Pub Date : 2024-11-07DOI: 10.1016/j.ensm.2024.103897
Ziyu Wang , Rui Liu , Junjie Wang , Baoling Wang , Mingshan Zhu , Sujuan Hu
The issue of energy supply in outdoor and remote areas has become a significant challenge. Solar-powered self-sustaining rechargeable zinc-air batteries (RZABs) offer a viable energy solution for off-grid regions. However, there has been no specific study on the technical compatibility and adaptability of the solar power generation system and RZABs system, as well as the efficiency of energy conversion and storage in such solar-powered RZABs systems. To address these challenges, this study developed a solar-powered self-sustaining photo-assisted RZABs system based on a photo-responsive polyterthiophene (pTTh) cathode. This system employs pTTh with photo-responsive properties as the cathode catalyst for RZABs, which not only significantly reduces the overpotential of the cathode but also enhances the performance of the RZABs and the overall energy conversion efficiency (reaching 16.2 %). In practical applications, the system exhibits excellent stability, operating continuously within a wide temperature range of -15 to 40 °C, and demonstrating a stable cycling operation capability of up to 33 days. It provides reliable, low-cost power support for electronic devices such as mobile phones, flashlights, GPS units, and small pollutant detection systems, greatly improving the practicality of these devices in off-grid areas.
{"title":"High energy conversion efficiency and cycle durability of solar-powered self-sustaining light-assisted rechargeable zinc–air batteries system","authors":"Ziyu Wang , Rui Liu , Junjie Wang , Baoling Wang , Mingshan Zhu , Sujuan Hu","doi":"10.1016/j.ensm.2024.103897","DOIUrl":"10.1016/j.ensm.2024.103897","url":null,"abstract":"<div><div>The issue of energy supply in outdoor and remote areas has become a significant challenge. Solar-powered self-sustaining rechargeable zinc-air batteries (RZABs) offer a viable energy solution for off-grid regions. However, there has been no specific study on the technical compatibility and adaptability of the solar power generation system and RZABs system, as well as the efficiency of energy conversion and storage in such solar-powered RZABs systems. To address these challenges, this study developed a solar-powered self-sustaining photo-assisted RZABs system based on a photo-responsive polyterthiophene (pTTh) cathode. This system employs pTTh with photo-responsive properties as the cathode catalyst for RZABs, which not only significantly reduces the overpotential of the cathode but also enhances the performance of the RZABs and the overall energy conversion efficiency (reaching 16.2 %). In practical applications, the system exhibits excellent stability, operating continuously within a wide temperature range of -15 to 40 °C, and demonstrating a stable cycling operation capability of up to 33 days. It provides reliable, low-cost power support for electronic devices such as mobile phones, flashlights, GPS units, and small pollutant detection systems, greatly improving the practicality of these devices in off-grid areas.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"74 ","pages":"Article 103897"},"PeriodicalIF":18.9,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589210","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 : 2024-11-07DOI: 10.1016/j.ensm.2024.103890
Pengfei Dai , Jiangfeng Huang , Xin Cao , Jianwei Zhao , Liang Xue , Yawen Tang , Ping Wu
Prussian blue analogues, particularly metal hexacyanoferrates with double octahedral coordination (DOC) structures, hold great promise as cathode materials for sodium-ion batteries. However, their practical application is hindered by limited structural stability and restricted ionic diffusion channels inherent to the DOC structure. In this study, we have successfully integrated a mixed tetrahedral and octahedral coordination (TOC) structure with the DOC structure by a dual polymerization and high-entropy strategy, thereby optimizing the central metal coordination environment in hexacyanoferrate cathodes. It leverages the TOC structure's superiorities in structural stability and ionic diffusion, resulting in a hexacyanoferrate-based cathode that exhibits exceptional performance, with a capacity retention of 81.6% after 1000 cycles at 0.5 A g-1 and high rate capabilities of 96.7 and 89.1 mAh g-1 at 0.5 and 1 A g-1, respectively. These findings not only underscore the potential of the TOC design for prussian blue cathodes but also pave the way for the development of high-performance, durable sodium-ion battery systems.
普鲁士蓝类似物，特别是具有双八面体配位（DOC）结构的金属六氰基铁氧体，有望成为钠离子电池的阴极材料。然而，DOC 结构固有的有限结构稳定性和离子扩散通道限制阻碍了它们的实际应用。在本研究中，我们通过双聚合和高熵策略，成功地将四面体和八面体混合配位（TOC）结构与 DOC 结构整合在一起，从而优化了六氰基铁酸酯阴极中的中心金属配位环境。它充分利用了 TOC 结构在结构稳定性和离子扩散方面的优势，从而使基于六氰基铁氧体的阴极表现出卓越的性能，在 0.5 A g-1 条件下循环 1000 次后容量保持率达到 81.6%，在 0.5 A g-1 和 1 A g-1 条件下的高倍率能力分别为 96.7 mAh g-1 和 89.1 mAh g-1。这些发现不仅凸显了镨蓝阴极 TOC 设计的潜力，还为开发高性能、耐用的钠离子电池系统铺平了道路。
{"title":"Central metal coordination environment optimization enhances Na diffusion and structural stability in Prussian blue analogues","authors":"Pengfei Dai , Jiangfeng Huang , Xin Cao , Jianwei Zhao , Liang Xue , Yawen Tang , Ping Wu","doi":"10.1016/j.ensm.2024.103890","DOIUrl":"10.1016/j.ensm.2024.103890","url":null,"abstract":"<div><div>Prussian blue analogues, particularly metal hexacyanoferrates with double octahedral coordination (DOC) structures, hold great promise as cathode materials for sodium-ion batteries. However, their practical application is hindered by limited structural stability and restricted ionic diffusion channels inherent to the DOC structure. In this study, we have successfully integrated a mixed tetrahedral and octahedral coordination (TOC) structure with the DOC structure by a dual polymerization and high-entropy strategy, thereby optimizing the central metal coordination environment in hexacyanoferrate cathodes. It leverages the TOC structure's superiorities in structural stability and ionic diffusion, resulting in a hexacyanoferrate-based cathode that exhibits exceptional performance, with a capacity retention of 81.6% after 1000 cycles at 0.5 A g-1 and high rate capabilities of 96.7 and 89.1 mAh g-1 at 0.5 and 1 A g-1, respectively. These findings not only underscore the potential of the TOC design for prussian blue cathodes but also pave the way for the development of high-performance, durable sodium-ion battery systems.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"74 ","pages":"Article 103890"},"PeriodicalIF":18.9,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594577","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 : 2024-11-07DOI: 10.1016/j.ensm.2024.103872
Ahmed Bahrawy , Przemyslaw Galek , Christin Gellrich , Nick Niese , Julia Grothe , Stefan Kaskel
Iontronic architectures operate via multiple ions or redox processes mimicking neural systems capable to operate with complex ions and biological transmitters with high energy efficiency. Recently, ultracapacitors have emerged as novel iontronic switchable devices with a high on/off ratio. We propose a novel iontronic device offering flexible control of the current output of a switchable electrochemical capacitor diode (CAPode) by introducing an additional “gate” electrode. This device mimics field-effect transistor (FET) semiconductors in controlling current output and recovers energy consumed during the forward charging, marking a significant breakthrough. A recently developed unidirectional CAPode system (Ni3Bi2S2@Ni I 1 mol L-1 KOH I AC@Ni) serves as the “working” capacitor (W-Cap) in the novel architecture. The proposed G-CAPode (gate-controlled CAPode) features a third voltage-controlled connection between the “gate” and the counter electrode of the W-Cap. By varying this third voltage channel the electrodes of W-Cap are shifted in potential toward negative or positive potential windows. Hence, by external voltage control the rectification ratios and blocking efficacy can be tuned which is essential for fully controlling the output signal in logic gates. A new circuit monitors the current and potential distribution of the NOT gate: The G-CAPode system exhibits transistor-like characteristics with a −1.2 V bias. This investigation highlights the versatility of the G-CAPode system across applications where transistor-like behavior and accurate current regulation are beneficial, promising advancements in ionologic devices, sensors, and energy storage systems.
离子电子架构通过多种离子或氧化还原过程模拟神经系统运行，能够以高能量效率与复杂离子和生物发射器一起运行。最近，超级电容器作为具有高开/关比率的新型离子电子开关器件出现了。我们提出了一种新型离子电子器件，通过引入额外的 "栅极 "电极，灵活控制可开关电化学电容器二极管（CAPode）的电流输出。该器件模仿场效应晶体管（FET）半导体控制电流输出，并能回收正向充电时消耗的能量，是一项重大突破。新近开发的单向 CAPode 系统（Ni3Bi2S2@Ni I 1 mol L-1 KOH I AC@Ni）可作为新型结构中的 "工作 "电容器（W-Cap）。所提出的 G-CAPode（栅极控制 CAPode）在 W-Cap 的 "栅极 "和反电极之间具有第三个电压控制连接。通过改变这第三个电压通道，W-Cap 电极的电位会向负或正电位窗口移动。因此，通过外部电压控制可以调整整流比和阻断效率，这对于完全控制逻辑门的输出信号至关重要。新电路可监测 "NOT "门的电流和电位分布：G-CAPode 系统在 -1.2 V 偏置下表现出类似晶体管的特性。这项研究凸显了 G-CAPode 系统在各种应用中的多功能性，在这些应用中，类似晶体管的行为和精确的电流调节非常有益，有望推动离子装置、传感器和储能系统的发展。
{"title":"A gated highly variable pseudocapacitor based on redox-window control (G-CAPode)","authors":"Ahmed Bahrawy , Przemyslaw Galek , Christin Gellrich , Nick Niese , Julia Grothe , Stefan Kaskel","doi":"10.1016/j.ensm.2024.103872","DOIUrl":"10.1016/j.ensm.2024.103872","url":null,"abstract":"<div><div>Iontronic architectures operate via multiple ions or redox processes mimicking neural systems capable to operate with complex ions and biological transmitters with high energy efficiency. Recently, ultracapacitors have emerged as novel iontronic switchable devices with a high on/off ratio. We propose a novel iontronic device offering flexible control of the current output of a switchable electrochemical capacitor diode (CAPode) by introducing an additional “gate” electrode. This device mimics field-effect transistor (FET) semiconductors in controlling current output and recovers energy consumed during the forward charging, marking a significant breakthrough. A recently developed unidirectional CAPode system (Ni<sub>3</sub>Bi<sub>2</sub>S<sub>2</sub>@Ni I 1 mol L<sup>-1</sup> KOH I AC@Ni) serves as the “working” capacitor (W-Cap) in the novel architecture. The proposed G-CAPode (gate-controlled CAPode) features a third voltage-controlled connection between the “gate” and the counter electrode of the W-Cap. By varying this third voltage channel the electrodes of W-Cap are shifted in potential toward negative or positive potential windows. Hence, by external voltage control the rectification ratios and blocking efficacy can be tuned which is essential for fully controlling the output signal in logic gates. A new circuit monitors the current and potential distribution of the NOT gate: The G-CAPode system exhibits transistor-like characteristics with a −1.2 V bias. This investigation highlights the versatility of the G-CAPode system across applications where transistor-like behavior and accurate current regulation are beneficial, promising advancements in ionologic devices, sensors, and energy storage systems.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"74 ","pages":"Article 103872"},"PeriodicalIF":18.9,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597868","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-06DOI: 10.1016/j.ensm.2024.103893
Cong Li , Jinzhong Liu , Yuefeng Su , Jinyang Dong , Hongyun Zhang , Meng Wang , Yibiao Guan , Kang Yan , Na Liu , Yun Lu , Ning Li , Yu Su , Feng Wu , Lai Chen
Ni-rich cathode, recognized for high specific capacities and cost-effectiveness, are deemed promising candidates for high-energy Li-ion batteries. However, these cathodes display notable structural instability and experience severe strain propagation during rapid charging and extended cycling under high voltage, hindering their widespread commercialization. To tackle this chemo-mechanical instability without compromising energy and power density, we propose an efficient modification strategy involving hexavalent metal cation-induced three-in-one modification to reconstruct the nanoscale surface phase. This strategy includes uniform W-doping, integration of cation-mixed phases, and Li2WO4 nanolayers on the surface of Ni-rich cathode microspheres. W-doping strengthen the bond to oxygen, thereby enhancing structural stability and suppressing oxygen loss linked to a layered-to-rock salt phase transition during deep delithiation process. Additionally, establishing a cation-mixing domain with an optimal thickness on the cathode surface enhances Li⁺ diffusivity and alleviates particle structural degradation. Moreover, Li2WO4 nanolayers reduce electrolyte side reactions and act as a damping medium against cycling stresses. Importantly, detailed investigations into structural changes before and after modification at varying current rates were conducted to better comprehend the rate-dependent degradation mechanism. These findings yield valuable mechanistic insights into the high-rate utilization of a viable Ni-rich cathode, ensuring prolonged service life in electric vehicles.
富镍阴极具有高比容量和成本效益，被认为是高能锂离子电池的理想候选材料。然而，这些阴极显示出明显的结构不稳定性，在高压下快速充电和长时间循环时会出现严重的应变传播，阻碍了它们的广泛商业化。为了在不影响能量和功率密度的情况下解决这种化学机械不稳定性问题，我们提出了一种高效的改性策略，包括六价金属阳离子诱导的三合一改性，以重建纳米级表面相。该策略包括在富镍阴极微球表面均匀掺杂 W、整合阳离子混合相和 Li2WO4 纳米层。掺杂 W 可加强与氧的结合，从而提高结构的稳定性，抑制深度脱硫过程中从层状到岩盐相转变过程中的氧损耗。此外，在阴极表面建立一个具有最佳厚度的阳离子混合域可提高锂的扩散性，缓解粒子结构退化。此外，Li2WO4 纳米层还能减少电解质副反应，并作为阻尼介质抵御循环应力。重要的是，为了更好地理解速率依赖性降解机制，我们对不同电流速率下改性前后的结构变化进行了详细研究。这些发现为高速利用可行的富镍阴极、确保延长电动汽车的使用寿命提供了宝贵的机理见解。
{"title":"Enhancing chemomechanical stability and high-rate performance of nickel-rich cathodes for lithium-ion batteries through three-in-one modification","authors":"Cong Li , Jinzhong Liu , Yuefeng Su , Jinyang Dong , Hongyun Zhang , Meng Wang , Yibiao Guan , Kang Yan , Na Liu , Yun Lu , Ning Li , Yu Su , Feng Wu , Lai Chen","doi":"10.1016/j.ensm.2024.103893","DOIUrl":"10.1016/j.ensm.2024.103893","url":null,"abstract":"<div><div>Ni-rich cathode, recognized for high specific capacities and cost-effectiveness, are deemed promising candidates for high-energy Li-ion batteries. However, these cathodes display notable structural instability and experience severe strain propagation during rapid charging and extended cycling under high voltage, hindering their widespread commercialization. To tackle this chemo-mechanical instability without compromising energy and power density, we propose an efficient modification strategy involving hexavalent metal cation-induced three-in-one modification to reconstruct the nanoscale surface phase. This strategy includes uniform W-doping, integration of cation-mixed phases, and Li<sub>2</sub>WO<sub>4</sub> nanolayers on the surface of Ni-rich cathode microspheres. W-doping strengthen the bond to oxygen, thereby enhancing structural stability and suppressing oxygen loss linked to a layered-to-rock salt phase transition during deep delithiation process. Additionally, establishing a cation-mixing domain with an optimal thickness on the cathode surface enhances Li⁺ diffusivity and alleviates particle structural degradation. Moreover, Li<sub>2</sub>WO<sub>4</sub> nanolayers reduce electrolyte side reactions and act as a damping medium against cycling stresses. Importantly, detailed investigations into structural changes before and after modification at varying current rates were conducted to better comprehend the rate-dependent degradation mechanism. These findings yield valuable mechanistic insights into the high-rate utilization of a viable Ni-rich cathode, ensuring prolonged service life in electric vehicles.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"74 ","pages":"Article 103893"},"PeriodicalIF":18.9,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588382","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 : 2024-11-06DOI: 10.1016/j.ensm.2024.103892
Yingchun Yan, Zheng Liu, Weining Li, Fan Feng, Xinhou Yang, Bin Qi, Min Gong, Zhiyuan Li, Tong Wei, Zhuangjun Fan
Quasi-solid-state electrolytes (QSSEs) are regarded as the most promising alternative for next-generation battery technology due to the compatibility of assemble process and high safety. However, the rational design of solid hosts to ensure the high-efficiency utilization of tiny liquid electrolytes and the deep understanding of ion transport mechanisms at heterogeneous structures are still challenging. Herein, inspired by the ion transport in biological blood vessels, we propose a nitrogen vacancy modified glassy metal-organic framework (MOF) as Na-ion QSSEs host, which shows multilevel ions transport channels, isotropy property, and no grain boundaries. The vascularized glassy MOF enables the reasonable distribution of a small amount of solvent (14 wt.% (solvent as a percentage of QSSE by mass)) in both macro and microenvironments with specific functions, boosting the fast Na-ion transport (1.18 × 10−4 S cm–1, 30°C) and Na-ion transfer number (0.92), and homogeneous Na-ion nucleation/propagation even at -50°C. Meanwhile, the quasi-solid-state Na||Na3V2(PO4)3/C cell demonstrates excellent rate capability and long cycling stability (0.0288% capacity decay per cycle after 500 cycles). The bioinspired design of glassy MOF will shed light on new avenues for the development of energy storage and conversion.
准固态电解质（QSSE）因其组装工艺的兼容性和高安全性，被视为下一代电池技术最有前途的替代品。然而，如何合理设计固态宿主以确保高效利用微小的液态电解质，以及如何深入理解离子在异质结构中的传输机制，仍然是一项挑战。在此，我们受生物血管离子传输的启发，提出了一种氮空位修饰的玻璃态金属有机框架（MOF）作为纳离子 QSSEs 的宿主，它具有多级离子传输通道、各向同性和无晶界等特性。维管化的玻璃质 MOF 使少量溶剂（14 wt.%（溶剂占 QSSE 的质量百分比））在宏观和微观环境中合理分布，并具有特定功能，从而提高了 Na 离子的快速传输（1.18 × 10-4 S cm-1，30°C）和 Na 离子转移数（0.92），即使在 -50°C 下也能实现均匀的 Na 离子成核/扩散。同时，准固态 Na||Na3V2(PO4)3/C电池表现出卓越的速率能力和长期循环稳定性（500 次循环后每次循环的容量衰减为 0.0288%）。玻璃状 MOF 的生物启发设计将为能源存储和转换的发展提供新的途径。
{"title":"Bioinspired Design of Vascularized Glassy Metal-Organic Frameworks Electrolyte for Quasi-Solid-State Sodium Batteries","authors":"Yingchun Yan, Zheng Liu, Weining Li, Fan Feng, Xinhou Yang, Bin Qi, Min Gong, Zhiyuan Li, Tong Wei, Zhuangjun Fan","doi":"10.1016/j.ensm.2024.103892","DOIUrl":"https://doi.org/10.1016/j.ensm.2024.103892","url":null,"abstract":"Quasi-solid-state electrolytes (QSSEs) are regarded as the most promising alternative for next-generation battery technology due to the compatibility of assemble process and high safety. However, the rational design of solid hosts to ensure the high-efficiency utilization of tiny liquid electrolytes and the deep understanding of ion transport mechanisms at heterogeneous structures are still challenging. Herein, inspired by the ion transport in biological blood vessels, we propose a nitrogen vacancy modified glassy metal-organic framework (MOF) as Na-ion QSSEs host, which shows multilevel ions transport channels, isotropy property, and no grain boundaries. The vascularized glassy MOF enables the reasonable distribution of a small amount of solvent (14 wt.% (solvent as a percentage of QSSE by mass)) in both macro and microenvironments with specific functions, boosting the fast Na-ion transport (1.18 × 10<sup>−4</sup> S cm<sup>–1</sup>, 30°C) and Na-ion transfer number (0.92), and homogeneous Na-ion nucleation/propagation even at -50°C. Meanwhile, the quasi-solid-state Na||Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>/C cell demonstrates excellent rate capability and long cycling stability (0.0288% capacity decay per cycle after 500 cycles). The bioinspired design of glassy MOF will shed light on new avenues for the development of energy storage and conversion.","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"13 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588384","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 : 2024-11-05DOI: 10.1016/j.ensm.2024.103889
Seol Yeon Kang , Woon-Bae Park , Jung Yong Seo , Kee-Sun Sohn , Young-Kook Lee , Joon Seop Kwak , Myoungho Pyo
Na5.6Zn0.6Ga0.4S4, which retains the crystalline structure of its parent form Na6ZnS4, is described as a new class of Na-conducting solid-state electrolytes (SSEs) for all-solid-state batteries. We demonstrate that while Na6ZnS4 is ionically insulating (1.4 nS cm-1), Ga-substitution results in an astonishing improvement of ionic conductivity (σion) to 70.1 μS cm-1, making Na5.6Zn0.6Ga0.4S4 a practical SSE. This dramatic increase in σion (5 × 104 fold) is associated with an increased Na+ occupancy in interstitial sites as ‘x’ increases in Na6-xZn1-xGaxS4, where interstitial Na ions facilitate long-range Na+ conduction, which is otherwise immobile. Ga-substitution also results in phase-pure Na6-xZn1-xGaxS4, contributing at least partially to the enhancement of σion. Furthermore, Na6-xZn1-xGaxS4 exhibits neither releasing H2S gas nor compromising its crystalline structure for several hours under ambient conditions. Ga-substitution also enhances electrochemical stability. While the anodic limit remains largely unchanged, the cathodic limit is significantly lowered from 0.99 V vs. Na2Sn in Na6ZnS4 to 0.35 V in Na5.6Zn0.6Ga0.4S4, resulting in stable Na alloying/dealloying reactions in a symmetric Na2Sn ‖ Na2Sn cell. These findings are comprehensively supported by various experimental and theoretical methods. Finally, we construct a full cell (Na2Sn ‖ TiS2) and demonstrate the practicality of Na5.6Zn0.6Ga0.4S4 as a promising SSE in all solid-state Na ion batteries.
{"title":"Conduction channel creation by interstitial site engineering in otherwise insulating Na6ZnS4 for Na-conducting solid-state electrolytes","authors":"Seol Yeon Kang , Woon-Bae Park , Jung Yong Seo , Kee-Sun Sohn , Young-Kook Lee , Joon Seop Kwak , Myoungho Pyo","doi":"10.1016/j.ensm.2024.103889","DOIUrl":"10.1016/j.ensm.2024.103889","url":null,"abstract":"<div><div>Na<sub>5.6</sub>Zn<sub>0.6</sub>Ga<sub>0.4</sub>S<sub>4</sub>, which retains the crystalline structure of its parent form Na<sub>6</sub>ZnS<sub>4</sub>, is described as a new class of Na-conducting solid-state electrolytes (SSEs) for all-solid-state batteries. We demonstrate that while Na<sub>6</sub>ZnS<sub>4</sub> is ionically insulating (1.4 nS cm<sup>-1</sup>), Ga-substitution results in an astonishing improvement of ionic conductivity (σ<sub>ion</sub>) to 70.1 μS cm<sup>-1</sup>, making Na<sub>5.6</sub>Zn<sub>0.6</sub>Ga<sub>0.4</sub>S<sub>4</sub> a practical SSE. This dramatic increase in σ<sub>ion</sub> (5 × 10<sup>4</sup> fold) is associated with an increased Na<sup>+</sup> occupancy in interstitial sites as ‘x’ increases in Na<sub>6-x</sub>Zn<sub>1-x</sub>Ga<sub>x</sub>S<sub>4</sub>, where interstitial Na ions facilitate long-range Na<sup>+</sup> conduction, which is otherwise immobile. Ga-substitution also results in phase-pure Na<sub>6-x</sub>Zn<sub>1-x</sub>Ga<sub>x</sub>S<sub>4</sub>, contributing at least partially to the enhancement of σ<sub>ion</sub>. Furthermore, Na<sub>6-x</sub>Zn<sub>1-x</sub>Ga<sub>x</sub>S<sub>4</sub> exhibits neither releasing H<sub>2</sub>S gas nor compromising its crystalline structure for several hours under ambient conditions. Ga-substitution also enhances electrochemical stability. While the anodic limit remains largely unchanged, the cathodic limit is significantly lowered from 0.99 V vs. Na<sub>2</sub>Sn in Na<sub>6</sub>ZnS<sub>4</sub> to 0.35 V in Na<sub>5.6</sub>Zn<sub>0.6</sub>Ga<sub>0.4</sub>S<sub>4</sub>, resulting in stable Na alloying/dealloying reactions in a symmetric Na<sub>2</sub>Sn ‖ Na<sub>2</sub>Sn cell. These findings are comprehensively supported by various experimental and theoretical methods. Finally, we construct a full cell (Na<sub>2</sub>Sn ‖ TiS<sub>2</sub>) and demonstrate the practicality of Na<sub>5.6</sub>Zn<sub>0.6</sub>Ga<sub>0.4</sub>S<sub>4</sub> as a promising SSE in all solid-state Na ion batteries.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"74 ","pages":"Article 103889"},"PeriodicalIF":18.9,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588401","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 : 2024-11-05DOI: 10.1016/j.ensm.2024.103891
Ledi Chen , Zaka Ullah , Houliang Sun , Shiwei Yu , Wanting Li , Mingliang Chen , Liwei Liu , Qi Li
Integration of photoactive and lithium storing units into a single cathode endows it with notable capacity in the presence of suitable light. However, the interfacial effect between the two materials causes significant loss of photogenerated electrons during their transfer which is one of the biggest obstacles in the development of current photo-assisted rechargeable batteries. In this paper, a bifunctional cobalt-coordinated organic cathode is fabricated by combining 2,2′-bpy and DHBQ via Co by adopting the spin evaporation technique. It optimizes the pristine interfaces of photoactive and lithium storage units into a photoactive unit-metal interface and a metal-lithium storage unit interface through application of Co. In the presence of light, Co causes a strong metal-ligand charge transfer. Meanwhile, ligand-ligand charge transfer also takes place between the multi-ligands. The synergistic effect of these two phenomena offers a discharge capacity of 387 mAh g -1 which is significantly higher than that of 316 mAh g -1 recorded in the absence of light. The demonstrated design of bifunctional metal-ligand cathode by incorporation of photoactive ligands into lithium storage ligands through applications of metal centers can open the pathways for establishing a new type of photo-assisted lithium-ion batteries with higher efficiency and lower cost.
将光活性单元和锂存储单元集成到一个阴极中，可在适当的光照下产生显著的容量。然而，这两种材料之间的界面效应会导致光生电子在传输过程中大量损失，这是目前光助充电电池发展的最大障碍之一。本文采用自旋蒸发技术，通过 Co 将 2,2′-铋和 DHBQ 结合在一起，制备了一种双功能钴配位有机阴极。在光的作用下，Co 能使金属-配体发生强烈的电荷转移。同时，多配体之间也会发生配体-配体电荷转移。在这两种现象的协同作用下，放电容量达到 387 mAh g -1 ，明显高于无光条件下的 316 mAh g -1 。通过应用金属中心将光活性配体融入锂储能配体，展示了双功能金属配体阴极的设计，这将为建立一种新型光辅助锂离子电池开辟道路，使其具有更高的效率和更低的成本。
{"title":"Dramatic enhancement in lithium-ion battery capacity through synergistic effects of electronic transitions in light-assisted organic coordination cathode material Co(bpy)(dhbq)2","authors":"Ledi Chen , Zaka Ullah , Houliang Sun , Shiwei Yu , Wanting Li , Mingliang Chen , Liwei Liu , Qi Li","doi":"10.1016/j.ensm.2024.103891","DOIUrl":"10.1016/j.ensm.2024.103891","url":null,"abstract":"<div><div>Integration of photoactive and lithium storing units into a single cathode endows it with notable capacity in the presence of suitable light. However, the interfacial effect between the two materials causes significant loss of photogenerated electrons during their transfer which is one of the biggest obstacles in the development of current photo-assisted rechargeable batteries. In this paper, a bifunctional cobalt-coordinated organic cathode is fabricated by combining 2,2′-bpy and DHBQ via Co by adopting the spin evaporation technique. It optimizes the pristine interfaces of photoactive and lithium storage units into a photoactive unit-metal interface and a metal-lithium storage unit interface through application of Co. In the presence of light, Co causes a strong metal-ligand charge transfer. Meanwhile, ligand-ligand charge transfer also takes place between the multi-ligands. The synergistic effect of these two phenomena offers a discharge capacity of 387 mAh g <sup>-1</sup> which is significantly higher than that of 316 mAh g <sup>-1</sup> recorded in the absence of light. The demonstrated design of bifunctional metal-ligand cathode by incorporation of photoactive ligands into lithium storage ligands through applications of metal centers can open the pathways for establishing a new type of photo-assisted lithium-ion batteries with higher efficiency and lower cost.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"74 ","pages":"Article 103891"},"PeriodicalIF":18.9,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588403","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 : 2024-11-05DOI: 10.1016/j.ensm.2024.103886
Zhangxing He , Xinyan Zhu , Yang Song , Bin Li , Xieyu Xu , Zekun Zhang , Ningning Zhao , Yangyang Liu , Jing Zhu , Ling Wang , Lei Dai , Huajun Tian
Aqueous zinc ion batteries (AZIBs) have been regarded as one of the most promising energy storage systems because of their security, high specific capacity and abundant zinc resources, etc. Despite the promising prospects of AZIBs, their practical application is still plagued by dendrite and side reactions on zinc surface. In this paper, glass fiber separators were modified by in-situ loading metal-organic framework MIL-125 (M-125) and its -NH2-functionalized material (NM-125). The designed separator pore structure was successfully adjusted and endowed with -NH2 functional groups, which can ultimately dramatically enhance the electrochemical performance of AZIBs under practical operation conditions. The functionalized NM-125 with smaller pore size and particle size enables NM-125-GF to prevent the transport of macromolecular anions in the electrolyte, guiding and promoting zinc ions to undergo an orderly migration. In addition, -NH2 of NM-125 can adsorb Zn2+ and detach them from the solvated structure, inhibiting the generation of anode-side reactions and optimizing battery performance. Notably, Zn||MnO2 full cell assembled with -NH2 functionalized separator also shows a high initial discharge specific capacity (160.2 mAh g-1) with a high capacity retention of ∼99.8% even after 700 cycles. The rational design of the functionalized separator provides a useful guideline for optimizing high-performance AZIBs.
{"title":"Separator functionalization realizing stable zinc anode through microporous metal-organic framework with special functional group","authors":"Zhangxing He , Xinyan Zhu , Yang Song , Bin Li , Xieyu Xu , Zekun Zhang , Ningning Zhao , Yangyang Liu , Jing Zhu , Ling Wang , Lei Dai , Huajun Tian","doi":"10.1016/j.ensm.2024.103886","DOIUrl":"10.1016/j.ensm.2024.103886","url":null,"abstract":"<div><div>Aqueous zinc ion batteries (AZIBs) have been regarded as one of the most promising energy storage systems because of their security, high specific capacity and abundant zinc resources, etc. Despite the promising prospects of AZIBs, their practical application is still plagued by dendrite and side reactions on zinc surface. In this paper, glass fiber separators were modified by <em>in-situ</em> loading metal-organic framework MIL-125 (M-125) and its -NH<sub>2</sub>-functionalized material (NM-125). The designed separator pore structure was successfully adjusted and endowed with -NH<sub>2</sub> functional groups, which can ultimately dramatically enhance the electrochemical performance of AZIBs under practical operation conditions. The functionalized NM-125 with smaller pore size and particle size enables NM-125-GF to prevent the transport of macromolecular anions in the electrolyte, guiding and promoting zinc ions to undergo an orderly migration. In addition, -NH<sub>2</sub> of NM-125 can adsorb Zn<sup>2+</sup> and detach them from the solvated structure, inhibiting the generation of anode-side reactions and optimizing battery performance. Notably, Zn||MnO<sub>2</sub> full cell assembled with -NH<sub>2</sub> functionalized separator also shows a high initial discharge specific capacity (160.2 mAh g<sup>-1</sup>) with a high capacity retention of ∼99.8% even after 700 cycles. The rational design of the functionalized separator provides a useful guideline for optimizing high-performance AZIBs.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"74 ","pages":"Article 103886"},"PeriodicalIF":18.9,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588404","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 : 2024-11-05DOI: 10.1016/j.ensm.2024.103888
Shengyang Dong , Hang Ren , Jinyao Yang , Jingyuan Zhang , Zeyu Cao , Lifen Long , Zikang Xu , Huaiyu Shao , Xiaogang Zhang
Aqueous proton batteries (APBs) have attracted much attention owing to their fast kinetics, low cost and sustainability. However, the most reported APBs operate under acidic conditions, which will lead to serious hydrogen evolution reaction (HER) and corrosion problem, inevitably. Here, a small molecule organic compound, azobenzene (AB) containing an azo group (N = N), is explored as an anode material for APBs under alkaline electrolyte with a low redox potential of around -0.6 V (vs. Hg/HgO). AB anode achieves high-rate capacity of 151 mAh g-1 at a high current density of 10 A g-1 and excellent cycling stability over 12,500 cycles under 2 M KOH electrolyte. The experimental results and theoretical calculations confirm that AB performs a two-electron redox reaction involving a central N = N group with two protons from H2O molecules. This work reveals the protonation in azo-materials and promotes new insights on design small organic molecules with multi-electron redox reactions in advanced proton secondary batteries.
水质质子电池（APB）因其快速的动力学、低成本和可持续性而备受关注。然而，大多数报道的水质子电池都是在酸性条件下工作的，这将不可避免地导致严重的氢进化反应（HER）和腐蚀问题。在此，我们探索了一种含有偶氮基团（N=N）的小分子有机化合物偶氮苯（AB），将其作为碱性电解质下的 APB 阳极材料，其氧化还原电位约为 -0.6 V（相对于 Hg/HgO）。AB 阳极在 10 A g-1 的高电流密度下实现了 151 mAh g-1 的高倍率容量，并在 2 M KOH 电解液下实现了 12,500 次循环的出色稳定性。实验结果和理论计算证实，AB 发生了双电子氧化还原反应，涉及一个中心 N=N 基团与来自 H2O 分子的两个质子。这项研究揭示了偶氮材料中的质子化现象，为设计先进质子二次电池中具有多电子氧化还原反应的有机小分子提供了新的思路。
{"title":"An aqueous proton battery under alkaline electrolyte","authors":"Shengyang Dong , Hang Ren , Jinyao Yang , Jingyuan Zhang , Zeyu Cao , Lifen Long , Zikang Xu , Huaiyu Shao , Xiaogang Zhang","doi":"10.1016/j.ensm.2024.103888","DOIUrl":"10.1016/j.ensm.2024.103888","url":null,"abstract":"<div><div>Aqueous proton batteries (APBs) have attracted much attention owing to their fast kinetics, low cost and sustainability. However, the most reported APBs operate under acidic conditions, which will lead to serious hydrogen evolution reaction (HER) and corrosion problem, inevitably. Here, a small molecule organic compound, azobenzene (AB) containing an azo group (<em>N</em> = <em>N</em>), is explored as an anode material for APBs under alkaline electrolyte with a low redox potential of around -0.6 V (vs. Hg/HgO). AB anode achieves high-rate capacity of 151 mAh g<sup>-1</sup> at a high current density of 10 A g<sup>-1</sup> and excellent cycling stability over 12,500 cycles under 2 M KOH electrolyte. The experimental results and theoretical calculations confirm that AB performs a two-electron redox reaction involving a central <em>N</em> = <em>N</em> group with two protons from H<sub>2</sub>O molecules. This work reveals the protonation in azo-materials and promotes new insights on design small organic molecules with multi-electron redox reactions in advanced proton secondary batteries.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"74 ","pages":"Article 103888"},"PeriodicalIF":18.9,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588402","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 : 2024-11-05DOI: 10.1016/j.ensm.2024.103887
Junpeng Li , Xubo Yang , Jinwei Wang , Chunjie Ma , Tingxia Wang , Nailiang Liu , Xiufen Pang , Qian Zhang , Chao Wu , Xifei Li
The dissolution of Mn-based oxides cathodes is an urgent issue, as it leads to electrochemically irreversible byproducts and, finally, battery failure. In this work, activated NiMn-LDHv nanosheets with H vacancies are proposed as the cathode material for durable zinc ion batteries. The H vacancies promote Mn2+ deposition by redistributing the electron density and building strong Mn-O bonds, as a result, endowing NiMn-LDHv with the ability of controllable back-deposition of Mn2+. It's verified that MnO2 is deposited on the NiMn-LHDv substrate during charging, the dissolution and the Zn2+/H+ co-intercalation of MnO2 have a combined contribution to the discharge capacity. The full battery with NiMn-LDHv cathode delivers rate capacity of 258 mAh g−1 at 0.3 A g−1, and even 90 mAh g−1 at 11.0 A g−1. Furthermore, the irreversible Mn-based byproducts are inhibited, resulting in durable cycling performance. After 2500 charge/discharge cycles, the initial capacity remains 91 %. This work provides an important strategy to utilize Mn2+ efficiently and develop a robust Mn-based cathode, which could greatly prompt the practical application of aqueous zinc ion batteries.
锰基氧化物阴极的溶解是一个亟待解决的问题，因为它会导致电化学不可逆的副产品，最终导致电池失效。在这项研究中，我们提出将具有 H 空位的活化镍锰-LDHv 纳米片作为耐用锌离子电池的阴极材料。H 空位通过重新分配电子密度和建立强 Mn-O 键来促进 Mn2+ 的沉积，从而使 NiMn-LDHv 具有可控的 Mn2+ 反沉积能力。实验验证了 MnO2 在充电过程中沉积在镍锰-LHDv 衬底上，MnO2 的溶解和 Zn2+/H+ 共掺杂对放电容量有综合贡献。采用镍锰-LDHv 正极的全电池在 0.3 A g-1 时的速率容量为 258 mAh g-1，在 11.0 A g-1 时的速率容量甚至达到 90 mAh g-1。此外，还抑制了不可逆的锰基副产物，从而实现了持久的循环性能。经过 2500 次充放电循环后，初始容量仍保持在 91%。这项研究为高效利用 Mn2+ 和开发坚固的锰基阴极提供了重要策略，这将极大地促进锌离子水电池的实际应用。
{"title":"Highly efficient Mn2+ deposition induced by H-vacancies of NiMn-LDH nanosheets for durable zinc ion batteries","authors":"Junpeng Li , Xubo Yang , Jinwei Wang , Chunjie Ma , Tingxia Wang , Nailiang Liu , Xiufen Pang , Qian Zhang , Chao Wu , Xifei Li","doi":"10.1016/j.ensm.2024.103887","DOIUrl":"10.1016/j.ensm.2024.103887","url":null,"abstract":"<div><div>The dissolution of Mn-based oxides cathodes is an urgent issue, as it leads to electrochemically irreversible byproducts and, finally, battery failure. In this work, activated NiMn-LDHv nanosheets with H vacancies are proposed as the cathode material for durable zinc ion batteries. The H vacancies promote Mn<sup>2+</sup> deposition by redistributing the electron density and building strong Mn-O bonds, as a result, endowing NiMn-LDHv with the ability of controllable back-deposition of Mn<sup>2+</sup>. It's verified that MnO<sub>2</sub> is deposited on the NiMn-LHDv substrate during charging, the dissolution and the Zn<sup>2+</sup>/H<sup>+</sup> co-intercalation of MnO<sub>2</sub> have a combined contribution to the discharge capacity. The full battery with NiMn-LDHv cathode delivers rate capacity of 258 mAh g<sup>−1</sup> at 0.3 A g<sup>−1</sup>, and even 90 mAh g<sup>−1</sup> at 11.0 A g<sup>−1</sup>. Furthermore, the irreversible Mn-based byproducts are inhibited, resulting in durable cycling performance. After 2500 charge/discharge cycles, the initial capacity remains 91 %. This work provides an important strategy to utilize Mn<sup>2+</sup> efficiently and develop a robust Mn-based cathode, which could greatly prompt the practical application of aqueous zinc ion batteries.</div></div>","PeriodicalId":306,"journal":{"name":"Energy Storage Materials","volume":"74 ","pages":"Article 103887"},"PeriodicalIF":18.9,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588405","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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