KVPO4F with excellent structural stability and high operating voltage has been identified as a promising cathode for potassium-ion batteries (PIBs), but limits in sluggish ion transport and severe volume change cause insufficient potassium storage capability. Here, a high-energy and low-strain KVPO4F composite cathode assisted by multifunctional K2C4O4 electrode stabilizer is exquisitely designed. Systematical electrochemical investigations demonstrate that this composite cathode can deliver a remarkable energy density up to 530 Wh kg−1 with 142.7 mAh g−1 of reversible capacity at 25 mA g−1, outstanding rate capability of 70.6 mAh g−1 at 1000 mA g−1, and decent cycling stability. Furthermore, slight volume change (~5%) and increased interfacial stability with thin and even cathode–electrolyte interphase can be observed through in situ and ex situ characterizations, which are attributed to the synergistic effect from in situ potassium compensation and carbon deposition through self-sacrificing K2C4O4 additive. Moreover, potassium-ion full cells manifest significant improvement in energy density and cycling stability. This work demonstrates a positive impact of K2C4O4 additive on the comprehensive electrochemical enhancement, especially the activation of high-voltage plateau capacity and provides an efficient strategy to enlighten the design of other high-voltage cathodes for advanced high-energy batteries.
KVPO4F 具有优异的结构稳定性和较高的工作电压,被认为是一种很有前途的钾离子电池(PIB)阴极,但由于离子传输迟缓和体积变化严重等限制,导致钾储存能力不足。在此,我们精心设计了一种由多功能 K2C4O4 电极稳定剂辅助的高能量、低应变 KVPO4F 复合阴极。系统的电化学研究表明,这种复合阴极的能量密度高达 530 Wh kg-1,在 25 mA g-1 下的可逆容量为 142.7 mAh g-1,在 1000 mA g-1 下的速率能力为 70.6 mAh g-1,并且具有良好的循环稳定性。此外,通过原位和非原位表征,可以观察到微小的体积变化(约 5%)和更高的界面稳定性,阴极-电解质间相薄而均匀,这归因于原位钾补偿和通过自牺牲 K2C4O4 添加剂进行碳沉积的协同效应。此外,钾离子全电池在能量密度和循环稳定性方面也有显著改善。这项工作证明了 K2C4O4 添加剂对全面提高电化学性能,特别是激活高电压高原容量的积极影响,并为先进高能电池的其他高电压阴极的设计提供了一种有效的启迪策略。
{"title":"Low-Strain and High-Energy KVPO4F Cathode with Multifunctional Stabilizer for Advanced Potassium-Ion Batteries","authors":"Yongli Heng, Zhenyi Gu, Jinzhi Guo, Haojie Liang, Yan Liu, Wei Guo, Xinxin Zhao, Xiaotong Wang, Xinglong Wu","doi":"10.1002/eem2.12721","DOIUrl":"10.1002/eem2.12721","url":null,"abstract":"<p>KVPO<sub>4</sub>F with excellent structural stability and high operating voltage has been identified as a promising cathode for potassium-ion batteries (PIBs), but limits in sluggish ion transport and severe volume change cause insufficient potassium storage capability. Here, a high-energy and low-strain KVPO<sub>4</sub>F composite cathode assisted by multifunctional K<sub>2</sub>C<sub>4</sub>O<sub>4</sub> electrode stabilizer is exquisitely designed. Systematical electrochemical investigations demonstrate that this composite cathode can deliver a remarkable energy density up to 530 Wh kg<sup>−1</sup> with 142.7 mAh g<sup>−1</sup> of reversible capacity at 25 mA g<sup>−1</sup>, outstanding rate capability of 70.6 mAh g<sup>−1</sup> at 1000 mA g<sup>−1</sup>, and decent cycling stability. Furthermore, slight volume change (~5%) and increased interfacial stability with thin and even cathode–electrolyte interphase can be observed through in situ and ex situ characterizations, which are attributed to the synergistic effect from in situ potassium compensation and carbon deposition through self-sacrificing K<sub>2</sub>C<sub>4</sub>O<sub>4</sub> additive. Moreover, potassium-ion full cells manifest significant improvement in energy density and cycling stability. This work demonstrates a positive impact of K<sub>2</sub>C<sub>4</sub>O<sub>4</sub> additive on the comprehensive electrochemical enhancement, especially the activation of high-voltage plateau capacity and provides an efficient strategy to enlighten the design of other high-voltage cathodes for advanced high-energy batteries.</p>","PeriodicalId":11554,"journal":{"name":"Energy & Environmental Materials","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/eem2.12721","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140663853","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
FeS2 cathode is promising for all-solid-state lithium batteries due to its ultra-high capacity, low cost, and environmental friendliness. However, the poor performances, induced by limited electrode-electrolyte interface, severe volume expansion, and polysulfide shuttle, hinder the application of FeS2 in all-solid-state lithium batteries. Herein, an integrated 3D FeS2 electrode with full infiltration of Li6PS5Cl sulfide electrolytes is designed to address these challenges. Such a 3D integrated design not only achieves intimate and maximized interfacial contact between electrode and sulfide electrolytes, but also effectively buffers the inner volume change of FeS2 and completely eliminates the polysulfide shuttle through direct solid–solid conversion of Li2S/S. Besides, the vertical 3D arrays guarantee direct electron transport channels and horizontally shortened ion diffusion paths, endowing the integrated electrode with a remarkably reduced interfacial impedance and enhanced reaction kinetics. Benefiting from these synergies, the integrated all-solid-state lithium battery exhibits the largest reversible capacity (667 mAh g−1), best rate performance, and highest capacity retention of 82% over 500 cycles at 0.1 C compared to both a liquid battery and non-integrated all-solid-state lithium battery. The cycling performance is among the best reported for FeS2-based all-solid-state lithium batteries. This work presents an innovative synergistic strategy for designing long-cycling high-energy all-solid-state lithium batteries, which can be readily applied to other battery systems, such as lithium-sulfur batteries.
{"title":"Synergistic Coupling of Sulfide Electrolyte and Integrated 3D FeS2 Electrode Toward Long-Cycling All-Solid-State Lithium Batteries","authors":"Wenyi Liu, Yongzhi Zhao, Chengjun Yi, Weifei Hu, Jiale Xia, Yuanyuan Li, Jinping Liu","doi":"10.1002/eem2.12719","DOIUrl":"10.1002/eem2.12719","url":null,"abstract":"<p>FeS<sub>2</sub> cathode is promising for all-solid-state lithium batteries due to its ultra-high capacity, low cost, and environmental friendliness. However, the poor performances, induced by limited electrode-electrolyte interface, severe volume expansion, and polysulfide shuttle, hinder the application of FeS<sub>2</sub> in all-solid-state lithium batteries. Herein, an integrated 3D FeS<sub>2</sub> electrode with full infiltration of Li<sub>6</sub>PS<sub>5</sub>Cl sulfide electrolytes is designed to address these challenges. Such a 3D integrated design not only achieves intimate and maximized interfacial contact between electrode and sulfide electrolytes, but also effectively buffers the inner volume change of FeS<sub>2</sub> and completely eliminates the polysulfide shuttle through direct solid–solid conversion of Li<sub>2</sub>S/S. Besides, the vertical 3D arrays guarantee direct electron transport channels and horizontally shortened ion diffusion paths, endowing the integrated electrode with a remarkably reduced interfacial impedance and enhanced reaction kinetics. Benefiting from these synergies, the integrated all-solid-state lithium battery exhibits the largest reversible capacity (667 mAh g<sup>−1</sup>), best rate performance, and highest capacity retention of 82% over 500 cycles at 0.1 C compared to both a liquid battery and non-integrated all-solid-state lithium battery. The cycling performance is among the best reported for FeS<sub>2</sub>-based all-solid-state lithium batteries. This work presents an innovative synergistic strategy for designing long-cycling high-energy all-solid-state lithium batteries, which can be readily applied to other battery systems, such as lithium-sulfur batteries.</p>","PeriodicalId":11554,"journal":{"name":"Energy & Environmental Materials","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/eem2.12719","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140661091","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jinxin Bi, Shaoyin Li, Dongtao Liu, Bowei Li, Kai Yang, Ming Xu, Chaopeng Fu, Yunlong Zhao, Wei Zhang
Perovskite solar cells have emerged as a promising technology for renewable energy generation. However, the successful integration of perovskite solar cells with energy storage devices to establish high-efficiency and long-term stable photorechargeable systems remains a persistent challenge. Issues such as electrical mismatch and restricted integration levels contribute to elevated internal resistance, leading to suboptimal overall efficiency (ηoverall) within photorechargeable systems. Additionally, the compatibility of perovskite solar cells with electrolytes from energy storage devices poses another significant concern regarding their stability. To address these limitations, we demonstrate a highly integrated photorechargeable system that combines perovskite solar cells with a solid-state zinc-ion hybrid capacitor using a streamlined process. Our study employs a novel ultraviolet-cured ionogel electrolyte to prevent moisture-induced degradation of the perovskite layer in integrated photorechargeable system, enabling perovskite solar cells to achieve maximum power conversion efficiencies and facilitating the monolithic design of the system with minimal energy loss. By precisely matching voltages between the two modules and leveraging the superior energy storage efficiency, our integrated photorechargeable system achieves a remarkable ηoverall of 10.01% while maintaining excellent cycling stability. This innovative design and the comprehensive investigations of the dynamic photocharging process in monolithic systems, not only offer a reliable and enduring power source but also provide guidelines for future development of self-power off-grid electronics.
{"title":"Highly Integrated Perovskite Solar Cells-Based Photorechargeable System with Excellent Photoelectric Conversion and Energy Storage Ability","authors":"Jinxin Bi, Shaoyin Li, Dongtao Liu, Bowei Li, Kai Yang, Ming Xu, Chaopeng Fu, Yunlong Zhao, Wei Zhang","doi":"10.1002/eem2.12728","DOIUrl":"10.1002/eem2.12728","url":null,"abstract":"<p>Perovskite solar cells have emerged as a promising technology for renewable energy generation. However, the successful integration of perovskite solar cells with energy storage devices to establish high-efficiency and long-term stable photorechargeable systems remains a persistent challenge. Issues such as electrical mismatch and restricted integration levels contribute to elevated internal resistance, leading to suboptimal overall efficiency (<i>η</i><sub>overall</sub>) within photorechargeable systems. Additionally, the compatibility of perovskite solar cells with electrolytes from energy storage devices poses another significant concern regarding their stability. To address these limitations, we demonstrate a highly integrated photorechargeable system that combines perovskite solar cells with a solid-state zinc-ion hybrid capacitor using a streamlined process. Our study employs a novel ultraviolet-cured ionogel electrolyte to prevent moisture-induced degradation of the perovskite layer in integrated photorechargeable system, enabling perovskite solar cells to achieve maximum power conversion efficiencies and facilitating the monolithic design of the system with minimal energy loss. By precisely matching voltages between the two modules and leveraging the superior energy storage efficiency, our integrated photorechargeable system achieves a remarkable η<sub>overall</sub> of 10.01% while maintaining excellent cycling stability. This innovative design and the comprehensive investigations of the dynamic photocharging process in monolithic systems, not only offer a reliable and enduring power source but also provide guidelines for future development of self-power off-grid electronics.</p>","PeriodicalId":11554,"journal":{"name":"Energy & Environmental Materials","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/eem2.12728","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140662510","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiao Li, Yibin Zhang, Bao Qiu, Guoxin Chen, Yuhuan Zhou, Qingwen Gu, Zhaoping Liu
The undesirable capacity loss after first cycle is universal among layered cathode materials, which results in the capacity and energy decay. The key to resolving this obstacle lies in understanding the effect and origin of specific active Li sites during discharge process. In this study, focusing on Ah-level pouch cells for reliability, an ultrahigh initial Coulombic efficiency (96.1%) is achieved in an archetypical Li-rich layered oxide material. Combining the structure and electrochemistry analysis, we demonstrate that the achievement of high-capacity reversibility is a kinetic effect, primarily related to the sluggish Li mobility during oxygen reduction. Activating oxygen reduction through small density would induce the oxygen framework contraction, which, according to Pauli repulsion, imposes a great repulsive force to hinder the transport of tetrahedral Li. The tetrahedral Li storage upon deep oxygen reduction is experimentally visualized and, more importantly, contributes to 6% Coulombic efficiency enhancement as well as 10% energy density improvement for pouch cells, which shows great potentials breaking through the capacity and energy limitation imposed by intercalation chemistry.
{"title":"Dependence of Initial Capacity Irreversibility on Oxygen Framework Chemistry in Li-Rich Layered Cathode Oxides","authors":"Xiao Li, Yibin Zhang, Bao Qiu, Guoxin Chen, Yuhuan Zhou, Qingwen Gu, Zhaoping Liu","doi":"10.1002/eem2.12722","DOIUrl":"10.1002/eem2.12722","url":null,"abstract":"<p>The undesirable capacity loss after first cycle is universal among layered cathode materials, which results in the capacity and energy decay. The key to resolving this obstacle lies in understanding the effect and origin of specific active Li sites during discharge process. In this study, focusing on Ah-level pouch cells for reliability, an ultrahigh initial Coulombic efficiency (96.1%) is achieved in an archetypical Li-rich layered oxide material. Combining the structure and electrochemistry analysis, we demonstrate that the achievement of high-capacity reversibility is a kinetic effect, primarily related to the sluggish Li mobility during oxygen reduction. Activating oxygen reduction through small density would induce the oxygen framework contraction, which, according to Pauli repulsion, imposes a great repulsive force to hinder the transport of tetrahedral Li. The tetrahedral Li storage upon deep oxygen reduction is experimentally visualized and, more importantly, contributes to 6% Coulombic efficiency enhancement as well as 10% energy density improvement for pouch cells, which shows great potentials breaking through the capacity and energy limitation imposed by intercalation chemistry.</p>","PeriodicalId":11554,"journal":{"name":"Energy & Environmental Materials","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/eem2.12722","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140680634","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Li Zhang, Peiyue Jin, Ze Wu, Bo Zhou, Junchang Jiang, Aomeng Deng, Qiuyue Li, Tanveer Hussain, Yiqiong Zhang, Hanwen Liu, Shuangyin Wang
The electrochemical coupling of biomass oxidation and nitrogen conversion presents a potential strategy for high value-added chemicals and nitrogen cycling. Herein, in this work, CuO/Co3O4 with heterogeneous interface is successfully constructed as a bifunctional catalyst for the electrooxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and the electroreduction of nitrate to ammonia (NH3). The open-circuit potential spontaneous experiment shows that more 5-hydroxymethylfurfural molecules are adsorbed in the Helmholtz layer of the CuO/Co3O4 composite, which certifies that the CuO/Co3O4 heterostructure is conducive to the kinetic adsorption of 5-hydroxymethylfurfural. In situ electrochemical impedance spectroscopy further shows that CuO/Co3O4 has faster reaction kinetics and lower reaction potential in oxygen evolution reaction and 5-hydroxymethylfurfural electrocatalytic oxidation. Moreover, CuO/Co3O4 also has a good reduction effect on