Aqueous aluminum ion batteries (AAIBs) have garnered extensive attention due to their environmental friendliness, high theoretical capacity, and low cost. However, the sluggish reaction kinetics and severe structural collapse of the cathode material, especially manganese oxide, during the cycling process have hindered its further application. Herein, Cu2+ pre-intercalated layered δ-MnO2 was synthesized via a hydrothermal method. The pre-intercalated Cu2+ ions not only improve the conductivity of MnO2 cathode but also stabilize the structure to enhance stability. X-ray absorption fine structure (XAFS) combined with density functional theory (DFT) calculations confirm the formation of the covalent bond between Cu and O, increasing the electronegativity of O atoms and enhancing the H+ adsorption energy. Moreover, ex-situ measurements not only elucidate the Al3+/H+ co-insertion energy storage mechanism but also demonstrate the high reversibility of the Cu-MnO2 cathode during cycling. This work provides a promising modification approach for the application of manganese oxides in AAIBs.
水性铝离子电池（AAIBs）因其环保、理论容量高和成本低而受到广泛关注。然而，在循环过程中，阴极材料（尤其是氧化锰）反应迟缓、结构严重坍塌，阻碍了其进一步应用。在此，我们通过水热法合成了 Cu2+ 预叠层 δ-MnO2。预镶层的 Cu2+ 离子不仅提高了 MnO2 阴极的导电性，而且稳定了结构，增强了稳定性。X 射线吸收精细结构（XAFS）结合密度泛函理论（DFT）计算证实了 Cu 和 O 之间形成共价键，从而提高了 O 原子的电负性，增强了 H+的吸附能。此外，原位测量不仅阐明了 Al3+/H+ 共插入储能机制，还证明了 Cu-MnO2 阴极在循环过程中的高可逆性。这项工作为锰氧化物在 AAIB 中的应用提供了一种前景广阔的改性方法。
{"title":"Enhancing H+ intercalation kinetics and stability in Cu2+ pre-intercalated δ-MnO2 for aqueous aluminum batteries","authors":"Hanqing Gu , Mingjun Chen , Zhibao Wang, Wenming Zhang, Zhanyu Li","doi":"10.1016/j.jechem.2024.10.031","DOIUrl":"10.1016/j.jechem.2024.10.031","url":null,"abstract":"<div><div>Aqueous aluminum ion batteries (AAIBs) have garnered extensive attention due to their environmental friendliness, high theoretical capacity, and low cost. However, the sluggish reaction kinetics and severe structural collapse of the cathode material, especially manganese oxide, during the cycling process have hindered its further application. Herein, Cu<sup>2+</sup> pre-intercalated layered <em>δ</em>-MnO<sub>2</sub> was synthesized via a hydrothermal method. The pre-intercalated Cu<sup>2+</sup> ions not only improve the conductivity of MnO<sub>2</sub> cathode but also stabilize the structure to enhance stability. X-ray absorption fine structure (XAFS) combined with density functional theory (DFT) calculations confirm the formation of the covalent bond between Cu and O, increasing the electronegativity of O atoms and enhancing the H<sup>+</sup> adsorption energy. Moreover, ex-situ measurements not only elucidate the Al<sup>3+</sup>/H<sup>+</sup> co-insertion energy storage mechanism but also demonstrate the high reversibility of the Cu-MnO<sub>2</sub> cathode during cycling. This work provides a promising modification approach for the application of manganese oxides in AAIBs.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 126-133"},"PeriodicalIF":13.1,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142701641","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Na-ion batteries are considered a promising next-generation battery alternative to Li-ion batteries, due to the abundant Na resources and low cost. Most efforts focus on developing new materials to enhance energy density and electrochemical performance to enable it comparable to Li-ion batteries, without considering thermal hazard of Na-ion batteries and comparison with Li-ion batteries. To address this issue, our work comprehensively compares commercial prismatic lithium iron phosphate (LFP) battery, lithium nickel cobalt manganese oxide (NCM523) battery and Na-ion battery of the same size from thermal hazard perspective using Accelerating Rate Calorimeter. The thermal hazard of the three cells is then qualitatively assessed from thermal stability, early warning and thermal runaway severity perspectives by integrating eight characteristic parameters. The Na-ion cell displays comparable thermal stability with LFP while LFP exhibits the lowest thermal runaway hazard and severity. However, the Na-ion cell displays the lowest safety venting temperature and the longest time interval between safety venting and thermal runaway, allowing the generated gas to be released as early as possible and detected in a timely manner, providing sufficient time for early warning. Finally, a database of thermal runaway characteristic temperature for Li-ion and Na-ion cells is collected and processed to delineate four thermal hazard levels for quantitative assessment. Overall, LFP cells exhibit the lowest thermal hazard, followed by the Na-ion cells and NCM523 cells. This work clarifies the thermal hazard discrepancy between the Na-ion cell and prevalent Li-ion cells, providing crucial guidance for development and application of Na-ion cell.
{"title":"Thermal hazard comparison and assessment of Li-ion battery and Na-ion battery","authors":"Wenxin Mei, Zhixiang Cheng, Longbao Wang, Anqi Teng, Zhiyuan Li, Kaiqiang Jin, Jinhua Sun, Qingsong Wang","doi":"10.1016/j.jechem.2024.10.036","DOIUrl":"10.1016/j.jechem.2024.10.036","url":null,"abstract":"<div><div>Na-ion batteries are considered a promising next-generation battery alternative to Li-ion batteries, due to the abundant Na resources and low cost. Most efforts focus on developing new materials to enhance energy density and electrochemical performance to enable it comparable to Li-ion batteries, without considering thermal hazard of Na-ion batteries and comparison with Li-ion batteries. To address this issue, our work comprehensively compares commercial prismatic lithium iron phosphate (LFP) battery, lithium nickel cobalt manganese oxide (NCM523) battery and Na-ion battery of the same size from thermal hazard perspective using Accelerating Rate Calorimeter. The thermal hazard of the three cells is then qualitatively assessed from thermal stability, early warning and thermal runaway severity perspectives by integrating eight characteristic parameters. The Na-ion cell displays comparable thermal stability with LFP while LFP exhibits the lowest thermal runaway hazard and severity. However, the Na-ion cell displays the lowest safety venting temperature and the longest time interval between safety venting and thermal runaway, allowing the generated gas to be released as early as possible and detected in a timely manner, providing sufficient time for early warning. Finally, a database of thermal runaway characteristic temperature for Li-ion and Na-ion cells is collected and processed to delineate four thermal hazard levels for quantitative assessment. Overall, LFP cells exhibit the lowest thermal hazard, followed by the Na-ion cells and NCM523 cells. This work clarifies the thermal hazard discrepancy between the Na-ion cell and prevalent Li-ion cells, providing crucial guidance for development and application of Na-ion cell.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 18-26"},"PeriodicalIF":13.1,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142701636","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rechargeable aqueous zinc-based batteries (RZBs) often suffer from poor cycling stability due to the instability of zinc deposition and etching processes. This work achieves dendrite-free zinc deposition with a smaller nucleation radius and rapid completion of the nucleation stage by a “triple regulation strategy” with trace chitosan oligosaccharide (COS) in ZnSO4 electrolyte (2 g L−1 COS). Theoretical and experimental results indicate that COS, with hydroxyl and amino functional groups, exhibits a high affinity for the (002)Zn and (100)Zn facets. Under the influence of a small amount of COS, the selective exposure of the (101)Zn facet is facilitated. The extensively exposed (101)Zn facet is protected by COS, which inhibits the occurrence of side reactions. Moreover, the presence of trace COS-02 changes the etching mode from three-dimensional (3D) to two-dimensional (2D), ensuring a uniform distribution of Zn2+ in the electric field during the deposition process. The unique 3D deposition and 2D etching mechanism induced by the COS additive result in exceptional cycling stability, exceeding 3800 h (1 mA cm−2) and 430 h (5 mA cm−2) in zinc symmetrical cells. Additionally, COS acts as a “molecular pillar” to stabilize VS2, enabling the Zn||VS2 full cell to achieve 1000 stable cycles with 89.6% capacity retention and an average coulombic efficiency of 99.95%. This work reveals a novel multiple regulation mechanism by using trace COS in RZBs, and provides a new approach for the development of long-term stable RZBs with preferential exposure facets.
由于锌沉积和蚀刻过程的不稳定性，可充电锌基水溶液电池（RZB）的循环稳定性通常较差。这项研究通过在 ZnSO4 电解液（2 g L-1 COS）中添加微量壳聚糖低聚糖（COS）的 "三重调节策略"，实现了无树枝状晶核的锌沉积，且成核半径更小，成核阶段快速完成。理论和实验结果表明，带有羟基和氨基官能团的 COS 对 (002)Zn 和 (100)Zn 面具有很高的亲和力。在少量 COS 的影响下，(101)Zn 面的选择性暴露得到了促进。广泛暴露的 (101)Zn 面受到 COS 的保护，从而抑制了副反应的发生。此外，痕量 COS-02 的存在将蚀刻模式从三维（3D）转变为二维（2D），确保了在沉积过程中 Zn2+ 在电场中的均匀分布。COS 添加剂诱导的独特三维沉积和二维蚀刻机制带来了卓越的循环稳定性，在锌对称电池中超过 3800 小时（1 mA cm-2）和 430 小时（5 mA cm-2）。此外，COS 还是稳定 VS2 的 "分子支柱"，使 Zn||VS2 全电池实现了 1000 次稳定循环，容量保持率达到 89.6%，平均库仑效率达到 99.95%。这项工作揭示了在 RZB 中使用痕量 COS 的新型多重调节机制，为开发具有优先暴露面的长期稳定 RZB 提供了一种新方法。
{"title":"Deposition and etching of (101)Zn facet exposed zinc electrode induced by trace COS achieving ultra-long cycle stability in zinc batteries","authors":"Keren Lu , Haiyan Jing , Qiubo Guo, Cai Liu, Boyuan Liu, Xifeng Xia, Fengyun Wang, Wu Lei, Mingzhu Xia, Qingli Hao","doi":"10.1016/j.jechem.2024.10.025","DOIUrl":"10.1016/j.jechem.2024.10.025","url":null,"abstract":"<div><div>Rechargeable aqueous zinc-based batteries (RZBs) often suffer from poor cycling stability due to the instability of zinc deposition and etching processes. This work achieves dendrite-free zinc deposition with a smaller nucleation radius and rapid completion of the nucleation stage by a “triple regulation strategy” with trace chitosan oligosaccharide (COS) in ZnSO<sub>4</sub> electrolyte (2 g L<sup>−1</sup> COS). Theoretical and experimental results indicate that COS, with hydroxyl and amino functional groups, exhibits a high affinity for the (002)<sub>Zn</sub> and (100)<sub>Zn</sub> facets. Under the influence of a small amount of COS, the selective exposure of the (101)<sub>Zn</sub> facet is facilitated. The extensively exposed (101)<sub>Zn</sub> facet is protected by COS, which inhibits the occurrence of side reactions. Moreover, the presence of trace COS-02 changes the etching mode from three-dimensional (3D) to two-dimensional (2D), ensuring a uniform distribution of Zn<sup>2+</sup> in the electric field during the deposition process. The unique 3D deposition and 2D etching mechanism induced by the COS additive result in exceptional cycling stability, exceeding 3800 h (1 mA cm<sup>−2</sup>) and 430 h (5 mA cm<sup>−2</sup>) in zinc symmetrical cells. Additionally, COS acts as a “molecular pillar” to stabilize VS<sub>2</sub>, enabling the Zn||VS<sub>2</sub> full cell to achieve 1000 stable cycles with 89.6% capacity retention and an average coulombic efficiency of 99.95%. This work reveals a novel multiple regulation mechanism by using trace COS in RZBs, and provides a new approach for the development of long-term stable RZBs with preferential exposure facets.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 37-48"},"PeriodicalIF":13.1,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142701638","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-30DOI: 10.1016/j.jechem.2024.10.027
Peng Wang , Shafidah Shafian , Feng Qiu , Xiao Zhang , Yuping Zhao , Bin Wu , Kyungkon Kim , Yong Hua , Lin Xie
2,2′,7,7′-Tetrakis(N,N-di(4-methoxyphenyl)amino)-9,9′-spirobifluorene (Spiro) is an essential hole-transport material used in perovskite solar cells (PSCs). However, the redox reaction of Spiro and its impact at the interface with the metal electrode are not yet fully understood. In this study, we introduced a crystalline additive (CA) to regulate the redox process of Spiro and its interface with an Ag electrode. Our findings indicate that CA functions as a molecular scaffold, improving the crystallinity and stability of radicals in Spiro throughout the entire redox reaction. This enhancement increases the hole mobility of Spiro and strengthens the internal electric field, thereby improving hole extraction and transport efficiency at both interfaces. Moreover, the optimized redox reaction of Spiro reduces energy loss at the Ag electrode, significantly boosting the power conversion efficiency to 25.21%. Furthermore, CA mitigates the aggregation of lithium salt and enhances the stability of the device. Our findings contribute to a deeper understanding of hole-transport mechanisms of Spiro and emphasize the importance of reducing energy loss at the Spiro/Ag electrode interface in PSCs.
{"title":"Improving redox reactions of Spiro-OMeTAD via p-type molecular scaffold to reduce energy loss at Ag-electrode in perovskite solar cells","authors":"Peng Wang , Shafidah Shafian , Feng Qiu , Xiao Zhang , Yuping Zhao , Bin Wu , Kyungkon Kim , Yong Hua , Lin Xie","doi":"10.1016/j.jechem.2024.10.027","DOIUrl":"10.1016/j.jechem.2024.10.027","url":null,"abstract":"<div><div>2,2′,7,7′-Tetrakis(<em>N</em>,<em>N</em>-di(4-methoxyphenyl)amino)-9,9′-spirobifluorene (Spiro) is an essential hole-transport material used in perovskite solar cells (PSCs). However, the redox reaction of Spiro and its impact at the interface with the metal electrode are not yet fully understood. In this study, we introduced a crystalline additive (CA) to regulate the redox process of Spiro and its interface with an Ag electrode. Our findings indicate that CA functions as a molecular scaffold, improving the crystallinity and stability of radicals in Spiro throughout the entire redox reaction. This enhancement increases the hole mobility of Spiro and strengthens the internal electric field, thereby improving hole extraction and transport efficiency at both interfaces. Moreover, the optimized redox reaction of Spiro reduces energy loss at the Ag electrode, significantly boosting the power conversion efficiency to 25.21%. Furthermore, CA mitigates the aggregation of lithium salt and enhances the stability of the device. Our findings contribute to a deeper understanding of hole-transport mechanisms of Spiro and emphasize the importance of reducing energy loss at the Spiro/Ag electrode interface in PSCs.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 151-160"},"PeriodicalIF":13.1,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142701586","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Textiles for health and sporting activity monitoring are on the rise with the advent of smart portable wearables. The intention of this work is to design wireless monitoring wearables, based on widely available textiles and low environmental impact production technologies. Herein we have developed a polymeric ink which is able to functionalize different types of textile fibers (including silver conducting fibers, cotton, and commercial textile) with polypyrrole. These fibers were weaved together with a thinner silver conducting fiber and carbon fiber to form a touch-sensitive energy harvesting system that would generate an electric output when mechanical pressure is applied to it. Different prototypes were manufactured with loom weaving accessories to simulate real textile cloths. By simple touch, the prototypes produced a maximum voltage of 244 V and a maximum power density of 2.29 W m−2. The current generated is then transformed into a digital signal, which is further utilized for human motion or gesture monitorization. The system comprises a wireless block for the Internet of Things (IoT) applicability that will be eventually extended to future remote health and sports monitoring systems.
随着智能便携式可穿戴设备的出现，用于健康和体育活动监测的纺织品也在不断增加。这项工作的目的是在广泛使用的纺织品和低环境影响生产技术的基础上，设计无线监测可穿戴设备。在此，我们开发了一种聚合墨水，能够将不同类型的纺织纤维（包括银导电纤维、棉花和商用纺织品）与聚吡咯功能化。我们将这些纤维与较细的银导电纤维和碳纤维编织在一起，形成了一个触敏能量采集系统，当机械压力施加在该系统上时，它就会产生电输出。我们用织布机编织配件制造了不同的原型，以模拟真实的纺织品。通过简单的触摸，原型产生的最大电压为 244 V，最大功率密度为 2.29 W m-2。产生的电流随后被转换成数字信号，进一步用于人体运动或手势监控。该系统包括一个适用于物联网（IoT）的无线模块，最终将扩展到未来的远程健康和运动监测系统。
{"title":"Energy harvesting and movement tracking by polypyrrole functionalized textile for wearable IoT applications","authors":"Guilherme Ferreira , Shubham Das , Guilherme Coelho , Rafael R.A. Silva , Sumita Goswami , Rui N. Pereira , Luís Pereira , Elvira Fortunato , Rodrigo Martins , Suman Nandy","doi":"10.1016/j.jechem.2024.10.028","DOIUrl":"10.1016/j.jechem.2024.10.028","url":null,"abstract":"<div><div>Textiles for health and sporting activity monitoring are on the rise with the advent of smart portable wearables. The intention of this work is to design wireless monitoring wearables, based on widely available textiles and low environmental impact production technologies. Herein we have developed a polymeric ink which is able to functionalize different types of textile fibers (including silver conducting fibers, cotton, and commercial textile) with polypyrrole. These fibers were weaved together with a thinner silver conducting fiber and carbon fiber to form a touch-sensitive energy harvesting system that would generate an electric output when mechanical pressure is applied to it. Different prototypes were manufactured with loom weaving accessories to simulate real textile cloths. By simple touch, the prototypes produced a maximum voltage of 244 V and a maximum power density of 2.29 W m<sup>−2</sup>. The current generated is then transformed into a digital signal, which is further utilized for human motion or gesture monitorization. The system comprises a wireless block for the Internet of Things (IoT) applicability that will be eventually extended to future remote health and sports monitoring systems.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 230-242"},"PeriodicalIF":13.1,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142701770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-30DOI: 10.1016/j.jechem.2024.10.029
Zhonghao Chen , Hongjiao Chen , Teng Li , Xing Tian , Kewei Zhang , Yijun Miao , Changlei Xia , Liping Cai , Bin Hui , Chaoji Chen
A high-activity and stable bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalyst is critical for seawater-based Zn-air batteries (ZABs). Herein, we report a wood-derived chainmail electrocatalyst containing defective nitrogen-doped carbon nanotubes encapsulating cobalt nanoparticles (Co@D-NCNT/CW) to enhance the ORR/OER activity and stability in seawater medium. During the preparation process, the introduction and removal of Zn increased the defect sites and pyridine N content in the carbon material, modulating charge distribution and influencing the adsorption and activation processes. The highly ordered open channels in Co@D-NCNT/CW promoted mass transfer of reactants and accelerated gas diffusion. The resultant chainmail electrocatalyst exhibited impressive bifunctional ORR and OER activities with an ultra-low gap of 0.67 V in seawater-based alkaline electrolyte. The Co@D-NCNT/CW-assembled seawater-based rechargeable liquid ZABs demonstrated a maximum power density of 245.3 mW cm−2 and a long-term cycling performance over 500 h. The seawater-based all-solid-state ZABs achieved the maximum power density of 48.2 mW cm−2 and stabilized over 30 h. Density functional theory revealed that the presence of defects and pyridine nitrogen in Co@D-NCNT/CW modulated the electronic structure of Co, optimizing the binding affinity of the Co sites with intermediates and weakening Cl− adsorption. This work provides a new approach to preparing high-activity and stable ORR/OER electrocatalyst utilizing wood nanostructures, boosting the development of seawater-based ZABs.
高活性、稳定的氧还原反应（ORR）和氧进化反应（OER）双功能电催化剂对于基于海水的锌空气电池（ZAB）至关重要。在此，我们报告了一种由木材衍生的链状电催化剂，该催化剂含有封装钴纳米颗粒的缺陷氮掺杂碳纳米管（Co@D-NCNT/CW），可提高海水介质中 ORR/OER 的活性和稳定性。在制备过程中，锌的引入和去除增加了碳材料中的缺陷位点和吡啶N含量，调节了电荷分布并影响了吸附和活化过程。Co@D-NCNT/CW 中高度有序的开放通道促进了反应物的传质并加速了气体扩散。由此产生的链锁电催化剂在海水碱性电解质中表现出令人印象深刻的 ORR 和 OER 双功能活性，并具有 0.67 V 的超低间隙。Co@D-NCNT/CW 组装的海水基可充电液体 ZABs 的最大功率密度为 245.3 mW cm-2，长期循环性能超过 500 h。密度泛函理论显示，Co@D-NCNT/CW 中缺陷和吡啶氮的存在调节了 Co 的电子结构，优化了 Co 位点与中间体的结合亲和力，削弱了对 Cl- 的吸附。这项工作为利用木质纳米结构制备高活性和稳定的 ORR/OER 电催化剂提供了一种新方法，推动了基于海水的 ZAB 的发展。
{"title":"Defective wood-based chainmail electrocatalysts boost performances of seawater-medium Zn-air batteries","authors":"Zhonghao Chen , Hongjiao Chen , Teng Li , Xing Tian , Kewei Zhang , Yijun Miao , Changlei Xia , Liping Cai , Bin Hui , Chaoji Chen","doi":"10.1016/j.jechem.2024.10.029","DOIUrl":"10.1016/j.jechem.2024.10.029","url":null,"abstract":"<div><div>A high-activity and stable bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalyst is critical for seawater-based Zn-air batteries (ZABs). Herein, we report a wood-derived chainmail electrocatalyst containing defective nitrogen-doped carbon nanotubes encapsulating cobalt nanoparticles (Co@D-NCNT/CW) to enhance the ORR/OER activity and stability in seawater medium. During the preparation process, the introduction and removal of Zn increased the defect sites and pyridine N content in the carbon material, modulating charge distribution and influencing the adsorption and activation processes. The highly ordered open channels in Co@D-NCNT/CW promoted mass transfer of reactants and accelerated gas diffusion. The resultant chainmail electrocatalyst exhibited impressive bifunctional ORR and OER activities with an ultra-low gap of 0.67 V in seawater-based alkaline electrolyte. The Co@D-NCNT/CW-assembled seawater-based rechargeable liquid ZABs demonstrated a maximum power density of 245.3 mW cm<sup>−2</sup> and a long-term cycling performance over 500 h. The seawater-based all-solid-state ZABs achieved the maximum power density of 48.2 mW cm<sup>−2</sup> and stabilized over 30 h. Density functional theory revealed that the presence of defects and pyridine nitrogen in Co@D-NCNT/CW modulated the electronic structure of Co, optimizing the binding affinity of the Co sites with intermediates and weakening Cl<sup>−</sup> adsorption. This work provides a new approach to preparing high-activity and stable ORR/OER electrocatalyst utilizing wood nanostructures, boosting the development of seawater-based ZABs.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 134-143"},"PeriodicalIF":13.1,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142701647","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-30DOI: 10.1016/j.jechem.2024.10.026
Tao Ren , Xinji Dong , Xiaolan Li , Haojie Zhu , Cheng Yang , Jinliang Zhu
{"title":"VP-VO core-shell heterostructure: Harmonizing adsorption and catalysis of polysulfides for high-performance Li-S batteries","authors":"Tao Ren , Xinji Dong , Xiaolan Li , Haojie Zhu , Cheng Yang , Jinliang Zhu","doi":"10.1016/j.jechem.2024.10.026","DOIUrl":"10.1016/j.jechem.2024.10.026","url":null,"abstract":"","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"101 ","pages":"Pages 837-843"},"PeriodicalIF":13.1,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142700845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-30DOI: 10.1016/j.jechem.2024.10.024
Wen-Jing Zhang , Yan-Cheng Hu , Yan-Hong Tan , Jia Li , Ning Li , Jing-Pei Cao
High-energy-density (HED) fuel (e.g. widely used JP-10 and RJ-4), featuring compact 3D polycyclic structure with high strain, is of critical importance for volume-limited military aircraft, since their high density and combustion heat can provide more propulsion energy. To reduce the reliance on petroleum source, it is highly desirable to develop renewable alternatives for the production of strained polycyclic HED fuel, but which remains a big challenge because of the inaccessibility caused by the high strain. We herein demonstrate a three-step catalytic route towards highly strained C17 and C18 spirofuel with biomass feedstocks. The process includes catalytic aldol condensation of renewable cyclohexanone/cyclopentanone with benzaldehyde, catalytic spiro Diels-Alder (D-A) reaction of aldol adduct with isoprene, and catalytic hydrodeoxygenation. The key spiro D-A reaction is enabled by the catalysis of heterogeneous Lewis acidic ionic liquid. The chloroaluminate IL, formed by benign urea and AlCl3, exhibits good catalytic performance and reusability for this step. An eventual hydrodeoxygenation (HDO) over Pd/C and H-Y produces strained tricyclic spirofuel with density >0.93 g/mL, combustion heat >41 MJ/L and freezing point < −40 °C, which are better than the properties of tactical fuel RJ-4. Therefore, it is anticipated that the as-prepared renewable fuels have the potential to replace traditional petroleum-derived HED fuels.
{"title":"Catalytic production of high-energy-density spiro polycyclic jet fuel with biomass derivatives","authors":"Wen-Jing Zhang , Yan-Cheng Hu , Yan-Hong Tan , Jia Li , Ning Li , Jing-Pei Cao","doi":"10.1016/j.jechem.2024.10.024","DOIUrl":"10.1016/j.jechem.2024.10.024","url":null,"abstract":"<div><div>High-energy-density (HED) fuel (e.g. widely used JP-10 and RJ-4), featuring compact 3D polycyclic structure with high strain, is of critical importance for volume-limited military aircraft, since their high density and combustion heat can provide more propulsion energy. To reduce the reliance on petroleum source, it is highly desirable to develop renewable alternatives for the production of strained polycyclic HED fuel, but which remains a big challenge because of the inaccessibility caused by the high strain. We herein demonstrate a three-step catalytic route towards highly strained C<sub>17</sub> and C<sub>18</sub> spirofuel with biomass feedstocks. The process includes catalytic aldol condensation of renewable cyclohexanone/cyclopentanone with benzaldehyde, catalytic spiro Diels-Alder (D-A) reaction of aldol adduct with isoprene, and catalytic hydrodeoxygenation. The key spiro D-A reaction is enabled by the catalysis of heterogeneous Lewis acidic ionic liquid. The chloroaluminate IL, formed by benign urea and AlCl<sub>3</sub>, exhibits good catalytic performance and reusability for this step. An eventual hydrodeoxygenation (HDO) over Pd/C and H-Y produces strained tricyclic spirofuel with density >0.93 g/mL, combustion heat >41 MJ/L and freezing point < −40 °C, which are better than the properties of tactical fuel RJ-4. Therefore, it is anticipated that the as-prepared renewable fuels have the potential to replace traditional petroleum-derived HED fuels.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"101 ","pages":"Pages 760-768"},"PeriodicalIF":13.1,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142664085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-29DOI: 10.1016/j.jechem.2024.09.071
Ziyi Cao , Haoteng Sun , Yi Zhang , Lixia Yuan , Yaqi Liao , Haijin Ji , Shuaipeng Hao , Zhen Li , Long Qie , Yunhui Huang
Micron-sized silicon (μSi) is a promising anode material for next-generation lithium-ion batteries due to its high specific capacity, low cost, and abundant reserves. However, the volume expansion that occurs during cycling leads to the accumulation of undesirable stresses, resulting in pulverization of silicon microparticles and shortened lifespan of the batteries. Herein, a composite film of Cu-PET-Cu is proposed as the current collector (CC) for μSi anodes to replace the conventional Cu CC. Cu-PET-Cu CC is prepared by depositing Cu on both sides of a polyethylene terephthalate (PET) film. The PET layer promises good ductility of the film, permitting the Cu-PET-Cu CC to accommodate the volumetric changes of silicon microparticles and facilitates the stress release through ductile deformation. As a result, the μSi electrode with Cu-PET-Cu CC retains a high specific capacity of 2181 mA h g−1, whereas the μSi electrode with Cu CC (μSi/Cu) exhibits a specific capacity of 1285 mA h g−1 after 80 cycles. The stress relieving effect of Cu-PET-Cu was demonstrated by in-situ fiber optic stress monitoring and multi-physics simulations. This work proposes an effective stress relief strategy at the electrode level for the practical implementation of μSi anodes.
微米级硅 (μSi)具有比容量高、成本低和储量丰富等优点，是下一代锂离子电池的理想负极材料。然而，在循环过程中发生的体积膨胀会导致不良应力的积累，从而导致硅微颗粒的粉碎和电池寿命的缩短。本文提出了一种 Cu-PET-Cu 复合薄膜作为微硅阳极的集流器（CC），以取代传统的 Cu CC。Cu-PET-Cu CC 是通过在聚对苯二甲酸乙二醇酯（PET）薄膜的两面沉积铜来制备的。PET 层保证了薄膜的良好延展性，使 Cu-PET-Cu CC 能够适应硅微颗粒的体积变化，并通过延展变形促进应力释放。因此，带有 Cu-PET-Cu CC 的微硅电极在 80 个循环后仍能保持 2181 mA h g-1 的高比容量，而带有 Cu CC 的微硅电极（μSi/Cu）的比容量为 1285 mA h g-1。原位光纤应力监测和多物理场仿真证明了 Cu-PET-Cu 的应力消除效果。这项研究提出了一种有效的电极应力消除策略，可用于μSi 阳极的实际应用。
{"title":"Metallized polymer current collector as “stress acceptor” for stable micron-sized silicon anodes","authors":"Ziyi Cao , Haoteng Sun , Yi Zhang , Lixia Yuan , Yaqi Liao , Haijin Ji , Shuaipeng Hao , Zhen Li , Long Qie , Yunhui Huang","doi":"10.1016/j.jechem.2024.09.071","DOIUrl":"10.1016/j.jechem.2024.09.071","url":null,"abstract":"<div><div>Micron-sized silicon (μSi) is a promising anode material for next-generation lithium-ion batteries due to its high specific capacity, low cost, and abundant reserves. However, the volume expansion that occurs during cycling leads to the accumulation of undesirable stresses, resulting in pulverization of silicon microparticles and shortened lifespan of the batteries. Herein, a composite film of Cu-PET-Cu is proposed as the current collector (CC) for μSi anodes to replace the conventional Cu CC. Cu-PET-Cu CC is prepared by depositing Cu on both sides of a polyethylene terephthalate (PET) film. The PET layer promises good ductility of the film, permitting the Cu-PET-Cu CC to accommodate the volumetric changes of silicon microparticles and facilitates the stress release through ductile deformation. As a result, the μSi electrode with Cu-PET-Cu CC retains a high specific capacity of 2181 mA h g<sup>−1</sup>, whereas the μSi electrode with Cu CC (μSi/Cu) exhibits a specific capacity of 1285 mA h g<sup>−1</sup> after 80 cycles. The stress relieving effect of Cu-PET-Cu was demonstrated by in-situ fiber optic stress monitoring and multi-physics simulations. This work proposes an effective stress relief strategy at the electrode level for the practical implementation of μSi anodes.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"101 ","pages":"Pages 786-794"},"PeriodicalIF":13.1,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142664011","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Electrolyte engineering with fluoroethers as solvents offers promising potential for high-performance lithium metal batteries. Despite recent progresses achieved in designing and synthesizing novel fluoroether solvents, a systematic understanding of how fluorination patterns impact electrolyte performance is still lacking. We investigate the effects of fluorination patterns on properties of electrolytes using fluorinated 1,2-diethoxyethane (FDEE) as single solvents. By employing quantum calculations, molecular dynamics simulations, and interpretable machine learning, we establish significant correlations between fluorination patterns and electrolyte properties. Higher fluorination levels enhance FDEE stability but decrease conductivity. The symmetry of fluorination sites is critical for stability and viscosity, while exerting minimal influence on ionic conductivity. FDEEs with highly symmetric fluorination sites exhibit favorable viscosity, stability, and overall electrolyte performance. Conductivity primarily depends on lithium-anion dissociation or association. These findings provide design principles for rational fluoroether electrolyte design, emphasizing the trade-offs between stability, viscosity, and conductivity. Our work underscores the significance of considering fluorination patterns and molecular symmetry in the development of fluoroether-based electrolytes for advanced lithium batteries.
{"title":"Design principles of fluoroether solvents for lithium metal battery electrolytes unveiled by extensive molecular simulation and machine learning","authors":"Xueying Yuan , Xiupeng Chen , Yuanxin Zhou , Zhiao Yu , Xian Kong","doi":"10.1016/j.jechem.2024.10.021","DOIUrl":"10.1016/j.jechem.2024.10.021","url":null,"abstract":"<div><div>Electrolyte engineering with fluoroethers as solvents offers promising potential for high-performance lithium metal batteries. Despite recent progresses achieved in designing and synthesizing novel fluoroether solvents, a systematic understanding of how fluorination patterns impact electrolyte performance is still lacking. We investigate the effects of fluorination patterns on properties of electrolytes using fluorinated 1,2-diethoxyethane (FDEE) as single solvents. By employing quantum calculations, molecular dynamics simulations, and interpretable machine learning, we establish significant correlations between fluorination patterns and electrolyte properties. Higher fluorination levels enhance FDEE stability but decrease conductivity. The symmetry of fluorination sites is critical for stability and viscosity, while exerting minimal influence on ionic conductivity. FDEEs with highly symmetric fluorination sites exhibit favorable viscosity, stability, and overall electrolyte performance. Conductivity primarily depends on lithium-anion dissociation or association. These findings provide design principles for rational fluoroether electrolyte design, emphasizing the trade-offs between stability, viscosity, and conductivity. Our work underscores the significance of considering fluorination patterns and molecular symmetry in the development of fluoroether-based electrolytes for advanced lithium batteries.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"102 ","pages":"Pages 52-62"},"PeriodicalIF":13.1,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142701640","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号