To address challenges in perovskite solar cells integrated with textured silicon, we developed a multilayer structured hole transport layer (HTL) on the basis of organometallic copper phthalocyanine (CuPc): N,N,N′,N′-tetra[(1,1′-biphenyl)-4-yl](1,1′:4′,1″-terphenyl)-4,4″-diamine (TaTm)/CuPc/Al2O3. Thermally evaporated CuPc provides stability and desired wettability for the perovskite solution. We identified a unique surface-bulk recombination pattern at the CuPc/perovskite interface that results in a high fill factor (FF = 87%) but a low open-circuit voltage (Voc) due to surface recombination losses. TaTm enhances electron blocking, while Al2O3 forms a porous insulator contact that mitigates nonradiative recombination. Double-sided optimization of CuPc with TaTm and Al2O3 effectively reduced the surface recombination without compromising the carrier extraction efficiency. This HTL structure achieved PCE values of 22.5% and 24.5% for 1.65 and 1.54 eV perovskite in p–i–n single cells and 28.9% in textured silicon/perovskite tandem cells. The conformal and wettable HTL structure promotes uniform perovskite coating, thereby reducing issues, such as pyramid puncturing, on textured Cz-Si wafers from production lines.
{"title":"Understanding and Engineering the Perovskite/Organometallic Hole Transport Interface for High-Performance p–i–n Single Cells and Textured Tandem Solar Cells","authors":"Shaojie Yuan, Kaitian Mao, Fengchun Cai, Zhengjie Zhu, Hongguang Meng, Tieqiang Li, Wei Peng, Xingyu Feng, Weiwei Chen, Jiahang Xu, Jixian Xu","doi":"10.1021/acsenergylett.4c01301","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01301","url":null,"abstract":"To address challenges in perovskite solar cells integrated with textured silicon, we developed a multilayer structured hole transport layer (HTL) on the basis of organometallic copper phthalocyanine (CuPc): <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-tetra[(1,1′-biphenyl)-4-yl](1,1′:4′,1″-terphenyl)-4,4″-diamine (TaTm)/CuPc/Al<sub>2</sub>O<sub>3</sub>. Thermally evaporated CuPc provides stability and desired wettability for the perovskite solution. We identified a unique surface-bulk recombination pattern at the CuPc/perovskite interface that results in a high fill factor (FF = 87%) but a low open-circuit voltage (<i>V</i><sub>oc</sub>) due to surface recombination losses. TaTm enhances electron blocking, while Al<sub>2</sub>O<sub>3</sub> forms a porous insulator contact that mitigates nonradiative recombination. Double-sided optimization of CuPc with TaTm and Al<sub>2</sub>O<sub>3</sub> effectively reduced the surface recombination without compromising the carrier extraction efficiency. This HTL structure achieved PCE values of 22.5% and 24.5% for 1.65 and 1.54 eV perovskite in p–i–n single cells and 28.9% in textured silicon/perovskite tandem cells. The conformal and wettable HTL structure promotes uniform perovskite coating, thereby reducing issues, such as pyramid puncturing, on textured Cz-Si wafers from production lines.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489755","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}
Lithium-ion battery (LIB) technology is important for electric transportation and large-scale energy storage, where a gas-related parasitic reaction is one of the constraints. Consequently, developing a gas analysis method for mechanism analysis and safety warnings is of practical significance but often challenging. Here, an operando pulse electrochemical mass spectrometry (p-EC-MS) technique is reported, featuring a specialized electrochemical cell, a programmed pulse collection system, a carrier gas inlet system, a gas replenishment system, and a quantitative algorithm. As a proof of concept, both model experiment and practical LIB operation are examined, showcasing its capability for nondestructive and long-term gas analysis. Furthermore, secondary parasitic reactions resulting from gas consumption (e.g., gas cross-talk) in LIBs, a phenomenon rarely detected by traditional differential electrochemical mass spectrometry, have been observed. We believe that the p-EC-MS technique can provide fundamental insights into gas behavior and design strategies to enhance the safety and durability of practical LIBs.
{"title":"Operando Pulse Electrochemical Mass Spectrometry for Nondestructive and Long-Term Gas Analysis in Practical Lithium-Ion Pouch Batteries","authors":"Long Pang, Haoran Li, Xin Feng, Zhiwei Zhao, Chuying Ouyang, Zhangquan Peng","doi":"10.1021/acsenergylett.4c01305","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01305","url":null,"abstract":"Lithium-ion battery (LIB) technology is important for electric transportation and large-scale energy storage, where a gas-related parasitic reaction is one of the constraints. Consequently, developing a gas analysis method for mechanism analysis and safety warnings is of practical significance but often challenging. Here, an operando pulse electrochemical mass spectrometry (p-EC-MS) technique is reported, featuring a specialized electrochemical cell, a programmed pulse collection system, a carrier gas inlet system, a gas replenishment system, and a quantitative algorithm. As a proof of concept, both model experiment and practical LIB operation are examined, showcasing its capability for nondestructive and long-term gas analysis. Furthermore, secondary parasitic reactions resulting from gas consumption (e.g., gas cross-talk) in LIBs, a phenomenon rarely detected by traditional differential electrochemical mass spectrometry, have been observed. We believe that the p-EC-MS technique can provide fundamental insights into gas behavior and design strategies to enhance the safety and durability of practical LIBs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489697","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 : 2024-07-01DOI: 10.1021/acsenergylett.4c01278
Osnat Zapata-Arteaga, Aleksandr Perevedentsev, Michela Prete, Stephan Busato, Paolo Sebastiano Floris, Jesika Asatryan, Riccardo Rurali, Jaime Martín, Mariano Campoy-Quiles
Chemical doping of organic semiconductors is an essential enabler for applications in electronic and energy-conversion devices such as thermoelectrics. Here, Lewis-paired complexes are advanced as high-performance dopants that address all the principal drawbacks of conventional dopants in terms of limited electrical conductivity, thermal stability, and generality. The study focuses on the Lewis acid B(C6F5)3 (BCF) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) bearing Lewis-basic −CN groups. Due to its high electron affinity, BCF:F4TCNQ dopes an exceptionally wide range of organic semiconductors, over 20 of which are investigated. Complex activation and microstructure control lead to conductivities for poly(3-hexylthiophene) (P3HT) exceeding 300 and 900 S cm–1 for isotropic and chain-oriented films, respectively, resulting in a 10 to 50 times larger thermoelectric power factor compared to those obtained with neat dopants. Moreover, BCF:F4TCNQ-doped P3HT exhibits a 3-fold higher thermal dedoping activation energy compared to that obtained with neat dopants and at least a factor of 10 better operational stability.
{"title":"A Universal, Highly Stable Dopant System for Organic Semiconductors Based on Lewis-Paired Dopant Complexes","authors":"Osnat Zapata-Arteaga, Aleksandr Perevedentsev, Michela Prete, Stephan Busato, Paolo Sebastiano Floris, Jesika Asatryan, Riccardo Rurali, Jaime Martín, Mariano Campoy-Quiles","doi":"10.1021/acsenergylett.4c01278","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01278","url":null,"abstract":"Chemical doping of organic semiconductors is an essential enabler for applications in electronic and energy-conversion devices such as thermoelectrics. Here, Lewis-paired complexes are advanced as high-performance dopants that address all the principal drawbacks of conventional dopants in terms of limited electrical conductivity, thermal stability, and generality. The study focuses on the Lewis acid B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> (BCF) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F<sub>4</sub>TCNQ) bearing Lewis-basic −CN groups. Due to its high electron affinity, BCF:F<sub>4</sub>TCNQ dopes an exceptionally wide range of organic semiconductors, over 20 of which are investigated. Complex activation and microstructure control lead to conductivities for poly(3-hexylthiophene) (P3HT) exceeding 300 and 900 S cm<sup>–1</sup> for isotropic and chain-oriented films, respectively, resulting in a 10 to 50 times larger thermoelectric power factor compared to those obtained with neat dopants. Moreover, BCF:F<sub>4</sub>TCNQ-doped P3HT exhibits a 3-fold higher thermal dedoping activation energy compared to that obtained with neat dopants and at least a factor of 10 better operational stability.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489731","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The dehydrogenation of solvents presents a significant challenge at the cathode–electrolyte interface (CEI) in high-voltage lithium-ion batteries (LIBs), resulting in the generation of corrosive HF and posing detrimental effects on the sustainability of LIBs. Herein, we propose an interfacial self-enhanced strategy mediated by H-transfer to mitigate solvent dehydrogenation at the CEI. As a proof of concept, trimethyl phosphate (TMP) was coupled with 1,1,2,2,3,3,4-heptafluorocyclopentane (HFCP) to prepare the high-voltage electrolyte, where TMP serves to capture H free radicals produced by the dehydrogenation of HFCP, while the dehydrogenated-HFCP radicals would in situ passivate the cathode/electrolyte interface. The TMP/HFCP electrolyte enables a 4.4 V graphite||LiNi0.8Co0.1Mn0.1O2 LIB to achieve over 90% capacity retention after 1300 cycles at 0.5 C. Furthermore, the TMP/HFCP electrolyte exhibits favorable properties in terms of nonflammability and minimal gas production during electrochemical and thermal tests. This work presents a promising pathway for realizing high-voltage and high-safety LIBs.
溶剂脱氢是高压锂离子电池（LIB）正负极电解质界面（CEI）上的一个重大挑战，会产生腐蚀性氢氟酸（HF），对 LIB 的可持续性造成不利影响。在此，我们提出了一种由氢转移介导的界面自增强策略，以缓解 CEI 中的溶剂脱氢。作为概念验证，磷酸三甲酯（TMP）与 1,1,2,2,3,3,4-七氟环戊烷（HFCP）结合制备高压电解质，其中 TMP 用于捕获 HFCP 脱氢产生的 H 自由基，而脱氢的 HFCP 自由基将原位钝化阴极/电解质界面。此外，TMP/HFCP 电解液在电化学和热测试中还表现出不易燃和产气少的良好特性。这项研究为实现高电压和高安全性的 LIB 提供了一条前景广阔的途径。
{"title":"H-Transfer Mediated Self-Enhanced Interphase for High-Voltage Lithium-Ion Batteries","authors":"Shihao Duan, Shuoqing Zhang, Yong Li, Rui Guo, Ling Lv, Ruhong Li, Zunchun Wu, Menglu Li, Shunrui Xiao, Lixin Chen, Yong Shi, Tao Deng, Xiulin Fan","doi":"10.1021/acsenergylett.4c00917","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c00917","url":null,"abstract":"The dehydrogenation of solvents presents a significant challenge at the cathode–electrolyte interface (CEI) in high-voltage lithium-ion batteries (LIBs), resulting in the generation of corrosive HF and posing detrimental effects on the sustainability of LIBs. Herein, we propose an interfacial self-enhanced strategy mediated by H-transfer to mitigate solvent dehydrogenation at the CEI. As a proof of concept, trimethyl phosphate (TMP) was coupled with 1,1,2,2,3,3,4-heptafluorocyclopentane (HFCP) to prepare the high-voltage electrolyte, where TMP serves to capture H free radicals produced by the dehydrogenation of HFCP, while the dehydrogenated-HFCP radicals would <i>in situ</i> passivate the cathode/electrolyte interface. The TMP/HFCP electrolyte enables a 4.4 V graphite||LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> LIB to achieve over 90% capacity retention after 1300 cycles at 0.5 C. Furthermore, the TMP/HFCP electrolyte exhibits favorable properties in terms of nonflammability and minimal gas production during electrochemical and thermal tests. This work presents a promising pathway for realizing high-voltage and high-safety LIBs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489790","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 : 2024-07-01DOI: 10.1021/acsenergylett.4c01397
Nam-Yung Park, Sang-Mun Han, Ji-Hyun Ryu, Myoung-Chan Kim, Jung-In Yoon, Jae-Ho Kim, Geon-Tae Park, Joop Enno Frerichs, Christoph Erk, Yang-Kook Sun
Crystallinity and microstructure, fundamental properties of cathode materials, are determined during the calcination process. Increasing the calcination temperature to improve crystallinity induces grain coarsening in multiple directions, resulting in the polygonal primary particles with heterogeneous size distribution. Here, grain coarsening was controlled by introducing Nb segregated at grain boundaries, and a microstructure with homogeneous primary particles evolved under a balanced coarsening force. The homogeneous size distribution of the primary particles improved not only the mechanical stability of the cathode particles but also the resistance to microcrack propagation during cycling. The Nb-doped Ni-rich cathode with homogeneous primary particle size retained 90.0% of its initial capacity after 500 cycles by suppressing electrolyte infiltration along the microcracks and subsequent degradation. This study demonstrates that improving the mechanical stability of cathode particles by tightly packing homogeneous primary particles is a key factor in improving the cycling stability of Ni-rich cathodes.
{"title":"Tailoring Primary Particle Size Distribution to Suppress Microcracks in Ni-Rich Cathodes via Controlled Grain Coarsening","authors":"Nam-Yung Park, Sang-Mun Han, Ji-Hyun Ryu, Myoung-Chan Kim, Jung-In Yoon, Jae-Ho Kim, Geon-Tae Park, Joop Enno Frerichs, Christoph Erk, Yang-Kook Sun","doi":"10.1021/acsenergylett.4c01397","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01397","url":null,"abstract":"Crystallinity and microstructure, fundamental properties of cathode materials, are determined during the calcination process. Increasing the calcination temperature to improve crystallinity induces grain coarsening in multiple directions, resulting in the polygonal primary particles with heterogeneous size distribution. Here, grain coarsening was controlled by introducing Nb segregated at grain boundaries, and a microstructure with homogeneous primary particles evolved under a balanced coarsening force. The homogeneous size distribution of the primary particles improved not only the mechanical stability of the cathode particles but also the resistance to microcrack propagation during cycling. The Nb-doped Ni-rich cathode with homogeneous primary particle size retained 90.0% of its initial capacity after 500 cycles by suppressing electrolyte infiltration along the microcracks and subsequent degradation. This study demonstrates that improving the mechanical stability of cathode particles by tightly packing homogeneous primary particles is a key factor in improving the cycling stability of Ni-rich cathodes.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489808","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 : 2024-06-28DOI: 10.1021/acsenergylett.4c01011
Yavuz Savsatli, Fan Wang, Hua Guo, Zeyuan Li, Andrew Hitt, Haizhou Zhan, Mingyuan Ge, Xianghui Xiao, Wah-Keat Lee, Harsh Agarwal, Ryan M. Stephens, Ming Tang
As a promising battery technology, zinc–air batteries still face significant challenges, including the formation of a mossy structure on the zinc metal anode in alkaline electrolyte. Because a similar phenomenon also plagues lithium and sodium metal batteries, elucidating its mechanism has important implications for progress in energy storage. Herein, operando X-ray nanotomography was employed to visualize zinc moss growth and dissolution at the individual colony level. By tracking its microstructure evolution, zinc moss was found to display irreversible plating/stripping behavior. While zinc moss exhibits self-limiting growth and zinc deposition occurs mainly in its outer region, zinc dissolution is more uniformly distributed inside the moss colony upon stripping, leading to the formation of “dead” zinc and capacity loss. A direct correlation is established between the moss amount and zinc plating/stripping efficiency. Results from this study offer new insights into mitigating the unstable zinc plating morphology and improving the cycle life of aqueous zinc–air batteries.
作为一种前景广阔的电池技术，锌空气电池仍然面临着巨大的挑战，包括锌金属阳极在碱性电解液中形成苔藓状结构。由于类似现象也困扰着锂电池和钠金属电池，因此阐明其机理对储能技术的进步具有重要意义。在此，我们采用了操作性 X 射线纳米层析技术来观察锌苔在单个菌落水平上的生长和溶解情况。通过跟踪其微观结构的演变，发现锌苔表现出不可逆的镀层/剥离行为。锌藓的生长具有自我限制性，锌主要沉积在其外部区域，而锌的溶解则在剥离时更均匀地分布在藓群内部，导致 "死 "锌的形成和容量的损失。苔藓数量与镀锌/剥离效率之间存在直接关联。这项研究的结果为缓解不稳定的镀锌形态和提高锌-空气水溶液电池的循环寿命提供了新的见解。
{"title":"In Situ and Operando Observation of Zinc Moss Growth and Dissolution in Alkaline Electrolyte for Zinc–Air Batteries","authors":"Yavuz Savsatli, Fan Wang, Hua Guo, Zeyuan Li, Andrew Hitt, Haizhou Zhan, Mingyuan Ge, Xianghui Xiao, Wah-Keat Lee, Harsh Agarwal, Ryan M. Stephens, Ming Tang","doi":"10.1021/acsenergylett.4c01011","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01011","url":null,"abstract":"As a promising battery technology, zinc–air batteries still face significant challenges, including the formation of a mossy structure on the zinc metal anode in alkaline electrolyte. Because a similar phenomenon also plagues lithium and sodium metal batteries, elucidating its mechanism has important implications for progress in energy storage. Herein, operando X-ray nanotomography was employed to visualize zinc moss growth and dissolution at the individual colony level. By tracking its microstructure evolution, zinc moss was found to display irreversible plating/stripping behavior. While zinc moss exhibits self-limiting growth and zinc deposition occurs mainly in its outer region, zinc dissolution is more uniformly distributed inside the moss colony upon stripping, leading to the formation of “dead” zinc and capacity loss. A direct correlation is established between the moss amount and zinc plating/stripping efficiency. Results from this study offer new insights into mitigating the unstable zinc plating morphology and improving the cycle life of aqueous zinc–air batteries.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463564","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 : 2024-06-28DOI: 10.1021/acsenergylett.4c01235
Yan Jing, Kiana Amini, Dawei Xi, Shijian Jin, Abdulrahman M. Alfaraidi, Emily F. Kerr, Roy G. Gordon, Michael J. Aziz
Electrochemically driven CO2 capture processes utilizing redox-active organics in aqueous flow chemistry show promise for nonflammability, continuous-flow engineering and the possibility of being driven at a high current density by inexpensive, clean electricity. We show that deprotonated hydroquinone–CO2 adducts, whose insolubility limits the utility of the quinone–hydroquinone redox couple, become soluble when alkylammonium cations are introduced. Consequently, we introduced alkylammonium groups to anthraquinone via covalent bonds, making the resulting bis[3-(trimethylammonio)propyl]anthraquinones (BTMAPAQs) soluble. We report the first aqueous quinone flow chemistry-enabled electrochemical CO2 capture/release process, which occurs at ambient temperature and pressure, and show that it proceeds via both pH-swing and nucleophilicity-swing mechanisms. 1,5-BTMAPAQ reaches the theoretical capture capacity of two CO2 molecules per quinone from 1-bar CO2–N2 mixtures, for which the CO2 partial pressure is as low as 0.05 bar, or the applied current density is as high as 100 mA/cm2, or the organic concentration is as high as 0.4 M. The energetic cost ranges from 48 to 140 kJ/mol CO2. In a crude simulated flue gas composed of 3% O2, 10% CO2, and 87% N2, 1,5-BTMAPAQ electrolyte reversibly captured and released 50% of the theoretical capacity during an exposure of over 4 h. It outperforms its isomeric counterparts 1,4-, and 1,8-BTMAPAQ in capture capacity and O2 tolerance, demonstrating a substituent position effect on the reactivity of isomers with CO2 and O2. The results provide fundamental insight into electrochemical CO2 capture with aqueous quinone flow chemistry and suggest that the oxygen tolerance of reduced quinones may be significantly advanced through molecular engineering.
{"title":"Electrochemically Induced CO2 Capture Enabled by Aqueous Quinone Flow Chemistry","authors":"Yan Jing, Kiana Amini, Dawei Xi, Shijian Jin, Abdulrahman M. Alfaraidi, Emily F. Kerr, Roy G. Gordon, Michael J. Aziz","doi":"10.1021/acsenergylett.4c01235","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01235","url":null,"abstract":"Electrochemically driven CO<sub>2</sub> capture processes utilizing redox-active organics in aqueous flow chemistry show promise for nonflammability, continuous-flow engineering and the possibility of being driven at a high current density by inexpensive, clean electricity. We show that deprotonated hydroquinone–CO<sub>2</sub> adducts, whose insolubility limits the utility of the quinone–hydroquinone redox couple, become soluble when alkylammonium cations are introduced. Consequently, we introduced alkylammonium groups to anthraquinone via covalent bonds, making the resulting bis[3-(trimethylammonio)propyl]anthraquinones (BTMAPAQs) soluble. We report the first aqueous quinone flow chemistry-enabled electrochemical CO<sub>2</sub> capture/release process, which occurs at ambient temperature and pressure, and show that it proceeds via both pH-swing and nucleophilicity-swing mechanisms. 1,5-BTMAPAQ reaches the theoretical capture capacity of two CO<sub>2</sub> molecules per quinone from 1-bar CO<sub>2</sub>–N<sub>2</sub> mixtures, for which the CO<sub>2</sub> partial pressure is as low as 0.05 bar, or the applied current density is as high as 100 mA/cm<sup>2</sup>, or the organic concentration is as high as 0.4 M. The energetic cost ranges from 48 to 140 kJ/mol CO<sub>2</sub>. In a crude simulated flue gas composed of 3% O<sub>2</sub>, 10% CO<sub>2</sub>, and 87% N<sub>2</sub>, 1,5-BTMAPAQ electrolyte reversibly captured and released 50% of the theoretical capacity during an exposure of over 4 h. It outperforms its isomeric counterparts 1,4-, and 1,8-BTMAPAQ in capture capacity and O<sub>2</sub> tolerance, demonstrating a substituent position effect on the reactivity of isomers with CO<sub>2</sub> and O<sub>2</sub>. The results provide fundamental insight into electrochemical CO<sub>2</sub> capture with aqueous quinone flow chemistry and suggest that the oxygen tolerance of reduced quinones may be significantly advanced through molecular engineering.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463536","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 : 2024-06-28DOI: 10.1021/acsenergylett.4c01444
Henry M. Woolley, Martin Lange, Elina Nazmutdinova, Nella M. Vargas-Barbosa
To address the challenges of tortuous partial ionic transport and chemomechanical failure due to the large volumetric changes of sulfur during all-solid-state battery cycling, we evaluate a hybrid electrolyte composed of the lithium chloride argyrodite Li6PS5Cl (LPSCl) and an ionic liquid-based lithium liquid electrolyte (ILE) in the cathode composite of Li–S half-cells. We confirm the stability of the LPSCl/ILE interface by coupling Raman and impedance spectroscopy measurements. Charge–discharge curves show a capacity improvement for the hybrid cells (1364 ± 151 mAh·g–1), compared to 904 ± 186 mAh·g–1 for pristine cells. Transport measurements quantify an increase in the partial ionic conductivity of proxy cathode layers from 0.2 to 0.4 mS·cm–1 in hybrid cells. Taken together, the use of the ILE increases the partial ionic transport and access to sulfur which results in higher and more stable discharge capacities.
{"title":"Toward High-Capacity Li–S Solid-State Batteries: The Role of Partial Ionic Transport in the Catholyte","authors":"Henry M. Woolley, Martin Lange, Elina Nazmutdinova, Nella M. Vargas-Barbosa","doi":"10.1021/acsenergylett.4c01444","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01444","url":null,"abstract":"To address the challenges of tortuous partial ionic transport and chemomechanical failure due to the large volumetric changes of sulfur during all-solid-state battery cycling, we evaluate a hybrid electrolyte composed of the lithium chloride argyrodite Li<sub>6</sub>PS<sub>5</sub>Cl (LPSCl) and an ionic liquid-based lithium liquid electrolyte (ILE) in the cathode composite of Li–S half-cells. We confirm the stability of the LPSCl/ILE interface by coupling Raman and impedance spectroscopy measurements. Charge–discharge curves show a capacity improvement for the hybrid cells (1364 ± 151 mAh·g<sup>–1</sup>), compared to 904 ± 186 mAh·g<sup>–1</sup> for pristine cells. Transport measurements quantify an increase in the partial ionic conductivity of proxy cathode layers from 0.2 to 0.4 mS·cm<sup>–1</sup> in hybrid cells. Taken together, the use of the ILE increases the partial ionic transport and access to sulfur which results in higher and more stable discharge capacities.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464001","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 : 2024-06-28DOI: 10.1021/acsenergylett.4c00591
Honghong Liang, Pushpendra Kumar, Zheng Ma, Fei Zhao, Haoran Cheng, Hongliang Xie, Zhen Cao, Luigi Cavallo, Qian Li, Jun Ming
The design of electrolytes that are compatible with graphite electrodes and incorporate flame-retardant properties in potassium-ion batteries (PIBs) can not only facilitate their commercialization but also improve the safety reliability. However, it remains challenging, particularly in propylene carbonate (PC)-based electrolytes. Herein, we achieved a highly reversible K+ (de)intercalation with graphite in PC-based electrolytes by introducing the fluoroethers. We identified the strength of interactions formed between fluoroethers (e.g., 1,1,2,2-tetrafluoroethy-2,2,3,3-tetrafluoropropyl ether (HFE), 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (TFTFE)) and PC by heteronuclear overhauser effect spectroscopy. We find that the interaction between HFE and PC is stronger, which can significantly weaken the K+-PC interaction, contributing to a reversible K+ (de)intercalation and also endowing electrolyte nonflammable features. The kinetic and thermodynamic properties of K+-solvent-anion complexes in the proposed interfacial model can elucidate the electrolyte and electrode stability, enabling the as-designed potassium-ion sulfur batteries to show high performance. This discovery offers a fresh perspective for designing and advancing electrolytes in PIBs and beyond.
在钾离子电池（PIB）中设计与石墨电极兼容并具有阻燃特性的电解质不仅能促进其商业化，还能提高其安全可靠性。然而，这仍然具有挑战性，尤其是在以碳酸丙烯酯（PC）为基础的电解质中。在此，我们通过引入氟醚，在 PC 基电解质中实现了 K+与石墨的高度可逆（脱）插层。我们通过异核过豪瑟效应光谱确定了氟醚（如 1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚 (HFE)、1,1,2,2-四氟乙基-2,2,2-三氟乙基醚 (TFTFE)）与 PC 之间形成的相互作用强度。我们发现，HFE 与 PC 之间的相互作用更强，可显著削弱 K+ 与 PC 之间的相互作用，从而促成 K+（脱）插层的可逆性，并赋予电解质不易燃的特性。在所提出的界面模型中，K+-溶剂-阴离子复合物的动力学和热力学性质可以阐明电解质和电极的稳定性，从而使设计的钾离子硫电池显示出高性能。这一发现为设计和推进 PIB 及其他领域的电解质提供了全新的视角。
{"title":"Electrolyte Intermolecular Interaction Mediated Nonflammable Potassium-Ion Sulfur Batteries","authors":"Honghong Liang, Pushpendra Kumar, Zheng Ma, Fei Zhao, Haoran Cheng, Hongliang Xie, Zhen Cao, Luigi Cavallo, Qian Li, Jun Ming","doi":"10.1021/acsenergylett.4c00591","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c00591","url":null,"abstract":"The design of electrolytes that are compatible with graphite electrodes and incorporate flame-retardant properties in potassium-ion batteries (PIBs) can not only facilitate their commercialization but also improve the safety reliability. However, it remains challenging, particularly in propylene carbonate (PC)-based electrolytes. Herein, we achieved a highly reversible K<sup>+</sup> (de)intercalation with graphite in PC-based electrolytes by introducing the fluoroethers. We identified the strength of interactions formed between fluoroethers (e.g., 1,1,2,2-tetrafluoroethy-2,2,3,3-tetrafluoropropyl ether (HFE), 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (TFTFE)) and PC by heteronuclear overhauser effect spectroscopy. We find that the interaction between HFE and PC is stronger, which can significantly weaken the K<sup>+</sup>-PC interaction, contributing to a reversible K<sup>+</sup> (de)intercalation and also endowing electrolyte nonflammable features. The kinetic and thermodynamic properties of K<sup>+</sup>-solvent-anion complexes in the proposed interfacial model can elucidate the electrolyte and electrode stability, enabling the as-designed potassium-ion sulfur batteries to show high performance. This discovery offers a fresh perspective for designing and advancing electrolytes in PIBs and beyond.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463655","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 : 2024-06-27DOI: 10.1021/acsenergylett.4c01072
Burak Aktekin, Elmar Kataev, Luise M. Riegger, Raul Garcia-Diez, Zora Chalkley, Juri Becker, Regan G. Wilks, Anja Henss, Marcus Bär, Jürgen Janek
It is crucial to understand at which potentials electrolyte decomposition reactions start and which chemical species are present in the subsequently formed decomposition films, e.g., solid electrolyte interphase (SEI). Herein, a new operando experimental approach is introduced to investigate such reactions by employing hard X-ray photoelectron spectroscopy (HAXPES). This approach enables the examination of the SEI formed below a thin metal film (e.g., 6 nm nickel) acting as the working electrode in an electrochemical cell with sulfide-based Li6PS5Cl solid electrolyte. Electrolyte reduction reactions already started at 1.75 V (vs Li+/Li) and resulted in considerable Li2S formation, particularly in the voltage range 1.5–1.0 V. A heterogeneous/layered microstructure of the SEI is observed (e.g., preferential Li2O and Li2S deposits near the current collector). The reversibility of side reactions is also observed, as Li2O and Li2S decompose in the 2–4 V potential window, generating oxidized sulfur species, sulfites, and sulfates.
了解电解质分解反应是在什么电位下开始的以及随后形成的分解膜（如固体电解质间相（SEI））中存在哪些化学物种至关重要。本文介绍了一种新的操作性实验方法，即利用硬 X 射线光电子能谱 (HAXPES) 来研究此类反应。通过这种方法，可以对硫化锂 6PS5Cl 固体电解质电化学电池中作为工作电极的金属薄膜（例如 6 纳米镍）下方形成的 SEI 进行检测。电解质还原反应在 1.75 V 时已经开始（相对于 Li+/Li），并导致大量 Li2S 的形成，尤其是在 1.5-1.0 V 的电压范围内。在 SEI 中观察到了异质/分层的微观结构（例如，Li2O 和 Li2S 在集流器附近优先沉积）。此外，还观察到副反应的可逆性，Li2O 和 Li2S 在 2-4 V 电位窗口中分解，生成氧化硫、亚硫酸盐和硫酸盐。
{"title":"Operando Photoelectron Spectroscopy Analysis of Li6PS5Cl Electrochemical Decomposition Reactions in Solid-State Batteries","authors":"Burak Aktekin, Elmar Kataev, Luise M. Riegger, Raul Garcia-Diez, Zora Chalkley, Juri Becker, Regan G. Wilks, Anja Henss, Marcus Bär, Jürgen Janek","doi":"10.1021/acsenergylett.4c01072","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01072","url":null,"abstract":"It is crucial to understand at which potentials electrolyte decomposition reactions start and which chemical species are present in the subsequently formed decomposition films, e.g., solid electrolyte interphase (SEI). Herein, a new operando experimental approach is introduced to investigate such reactions by employing hard X-ray photoelectron spectroscopy (HAXPES). This approach enables the examination of the SEI formed below a thin metal film (e.g., 6 nm nickel) acting as the working electrode in an electrochemical cell with sulfide-based Li<sub>6</sub>PS<sub>5</sub>Cl solid electrolyte. Electrolyte reduction reactions already started at 1.75 V (vs Li<sup>+</sup>/Li) and resulted in considerable Li<sub>2</sub>S formation, particularly in the voltage range 1.5–1.0 V. A heterogeneous/layered microstructure of the SEI is observed (e.g., preferential Li<sub>2</sub>O and Li<sub>2</sub>S deposits near the current collector). The reversibility of side reactions is also observed, as Li<sub>2</sub>O and Li<sub>2</sub>S decompose in the 2–4 V potential window, generating oxidized sulfur species, sulfites, and sulfates.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462010","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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