计策略。
{"title":"Constructing 3D Ion-Conductive Binder Networks for Boosted Prelithiation Kinetics and Interfacial Stability of High-Loading Si/C Anodes","authors":"Wenjie He, Zhigang Li, Zhuo Li, Zimu Su, Xu Chen, Kangsheng Huang, Yue Xiao, Jia Yang, Gai Wu, Xiangjun Chen, Jiangmin Jiang","doi":"10.1016/j.ensm.2026.105433","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105433","url":null,"abstract":"The practical application of high-loading silicon-carbon (Si/C) anodes is hindered by sluggish and non-uniform prelithiation, stemming from inadequate lithium-ion (Li<ce:sup loc=\"post\">+</ce:sup>) transport and large volume changes. To address this, we have designed a three-dimensional (3D) networked ion-conductive binder, which leverages abundant sulfonate (-SO<ce:inf loc=\"post\">3</ce:inf><ce:sup loc=\"post\">−</ce:sup>) groups as Li<ce:sup loc=\"post\">+</ce:sup> hopping sites, thus synergizing with dynamic hydrogen bonds to construct a continuous 3D Li<ce:sup loc=\"post\">+</ce:sup> transport network. This network not only accommodates volume changes but also enables rapid and homogeneous Li<ce:sup loc=\"post\">+</ce:sup> migration. By combining ex/in-situ characterization with theoretical simulations, we reveal that the -SO<ce:inf loc=\"post\">3</ce:inf><ce:sup loc=\"post\">−</ce:sup> groups facilitate Li<ce:sup loc=\"post\">+</ce:sup> desolvation and promote the formation of a robust, LiF-rich solid electrolyte interphase (SEI). As a result, the modified Si/C electrode achieves an exceptional initial Coulombic efficiency (ICE) of 102.7% and a high areal capacity of 4.63 mAh cm<ce:sup loc=\"post\">−2</ce:sup> after ∼3 minutes of prelithiation at 5 mg cm<ce:sup loc=\"post\">−2</ce:sup>. When paired with an NCM85 cathode, the full-cell delivers an ICE of 89.36% and retains an energy density of 484 Wh kg<ce:sup loc=\"post\">−1</ce:sup> after 50 cycles. This work elucidates the pivotal roles between prelithiation kinetics and interfacial stability, which establishes a functional-binder design strategy for overcoming the critical bottlenecks in high-capacity Si-based lithium-ion batteries.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"24 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148692046","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 : 2026-08-03DOI: 10.1016/j.ensm.2026.105431
Song Kyu Kang, Hyeonju Kim, Sung-Dae Kim, Sang Ho Lee, Won Bae Kim
To establish a generic design strategy for fast-charging and high-capacity-retention Si anode structures, synergistic control over the interactions between interfacial layers and electrolyte chemistry is considered essential. Here, we developed electronically polarized pyridinic interfacial layers on a Si-decorated carbon nanofiber architecture, with the ultimate goal to facilitate the formation of a stable LiF-rich solid–electrolyte interphase. Furthermore, the Lewis basicity of pyridinic nitrogen effectively modulated local Li+ coordination at the interface, thereby inducing effective lithiation kinetics even on the intrinsically sluggish Si (111) facet. As a result, the engineered Si anode architecture delivered a high discharge capacity of ∼ 1850 mAh g−1 at an ultrahigh current density of 10 A g−1 and sustained a reversible capacity of ∼ 1700 mAh g−1 over 300 cycles (∼ 90 % retention). Notably, full-cell configurations paired with LiNi0.8Co0.1Mn0.1O2-based cathodes retained outstanding cycling performance, with ∼ 90 % of the initial capacity at 0.5 C over 160 cycles, highlighting that bespoke interfacial dipole engineering offers a powerful strategy for regulating SEI chemistry and enabling high-performance Si anodes for next-generation lithium-ion storage systems.
为了建立快速充电和高容量保持硅阳极结构的通用设计策略，对界面层和电解质化学之间相互作用的协同控制被认为是必不可少的。在这里，我们在硅修饰的碳纳米纤维结构上开发了电子极化吡啶界面层，最终目标是促进形成稳定的富liff固体电解质界面。此外，吡啶氮的Lewis碱度有效地调节了界面上的局部Li+配位，从而诱导了有效的锂化动力学，即使在本质上是缓慢的Si（111）面。因此，设计的Si阳极结构在10 a g−1的超高电流密度下提供了~ 1850 mAh g−1的高放电容量，并在300次循环中保持了~ 1700 mAh g−1的可逆容量（保持率~ 90%）。值得注意的是，与基于lini0.8 co0.1 mn0.1 o2的阴极配对的全电池配置保留了出色的循环性能，在0.5 C下超过160次循环时具有初始容量的约90%，突出表明定制界面偶极子工程为调节SEI化学和为下一代锂离子存储系统提供高性能Si阳极提供了强大的策略。
{"title":"Pyridinic Dipole–Engineered Interfacial Design for Developing Fast-Charging and Ultra-Stable Silicon Anodes","authors":"Song Kyu Kang, Hyeonju Kim, Sung-Dae Kim, Sang Ho Lee, Won Bae Kim","doi":"10.1016/j.ensm.2026.105431","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105431","url":null,"abstract":"To establish a generic design strategy for fast-charging and high-capacity-retention Si anode structures, synergistic control over the interactions between interfacial layers and electrolyte chemistry is considered essential. Here, we developed electronically polarized pyridinic interfacial layers on a Si-decorated carbon nanofiber architecture, with the ultimate goal to facilitate the formation of a stable LiF-rich solid–electrolyte interphase. Furthermore, the Lewis basicity of pyridinic nitrogen effectively modulated local Li<ce:sup loc=\"post\">+</ce:sup> coordination at the interface, thereby inducing effective lithiation kinetics even on the intrinsically sluggish Si (111) facet. As a result, the engineered Si anode architecture delivered a high discharge capacity of ∼ 1850 mAh g<ce:sup loc=\"post\">−1</ce:sup> at an ultrahigh current density of 10 A g<ce:sup loc=\"post\">−1</ce:sup> and sustained a reversible capacity of ∼ 1700 mAh g<ce:sup loc=\"post\">−1</ce:sup> over 300 cycles (∼ 90 % retention). Notably, full-cell configurations paired with LiNi<ce:inf loc=\"post\">0.8</ce:inf>Co<ce:inf loc=\"post\">0.1</ce:inf>Mn<ce:inf loc=\"post\">0.1</ce:inf>O<ce:inf loc=\"post\">2</ce:inf>-based cathodes retained outstanding cycling performance, with ∼ 90 % of the initial capacity at 0.5 C over 160 cycles, highlighting that bespoke interfacial dipole engineering offers a powerful strategy for regulating SEI chemistry and enabling high-performance Si anodes for next-generation lithium-ion storage systems.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"36 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148692347","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}
Alloy-based anodes are promising for sodium-ion batteries but suffer from large volume variation during cycling. Although ether-based electrolytes benefit many alloy-based anodes, they fail for Sb. Here, mechanical property and volume variation are proposed to explain the greater challenge with Sb (versus Bi and Sn). Then, a high-concentration electrolyte is developed for commercial Sb powders (μ-Sb) by using THF as the solvent for its good solubility to sodium salts, low molecular polarity and small molecule size. Theoretical simulations indicate that the increasing salt concentration makes the anions in the solvation sheath shift from monodentate to polydentate. This change results in weakened P-F bonds, reduced LUMO energy levels and increased Na-ion number within one cluster, promoting the formation of a NaF-rich solid electrolyte interphase on the surface. Such an interphase greatly enhances ion conductivity and mechanical resilience, improving the electrochemical performance of μ-Sb. This electrolyte is also compatible to Sn and Bi. These results advance our understandings of solvation structures and interface chemistry critical for high-performance sodium-ion batteries.
{"title":"Revisit Solvation Chemistry in High-Concentration Ether-based Electrolytes to Stabilize Alloy-Type Anodes of Sodium Ion Batteries","authors":"Qian Yao, Cheng Zheng, Zhenjie Cheng, Gulian Wang, Jizhen Ma, Zhongchao Bai, Shixue Dou, Nana Wang, Guoxiu Wang, Jian Yang","doi":"10.1016/j.ensm.2026.105436","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105436","url":null,"abstract":"Alloy-based anodes are promising for sodium-ion batteries but suffer from large volume variation during cycling. Although ether-based electrolytes benefit many alloy-based anodes, they fail for Sb. Here, mechanical property and volume variation are proposed to explain the greater challenge with Sb (versus Bi and Sn). Then, a high-concentration electrolyte is developed for commercial Sb powders (μ-Sb) by using THF as the solvent for its good solubility to sodium salts, low molecular polarity and small molecule size. Theoretical simulations indicate that the increasing salt concentration makes the anions in the solvation sheath shift from monodentate to polydentate. This change results in weakened P-F bonds, reduced LUMO energy levels and increased Na-ion number within one cluster, promoting the formation of a NaF-rich solid electrolyte interphase on the surface. Such an interphase greatly enhances ion conductivity and mechanical resilience, improving the electrochemical performance of μ-Sb. This electrolyte is also compatible to Sn and Bi. These results advance our understandings of solvation structures and interface chemistry critical for high-performance sodium-ion batteries.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"101 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148692346","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}
Polymer-in-ceramic composite solid-state electrolytes (PICSEs) are a promising strategy for realizing next-generation solid-state batteries (SSBs). However, poor intrinsic interfacial compatibility between the ceramic and polymer matrix and inadequate contact at the electrode-electrolyte interfaces remain serious challenges. Herein, a multifunctional 3-(trimethoxysilyl) propylmethacrylate (TMSPM) molecule is grafted on the Li6.25Al0.25La3Zr2O12 (LALZO) particle’s surface. Consequently, we prepared a PICSE with 60 wt.% TMSPM-functionalized LALZO active filler and polymer matrix (hereafter denoted as PICSE60) via thermal extrusion blending. To further improve both the PICSE60/electrode interface and the ceramic/polymer matrix interface, PEGDMA crosslinking was sequentially engineered as an integrated interfacial interlayer (denoted as C-PICSE60). This molecular-level interface engineering helped bridge the ceramic/polymer matrix interphase and enhanced Li+ flux throughout the bulk PICSEs via multiple Li+ coordination with TMSPM (Li⋅⋅⋅- O=C) and PEO (Li⋅⋅⋅- O‒C). Experimental and computational modeling elucidated the role of TMSPM in molecular bridging between the composite components. Consequently, C-PICSE60, containing a small amount of LiDFOB/LiDFP-based liquid electrolyte, exhibited a high Li⁺ transference number (ca. 0.65), ionic conductivity (0.66 mS cm⁻¹, RT), a wide electrochemical window (5.21 V vs. Li/Li⁺), and stable symmetric-cell cycling for over 2900 h. The Li||LiFePO₄ full cells exhibited long cycling stability, retaining 90.83% capacity after 1150 cycles at 0.5 C/1 C. The full cell with a high-voltage polyacrylonitrile-coated single-crystal LiNi0.86Co0.05Mn0.05Al0.04O2 (PAN@SC-NCMA86) cathode exhibited 80.82% capacity retention after 550 cycles at 0.5 C (2.8–4.3 V). This work provides new insights into an integrated engineering strategy for achieving robust interfacial compatibility, enabling high-performance hybrid-SSBs.
聚合物陶瓷复合固态电解质（PICSEs）是实现下一代固态电池（ssb）的一种很有前途的策略。然而，陶瓷和聚合物基体之间的内在界面相容性差以及电极-电解质界面接触不足仍然是严峻的挑战。本文将一个多功能的3-（三甲氧基硅基）甲基丙烯酸丙酯（TMSPM）分子接枝在Li6.25Al0.25La3Zr2O12 （LALZO）粒子表面。因此，我们通过热挤压共混制备了含有60 wt.% tmspm功能化LALZO活性填料和聚合物基体（以下简称PICSE60）的PICSE。为了进一步改善PICSE60/电极界面和陶瓷/聚合物基体界面，PEGDMA交联被依次设计为集成界面中间层（记为C-PICSE60）。通过与TMSPM （Li⋅⋅- O=C）和PEO （Li⋅⋅- O - C）的多重Li+配位，这种分子级界面工程有助于桥接陶瓷/聚合物基质界面，并增强Li+通量。实验和计算模型阐明了TMSPM在复合组分之间的分子桥接中的作用。因此，含有少量LiDFOB/ lidfp基液体电解质的C-PICSE60表现出高的Li +转移数（约0.65）、离子电导率（0.66 mS cm⁻¹，RT）、宽的电化学窗口（5.21 V vs. Li/Li +）和稳定的对称电池循环超过2900 h。Li||LiFePO₄完整电池表现出长周期稳定性。采用高压聚丙烯腈包覆的单晶lini0.86 co0.05 mn0.05 al0.042 o2 （PAN@SC-NCMA86）阴极，在0.5 C （2.8-4.3 V）下循环550次后，电池容量保持率为80.82%。这项工作为实现强大的接口兼容性，实现高性能混合ssb的集成工程策略提供了新的见解。
{"title":"Enhanced Particle Interlocking and Interface Design in Dry-Processed Polymer-in-Ceramic Composite Electrolytes with Multifunctional Silane","authors":"Tamene Beshaw Tirfie, Desalegn Yilma Kibret, Tadesu Hailu Mengesha, Behrouz Bazri, Liang-Yin Kuo, Yi-Shiuan Wu, Jeng-Kuei Chang, Rajan Jose, Chun-Chen Yang","doi":"10.1016/j.ensm.2026.105434","DOIUrl":"https://doi.org/10.1016/j.ensm.2026.105434","url":null,"abstract":"Polymer-in-ceramic composite solid-state electrolytes (PICSEs) are a promising strategy for realizing next-generation solid-state batteries (SSBs). However, poor intrinsic interfacial compatibility between the ceramic and polymer matrix and inadequate contact at the electrode-electrolyte interfaces remain serious challenges. Herein, a multifunctional 3-(trimethoxysilyl) propylmethacrylate (TMSPM) molecule is grafted on the Li<ce:inf loc=\"post\">6.25</ce:inf>Al<ce:inf loc=\"post\">0.25</ce:inf>La<ce:inf loc=\"post\">3</ce:inf>Zr<ce:inf loc=\"post\">2</ce:inf>O<ce:inf loc=\"post\">12</ce:inf> (LALZO) particle’s surface. Consequently, we prepared a PICSE with 60 wt.% TMSPM-functionalized LALZO active filler and polymer matrix (hereafter denoted as PICSE60) via thermal extrusion blending. To further improve both the PICSE60/electrode interface and the ceramic/polymer matrix interface, PEGDMA crosslinking was sequentially engineered as an integrated interfacial interlayer (denoted as C-PICSE60). This molecular-level interface engineering helped bridge the ceramic/polymer matrix interphase and enhanced Li<ce:sup loc=\"post\">+</ce:sup> flux throughout the bulk PICSEs via multiple Li<ce:sup loc=\"post\">+</ce:sup> coordination with TMSPM (Li⋅⋅⋅- O=C) and PEO (Li⋅⋅⋅- O‒C). Experimental and computational modeling elucidated the role of TMSPM in molecular bridging between the composite components. Consequently, C-PICSE60, containing a small amount of LiDFOB/LiDFP-based liquid electrolyte, exhibited a high Li⁺ transference number (<ce:italic>ca.</ce:italic> 0.65), ionic conductivity (0.66 mS cm⁻¹, RT), a wide electrochemical window (5.21 V vs. Li/Li⁺), and stable symmetric-cell cycling for over 2900 h. The Li||LiFePO₄ full cells exhibited long cycling stability, retaining 90.83% capacity after 1150 cycles at 0.5 C/1 C. The full cell with a high-voltage polyacrylonitrile-coated single-crystal LiNi<ce:inf loc=\"post\">0.86</ce:inf>Co<ce:inf loc=\"post\">0.05</ce:inf>Mn<ce:inf loc=\"post\">0.05</ce:inf>Al<ce:inf loc=\"post\">0.04</ce:inf>O<ce:inf loc=\"post\">2</ce:inf> (PAN@SC-NCMA86) cathode exhibited 80.82% capacity retention after 550 cycles at 0.5 C (2.8–4.3 V). This work provides new insights into an integrated engineering strategy for achieving robust interfacial compatibility, enabling high-performance hybrid-SSBs.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"166 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2026-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148692400","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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