Solid-state lithium batteries have been regarded as a promising candidate to become the power supply for electric vehicles and smart grids due to their high energy density and reliable safety. The solid polymer electrolytes (SPEs) with light and thin features show distinctive potential in boosting the available energy density at battery level, whereas their ionic conductivity smaller than 10−4∼10−5 S cm−1 at room temperature constrains the ionic transfer kinetics, leading to low power density and short cycling life. To overcome such problem, the increase of lithium-salt concentration over 50 wt% evokes the conversion from “salt-in-polymer” to “polymer-in-salt” (PIS) of SPEs, which can make additional ionic migration pathway and thus the improved ionic conductivity. However, the abundant lithium-salt may also cause the reduced electrochemical window as well as mechanical properties, which restricts the compatibility with high-voltage cathodes and lowers the operation safety. In this review, the structures and characteristics of PIS electrolytes have been elucidated through clarifying the correlation between lithium-salt and polymer matrix. Then, the recent modification engineering progresses on PIS electrolytes are addressed from the aspects of component regulations including polymer matrices, lithium salts and fillers, novel preparation techniques, and extended application scenarios. The crucial challenges and possible research directions are finally proposed for the PIS electrolytes regarding both science and practical perspectives.
固态锂电池因其高能量密度和可靠的安全性,被视为电动汽车和智能电网电源的理想候选材料。具有轻薄特性的固体聚合物电解质(SPEs)在提高电池级可用能量密度方面显示出独特的潜力,但其在室温下小于 10-4∼10-5 S cm-1 的离子电导率限制了离子转移动力学,导致功率密度低和循环寿命短。为克服这一问题,将锂盐浓度提高到 50 wt% 以上,可促使固相萃取剂从 "聚合物中的盐 "转化为 "盐中聚合物"(PIS),从而增加离子迁移途径,提高离子导电率。然而,丰富的锂盐也可能导致电化学窗口和机械性能降低,从而限制了与高压正极的兼容性,降低了操作安全性。本综述通过阐明锂盐与聚合物基体之间的相关性,阐明了 PIS 电解质的结构和特性。然后,从聚合物基质、锂盐和填料等成分的规定、新型制备技术和扩展应用场景等方面,探讨了 PIS 电解质的最新改性工程进展。最后,从科学和实用角度提出了 PIS 电解质面临的关键挑战和可能的研究方向。
{"title":"Modification engineering of “polymer-in-salt” electrolytes toward high-stability solid-state lithium batteries","authors":"Xiaotong Chang, Kaiyue Liu, Mengyang Jia, Zhijie Bi, Xiangxin Guo","doi":"10.1002/ece2.59","DOIUrl":"https://doi.org/10.1002/ece2.59","url":null,"abstract":"<p>Solid-state lithium batteries have been regarded as a promising candidate to become the power supply for electric vehicles and smart grids due to their high energy density and reliable safety. The solid polymer electrolytes (SPEs) with light and thin features show distinctive potential in boosting the available energy density at battery level, whereas their ionic conductivity smaller than 10<sup>−4</sup>∼10<sup>−5</sup> S cm<sup>−1</sup> at room temperature constrains the ionic transfer kinetics, leading to low power density and short cycling life. To overcome such problem, the increase of lithium-salt concentration over 50 wt% evokes the conversion from “salt-in-polymer” to “polymer-in-salt” (PIS) of SPEs, which can make additional ionic migration pathway and thus the improved ionic conductivity. However, the abundant lithium-salt may also cause the reduced electrochemical window as well as mechanical properties, which restricts the compatibility with high-voltage cathodes and lowers the operation safety. In this review, the structures and characteristics of PIS electrolytes have been elucidated through clarifying the correlation between lithium-salt and polymer matrix. Then, the recent modification engineering progresses on PIS electrolytes are addressed from the aspects of component regulations including polymer matrices, lithium salts and fillers, novel preparation techniques, and extended application scenarios. The crucial challenges and possible research directions are finally proposed for the PIS electrolytes regarding both science and practical perspectives.</p>","PeriodicalId":100387,"journal":{"name":"EcoEnergy","volume":"2 3","pages":"433-447"},"PeriodicalIF":0.0,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ece2.59","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313384","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The electrochemical reduction reaction of CO2 (CO2RR) holds promise for converting CO2 into valuable fuels and chemicals, particularly when powered by renewable electricity, thereby aiding in reducing atmospheric CO2 levels and addressing climate change. Copper phthalocyanine and its derivatives (Cu-Pcs) have attracted significant attention as versatile electrocatalytic materials with high selectivity toward various hydrocarbon products. However, the real active sites of Cu-Pcs for different products vary, and there is a lack of comprehensive summary. To address this gap, we analyze and summarize previous research, yielding the following insights: Cu-Pcs undergo reconstruction and demetallization during CO2RR, with Cu(II) converting to Cu(0), forming transient copper nanoclusters (Cu NCs). The selectivity for CO2RR products closely correlates with the size of those derived Cu NCs. Specifically, reversible Cu NCs with ultrasmall sizes (≤2 nm), which revert to Cu-Pcs after electrolysis, exhibit high selectivity toward CH4. As Cu NCs increase in size, there is a higher CO coverage, promoting CO generation. When Cu NCs exceed a critical threshold size (approximately 15 nm), C-C coupling can occur, facilitating the formation of multicarbon (C2+) products. Furthermore, the structure of macrocycles, types of functional groups, and properties of carbon substrates influence the size and electron density of Cu NCs, thereby impacting the selectivity of CO2RR products.
二氧化碳的电化学还原反应(CO2RR)有望将二氧化碳转化为有价值的燃料和化学品,尤其是在使用可再生电力的情况下,从而有助于降低大气中的二氧化碳含量和应对气候变化。酞菁铜及其衍生物(Cu-Pcs)作为对各种碳氢化合物产品具有高选择性的多功能电催化材料,已经引起了广泛关注。然而,Cu-Pcs 对不同产物的真正活性位点各不相同,而且缺乏全面的总结。为了填补这一空白,我们分析并总结了以往的研究,得出以下见解:在 CO2RR 过程中,Cu-Pcs 经历了重构和脱金属过程,Cu(II) 转化为 Cu(0),形成瞬态纳米铜簇(Cu NCs)。CO2RR 产物的选择性与这些衍生 Cu NCs 的大小密切相关。具体来说,超小尺寸(≤2 纳米)的可逆 Cu NCs 在电解后会还原为 Cu-Pcs,对 CH4 具有高选择性。随着 Cu NCs 尺寸的增大,CO 的覆盖率也随之增大,从而促进了 CO 的生成。当 Cu NCs 的尺寸超过临界值(约 15 nm)时,就会发生 C-C 偶联,从而促进多碳(C2+)产物的形成。此外,大环的结构、官能团的类型以及碳基质的性质都会影响 Cu NCs 的尺寸和电子密度,从而影响 CO2RR 产物的选择性。
{"title":"Copper nanoclusters derived from copper phthalocyanine as real active sites for CO2 electroreduction: Exploring size dependency on selectivity - A mini review","authors":"Tengyi Liu, Hiroshi Yabu","doi":"10.1002/ece2.57","DOIUrl":"10.1002/ece2.57","url":null,"abstract":"<p>The electrochemical reduction reaction of CO<sub>2</sub> (CO<sub>2</sub>RR) holds promise for converting CO<sub>2</sub> into valuable fuels and chemicals, particularly when powered by renewable electricity, thereby aiding in reducing atmospheric CO<sub>2</sub> levels and addressing climate change. Copper phthalocyanine and its derivatives (Cu-Pcs) have attracted significant attention as versatile electrocatalytic materials with high selectivity toward various hydrocarbon products. However, the real active sites of Cu-Pcs for different products vary, and there is a lack of comprehensive summary. To address this gap, we analyze and summarize previous research, yielding the following insights: Cu-Pcs undergo reconstruction and demetallization during CO<sub>2</sub>RR, with Cu<sub>(II)</sub> converting to Cu<sub>(0)</sub>, forming transient copper nanoclusters (Cu NCs). The selectivity for CO<sub>2</sub>RR products closely correlates with the size of those derived Cu NCs. Specifically, reversible Cu NCs with ultrasmall sizes (≤2 nm), which revert to Cu-Pcs after electrolysis, exhibit high selectivity toward CH<sub>4</sub>. As Cu NCs increase in size, there is a higher CO coverage, promoting CO generation. When Cu NCs exceed a critical threshold size (approximately 15 nm), C-C coupling can occur, facilitating the formation of multicarbon (C<sub>2+</sub>) products. Furthermore, the structure of macrocycles, types of functional groups, and properties of carbon substrates influence the size and electron density of Cu NCs, thereby impacting the selectivity of CO<sub>2</sub>RR products.</p>","PeriodicalId":100387,"journal":{"name":"EcoEnergy","volume":"2 3","pages":"419-432"},"PeriodicalIF":0.0,"publicationDate":"2024-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ece2.57","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141922858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jin Uk Jang, Ashish Gaur, Sungwook Mhin, HyukSu Han
The potential of proton exchange membrane water electrolysis (PEMWE) is enormous in tackling worldwide environmental and energy issues in the face of increasing risks associated with climate change and energy scarcity. Nevertheless, the economic competitiveness of hydrogen production is hindered by the challenging operating conditions in acidic environments, resulting in a lower unit cost compared to alternative energy sources. Hence, numerous global research endeavors persist in enhancing the efficiency of essential components in PEMWE systems, specifically the porous transport layer (PTL). Additionally, investigating the interface between catalyst layer (CL) and PTL, which is directly associated with system performance, is imperative for future sustainability and cost reduction. This review focuses on the analysis of fabrication techniques, materials, and structural configurations to enhance the performance of PTLs. Additionally, we suggest the use of self-supported catalysts as potential solutions to enhance mass and charge transfer at the interface between CLs and PTLs, hence facilitating the production of hydrogen on a wide scale. In the last section we provide an overview of the future trajectory and potential of next-generation PEMWE in the context of efficient hydrogen production.
{"title":"Fabrication of self-supported catalysts via electrodeposition for proton exchange membrane water electrolysis: Emphasizing on the porous transport layers","authors":"Jin Uk Jang, Ashish Gaur, Sungwook Mhin, HyukSu Han","doi":"10.1002/ece2.55","DOIUrl":"https://doi.org/10.1002/ece2.55","url":null,"abstract":"<p>The potential of proton exchange membrane water electrolysis (PEMWE) is enormous in tackling worldwide environmental and energy issues in the face of increasing risks associated with climate change and energy scarcity. Nevertheless, the economic competitiveness of hydrogen production is hindered by the challenging operating conditions in acidic environments, resulting in a lower unit cost compared to alternative energy sources. Hence, numerous global research endeavors persist in enhancing the efficiency of essential components in PEMWE systems, specifically the porous transport layer (PTL). Additionally, investigating the interface between catalyst layer (CL) and PTL, which is directly associated with system performance, is imperative for future sustainability and cost reduction. This review focuses on the analysis of fabrication techniques, materials, and structural configurations to enhance the performance of PTLs. Additionally, we suggest the use of self-supported catalysts as potential solutions to enhance mass and charge transfer at the interface between CLs and PTLs, hence facilitating the production of hydrogen on a wide scale. In the last section we provide an overview of the future trajectory and potential of next-generation PEMWE in the context of efficient hydrogen production.</p>","PeriodicalId":100387,"journal":{"name":"EcoEnergy","volume":"2 3","pages":"381-399"},"PeriodicalIF":0.0,"publicationDate":"2024-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ece2.55","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313260","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Despite the prevailing dominance of lithium-ion batteries in consumer electronics and electric vehicle markets, the growing apprehension over lithium availability has ignited a quest for alternative high-energy-density electrochemical energy storage systems. Rechargeable batteries featuring calcium (Ca) metal as negative electrodes (anodes) present compelling prospects, promising notable advantages in energy density, cost-effectiveness, and safety. However, unlocking the full potential of rechargeable Ca metal batteries particularly hinges upon the strategic identification or design of high-energy-density positive electrode (cathode) materials. This imperative task demands expeditious synthetic routes tailored for their meticulous design. In this Perspective, we mainly highlight the development in the cathode materials for calcium batteries and accentuate the unparalleled promise of solid-state metathesis routes in designing a diverse array of high-performance electrode materials.
{"title":"Electrode materials for calcium batteries: Future directions and perspectives","authors":"Titus Masese, Godwill Mbiti Kanyolo","doi":"10.1002/ece2.53","DOIUrl":"10.1002/ece2.53","url":null,"abstract":"<p>Despite the prevailing dominance of lithium-ion batteries in consumer electronics and electric vehicle markets, the growing apprehension over lithium availability has ignited a quest for alternative high-energy-density electrochemical energy storage systems. Rechargeable batteries featuring calcium (Ca) metal as negative electrodes (anodes) present compelling prospects, promising notable advantages in energy density, cost-effectiveness, and safety. However, unlocking the full potential of rechargeable Ca metal batteries particularly hinges upon the strategic identification or design of high-energy-density positive electrode (cathode) materials. This imperative task demands expeditious synthetic routes tailored for their meticulous design. In this <i>Perspective</i>, we mainly highlight the development in the cathode materials for calcium batteries and accentuate the unparalleled promise of solid-state metathesis routes in designing a diverse array of high-performance electrode materials.</p>","PeriodicalId":100387,"journal":{"name":"EcoEnergy","volume":"2 3","pages":"339-368"},"PeriodicalIF":0.0,"publicationDate":"2024-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ece2.53","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141819056","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yang Dong, Bo Wang, Dongzhou Xie, Jun Lv, Jiewu Cui, Zhiyong Bao, Guangqing Xu, Wangqiang Shen
Photoelectrocatalytic technology (PEC) is an emerging green and sustainable technology for treating antibiotic wastewater. However, its effectiveness is limited by the recombination of photogenerated carriers. To address this issue, the Fenton reaction, an advanced oxidation process, can be coupled with PEC technology to enhance the oxidative degradation of antibiotic wastewater. This research involved creating a Zn0.5Ni0.5Fe2O4/silicon nanowires (SiNWs) Z-type heterojunction through the spin coating technique, which was then utilized in the PEC coupled Fenton reaction to break down antibiotic wastewater. The inherent electric field and the voltage applied hastened the segregation of e− and h+ within the system. These advantages make the Zn0.5Ni0.5Fe2O4/SiNWs heterojunction highly efficient in removing various antibiotics, including tetracycline (TC), ciprofloxacin (CIP), amoxicillin (AMX), and levofloxacin (LVX). In particular, the Zn0.5Ni0.5Fe2O4/SiNWs heterojunction demonstrated an 82.21% degradation efficiency for TC, exhibiting a kinetic constant (k) of 0.02688 min−1, a rate 2.82 times (4.80 times) greater than that of SiNWs. Experimental findings reveal that Zn0.5Ni0.5Fe2O4/SiNWs exhibit superior light absorption properties and a reduced rate of photogenerated charge recombination. The doping of Zn0.5Ni0.5Fe2O4 effectively improves the catalytic performance of SiNWs. This research offers fresh insights into researching PEC-coupled Fenton reaction methods for the degradation of antibiotics and paves the way for advancing the creation of more potent photoelectrochemical catalysts in the future.
{"title":"Synergistic photoelectrocatalytic degradation of tetracycline using a novel Z-scheme Zn0.5Ni0.5Fe2O4/SiNWs heterostructure: Towards sustainable antibiotic remediation","authors":"Yang Dong, Bo Wang, Dongzhou Xie, Jun Lv, Jiewu Cui, Zhiyong Bao, Guangqing Xu, Wangqiang Shen","doi":"10.1002/ece2.54","DOIUrl":"10.1002/ece2.54","url":null,"abstract":"<p>Photoelectrocatalytic technology (PEC) is an emerging green and sustainable technology for treating antibiotic wastewater. However, its effectiveness is limited by the recombination of photogenerated carriers. To address this issue, the Fenton reaction, an advanced oxidation process, can be coupled with PEC technology to enhance the oxidative degradation of antibiotic wastewater. This research involved creating a Zn<sub>0.5</sub>Ni<sub>0.5</sub>Fe<sub>2</sub>O<sub>4</sub>/silicon nanowires (SiNWs) Z-type heterojunction through the spin coating technique, which was then utilized in the PEC coupled Fenton reaction to break down antibiotic wastewater. The inherent electric field and the voltage applied hastened the segregation of <i>e</i><sup>−</sup> and <i>h</i><sup>+</sup> within the system. These advantages make the Zn<sub>0.5</sub>Ni<sub>0.5</sub>Fe<sub>2</sub>O<sub>4</sub>/SiNWs heterojunction highly efficient in removing various antibiotics, including tetracycline (TC), ciprofloxacin (CIP), amoxicillin (AMX), and levofloxacin (LVX). In particular, the Zn<sub>0.5</sub>Ni<sub>0.5</sub>Fe<sub>2</sub>O<sub>4</sub>/SiNWs heterojunction demonstrated an 82.21% degradation efficiency for TC, exhibiting a kinetic constant (<i>k</i>) of 0.02688 min<sup>−1</sup>, a rate 2.82 times (4.80 times) greater than that of SiNWs. Experimental findings reveal that Zn<sub>0.5</sub>Ni<sub>0.5</sub>Fe<sub>2</sub>O<sub>4</sub>/SiNWs exhibit superior light absorption properties and a reduced rate of photogenerated charge recombination. The doping of Zn<sub>0.5</sub>Ni<sub>0.5</sub>Fe<sub>2</sub>O<sub>4</sub> effectively improves the catalytic performance of SiNWs. This research offers fresh insights into researching PEC-coupled Fenton reaction methods for the degradation of antibiotics and paves the way for advancing the creation of more potent photoelectrochemical catalysts in the future.</p>","PeriodicalId":100387,"journal":{"name":"EcoEnergy","volume":"2 3","pages":"489-502"},"PeriodicalIF":0.0,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ece2.54","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141661883","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Understanding the intricate relationship between structure and properties is paramount in distinguishing nanocluster (NC) materials from their counterparts. Despite the progress in synthesizing new NCs, the sluggish exploration of their potential applications persists due to the difficulty in stabilizing these materials. However, recent investigations have unveiled their remarkable efficacy as catalysts in electrochemical CO2 reduction reactions, surpassing traditional materials. This discovery, addressing urgent global concerns, has quickly drawn significant attention to this field, leading to its rapid expansion. Hence, there is an urgent need to outline this research landscape and pinpoint effective strategies, marking a significant advancement. In this context, our endeavor is dedicated to offering researchers a thorough understanding of recently synthesized NC materials. We aim to elucidate their distinct structural architectures and associated properties essential for catalyst design. We envision that this systematic review will serve as a guiding beacon for future research endeavors in this burgeoning field.
{"title":"Advancing electrochemical CO2 reduction with group 11 metal nanoclusters for renewable energy solutions","authors":"Sourav Biswas, Yamato Shingyouchi, Masaki Ogami, Maho Kamiyama, Tokuhisa Kawawaki, Yuichi Negishi","doi":"10.1002/ece2.56","DOIUrl":"10.1002/ece2.56","url":null,"abstract":"<p>Understanding the intricate relationship between structure and properties is paramount in distinguishing nanocluster (NC) materials from their counterparts. Despite the progress in synthesizing new NCs, the sluggish exploration of their potential applications persists due to the difficulty in stabilizing these materials. However, recent investigations have unveiled their remarkable efficacy as catalysts in electrochemical CO<sub>2</sub> reduction reactions, surpassing traditional materials. This discovery, addressing urgent global concerns, has quickly drawn significant attention to this field, leading to its rapid expansion. Hence, there is an urgent need to outline this research landscape and pinpoint effective strategies, marking a significant advancement. In this context, our endeavor is dedicated to offering researchers a thorough understanding of recently synthesized NC materials. We aim to elucidate their distinct structural architectures and associated properties essential for catalyst design. We envision that this systematic review will serve as a guiding beacon for future research endeavors in this burgeoning field.</p>","PeriodicalId":100387,"journal":{"name":"EcoEnergy","volume":"2 3","pages":"400-418"},"PeriodicalIF":0.0,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ece2.56","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141659068","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiangyu Liu, Taiyu Wang, Haobin Ye, Wenjing Nan, Mingyu Chen, Jiale Fang, Feng Ru Fan
Liquid state thermocells (LTCs) offer a promising approach for harvesting low-grade heat. In exploring the impact of concentration difference (ΔCr) on the Seebeck coefficient (Se) in LTCs, previous studies mainly focused on two strategies: host–guest complexation and thermosensitive crystallization, which involved adding polymers or cation additives for targeted interaction with the redox couple. However, these methods face challenges in scalability and long-term application due to the selection and costs of additives, along with the stability of recognition. This study pioneers a unique strategy that utilizes solubility differences in an organic-aqueous biphasic system. We investigated an electrolyte consisting of an I−/