Ya Chen, Xin Gao, Zheng Zhen, Xiao Chen, Ling Huang, Deli Zhou, Tengfei Hu, Bozhen Ren, Runjing Xu, Jiayi Chen, Xiaodong Chen, Lifeng Cui, Guoxiu Wang
The electrochemical performance of all-solid-state Li metal batteries (ASSLMBs) can be prominently consolidated by resolving the challenges triggered by the uncontrolled growth of Li dendrites throughout the solid electrolytes (SEs). Herein, a well-defined composite of micron-Li6PS5Cl (LPSC) and nano-Li1.3Al0.3Ti1.7(PO4)3 (LATP) is architected as a LPSC-LATP interlayer sandwiched between LPSC electrolytes for ASSLMBs. This fabrication exerts the electron-blocking functionalities to alleviate the probability of reacting with Li+ ions for the formation of anode-initiated and grain boundaries (GBs)-initiated dendrites. More importantly, it also creates localized eliminated micro-environments of Li dendrites through the high transient reactivity between them and the remaining cracks can be dynamically and effectively filled by decomposition products, thereby prominently suppresses the Li dendrite nucleation, propagation and penetration as well as simultaneously contributing to the enhancement of battery performance and stability. With this approach, a fine-tuned LPSC-LATP (8S-2O) interlayer enables symmetrical Li/LPSC/8S-2O/LPSC/Li cells to achieve a ultra-high critical current density (CCD) of over 5 mA cm−2 at room temperature, and ultra-long cycles at current density of 10 mA cm−2 for over 1600 h. Additionally, ASSLMBs employing commercial LiCoO2 cathodes can deliver exceptional durability, with an extremely high 85.6% retention of initial discharge capacity and coulombic efficiency (CE) of >99.6% after 1200 cycles at 1C (1.28 mA cm-2). These experimental batteries demonstrate the application prospect of this configuration of SEs for the commercialization of ASSLMBs.
全固态锂金属电池（ASSLMB）的电化学性能可以通过解决锂枝晶在整个固体电解质（SE）中不受控制地生长所引发的挑战而得到显著提高。在这里，一种定义明确的微米级锂6PS5Cl（LPSC）和纳米级锂1.3Al0.3Ti1.7(PO4)3（LATP）复合材料被设计成夹在LPSC电解质之间的LPSC-LATP中间层，用于ASSLMB。这种结构具有电子阻断功能，可降低与 Li+ 离子反应形成阳极引发和晶界（GBs）引发的树枝状突起的概率。更重要的是，它还能通过锂枝晶之间的高瞬态反应性创造出局部消除锂枝晶的微环境，剩余裂纹可被分解产物动态有效地填充，从而显著抑制锂枝晶的成核、传播和渗透，同时有助于提高电池的性能和稳定性。利用这种方法，经过微调的 LPSC-LATP (8S-2O) 夹层可使对称的 Li/LPSC/8S-2O/LPSC/Li 电池在室温下达到超过 5 mA cm-2 的超高临界电流密度 (CCD)，并在 10 mA cm-2 的电流密度下实现超过 1600 小时的超长循环。此外，采用商用钴酸锂阴极的 ASSLMB 还具有极高的耐用性，在 1C 温度（1.28 mA cm-2）下循环 1200 次后，初始放电容量保持率高达 85.6%，库仑效率（CE）达 99.6%。这些实验电池证明了这种 SE 配置在 ASSLMB 商业化方面的应用前景。
{"title":"The Construction of Multifunctional Solid Electrolytes Interlayers for Stabilizing Li6PS5Cl-based All-Solid-State Lithium Metal Batteries","authors":"Ya Chen, Xin Gao, Zheng Zhen, Xiao Chen, Ling Huang, Deli Zhou, Tengfei Hu, Bozhen Ren, Runjing Xu, Jiayi Chen, Xiaodong Chen, Lifeng Cui, Guoxiu Wang","doi":"10.1039/d4ee03289f","DOIUrl":"https://doi.org/10.1039/d4ee03289f","url":null,"abstract":"The electrochemical performance of all-solid-state Li metal batteries (ASSLMBs) can be prominently consolidated by resolving the challenges triggered by the uncontrolled growth of Li dendrites throughout the solid electrolytes (SEs). Herein, a well-defined composite of micron-Li6PS5Cl (LPSC) and nano-Li1.3Al0.3Ti1.7(PO4)3 (LATP) is architected as a LPSC-LATP interlayer sandwiched between LPSC electrolytes for ASSLMBs. This fabrication exerts the electron-blocking functionalities to alleviate the probability of reacting with Li+ ions for the formation of anode-initiated and grain boundaries (GBs)-initiated dendrites. More importantly, it also creates localized eliminated micro-environments of Li dendrites through the high transient reactivity between them and the remaining cracks can be dynamically and effectively filled by decomposition products, thereby prominently suppresses the Li dendrite nucleation, propagation and penetration as well as simultaneously contributing to the enhancement of battery performance and stability. With this approach, a fine-tuned LPSC-LATP (8S-2O) interlayer enables symmetrical Li/LPSC/8S-2O/LPSC/Li cells to achieve a ultra-high critical current density (CCD) of over 5 mA cm−2 at room temperature, and ultra-long cycles at current density of 10 mA cm−2 for over 1600 h. Additionally, ASSLMBs employing commercial LiCoO2 cathodes can deliver exceptional durability, with an extremely high 85.6% retention of initial discharge capacity and coulombic efficiency (CE) of >99.6% after 1200 cycles at 1C (1.28 mA cm-2). These experimental batteries demonstrate the application prospect of this configuration of SEs for the commercialization of ASSLMBs.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":null,"pages":null},"PeriodicalIF":32.5,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486683","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}
Gi-Hyeok Lee, Suwon Lee, Jiliang Zhang, Bernardine Rinkel, Matthew J. Crafton, Zengqing Zhuo, Youngju Choi, Jialu Li, Junghoon Yang, Jongwook W. Heo, Byung-Chun Park, Bryan D. McCloskey, Maxim Avdeev, Wanli Yang, Yong-Mook Kang
The chemical reactions and phase transitions at high voltages are generally considered to determine the electrochemical properties of high-voltage layered cathodes such as Ni-rich rhombohedral oxides. Even if significantly higher SOCs (states-of-charge) are utilized above the capability of transition metal redox (primarily Ni and Co), the effect of oxygen redox on Ni-rich rhombohedral oxides still looks mysterious thereby necessitating research that can clarify the relationships between redox reactions and phase transitions. Here, we performed a comprehensive and comparative study of the cationic and anionic redox reactions, as well as the structural evolution of a series of commercial Ni-rich layered oxides with and without Al doping. We combined the results from X-ray spectroscopy, operando electrochemical mass spectrometry, and neutron diffraction with electrochemical properties, and revealed the different oxygen redox activities associated with structural and electrochemical degradations. We reveal that Al doping suppresses the irreversible oxygen release, however enhances the lattice oxygen oxidization. With this modulated oxygen redox activity, the Ni-rich layered oxides' notorious H2-H3 structural phase transition becomes highly reversible. Our findings disentangle the different oxygen redox activities during high-voltage cycling and clarify the role of dopants in the Ni-rich layered oxides in terms of structural and electrochemical stability, shedding lights on the future directions of optimizing layered cathode materials for safer high energy-density secondary batteries.
一般认为，高电压下的化学反应和相变决定了高压层状阴极（如富镍斜方氧化物）的电化学特性。即使利用的 SOC（电荷状态）大大高于过渡金属氧化还原（主要是镍和钴）的能力，氧氧化还原对富镍斜方氧化物的影响仍然是个谜，因此有必要进行研究，以阐明氧化还原反应和相变之间的关系。在此，我们对阳离子和阴离子氧化还原反应以及一系列掺杂和未掺杂铝的商用富镍层状氧化物的结构演变进行了全面的比较研究。我们将 X 射线光谱、操作电化学质谱和中子衍射的结果与电化学特性相结合，揭示了与结构和电化学退化相关的不同氧氧化还原活动。我们发现，铝掺杂抑制了不可逆氧释放，但却增强了晶格氧氧化。随着氧氧化还原活性的调节，富镍层状氧化物声名狼藉的 H2-H3 结构相变变得高度可逆。我们的研究结果揭示了高压循环过程中不同的氧氧化还原活性，阐明了掺杂剂在富镍层状氧化物的结构和电化学稳定性方面的作用，为优化层状正极材料以制造更安全的高能量密度二次电池指明了未来的方向。
{"title":"Oxygen Redox Activities Governing High-Voltage Charging Reversibility of Ni-Rich Layered Cathodes","authors":"Gi-Hyeok Lee, Suwon Lee, Jiliang Zhang, Bernardine Rinkel, Matthew J. Crafton, Zengqing Zhuo, Youngju Choi, Jialu Li, Junghoon Yang, Jongwook W. Heo, Byung-Chun Park, Bryan D. McCloskey, Maxim Avdeev, Wanli Yang, Yong-Mook Kang","doi":"10.1039/d4ee03832k","DOIUrl":"https://doi.org/10.1039/d4ee03832k","url":null,"abstract":"The chemical reactions and phase transitions at high voltages are generally considered to determine the electrochemical properties of high-voltage layered cathodes such as Ni-rich rhombohedral oxides. Even if significantly higher SOCs (states-of-charge) are utilized above the capability of transition metal redox (primarily Ni and Co), the effect of oxygen redox on Ni-rich rhombohedral oxides still looks mysterious thereby necessitating research that can clarify the relationships between redox reactions and phase transitions. Here, we performed a comprehensive and comparative study of the cationic and anionic redox reactions, as well as the structural evolution of a series of commercial Ni-rich layered oxides with and without Al doping. We combined the results from X-ray spectroscopy, operando electrochemical mass spectrometry, and neutron diffraction with electrochemical properties, and revealed the different oxygen redox activities associated with structural and electrochemical degradations. We reveal that Al doping suppresses the irreversible oxygen release, however enhances the lattice oxygen oxidization. With this modulated oxygen redox activity, the Ni-rich layered oxides' notorious H2-H3 structural phase transition becomes highly reversible. Our findings disentangle the different oxygen redox activities during high-voltage cycling and clarify the role of dopants in the Ni-rich layered oxides in terms of structural and electrochemical stability, shedding lights on the future directions of optimizing layered cathode materials for safer high energy-density secondary batteries.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":null,"pages":null},"PeriodicalIF":32.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452589","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}
Artificial nitrogen fixation has been pivotal in escalating agricultural productivity and sustaining exponential human population growth. Nonetheless, these practices have concurrently perturbed the natural nitrogen cycle, engendering a plethora of environmental challenges. The advent of electrochemical nitrogen transformation techniques represents a burgeoning avenue for rectifying the nitrogen cycle's imbalance and for synthesizing value-added nitrogenous products from atmospheric nitrogen. In this review, we delve into the recent progress concerning the electrocatalytic interconversion among key nitrogen species, namely N2, NOx(-), and NH3. Our examination encompasses a multifaceted analysis, including the elucidation of reaction mechanisms and a critical evaluation of the intrinsic challenges behind each reaction and the strategies to boost their translation to practical applications. Extending beyond primary nitrogen transformations, we also assess a spectrum of emergent and promising directions. These include lithium-mediated nitrogen fixation, carbon-nitrogen coupling reactions, and the development of electrochemical batteries harnessing nitrogen transformation chemistry. This review aims to offer a critical and forward-looking perspective on the role of electrocatalysis in modulating the nitrogen cycle and to highlight untapped opportunities for its application in a myriad of innovative domains.
{"title":"Electrocatalytic nitrogen cycle: mechanism, materials, and momentum","authors":"Laiquan Li, Linyuan Xu, Hanyun Wang, Haohong Wei, Cheng Tang, Guisheng Li, Yuhai Dou, Huakun Liu, Shi Xue Dou","doi":"10.1039/d4ee03156c","DOIUrl":"https://doi.org/10.1039/d4ee03156c","url":null,"abstract":"Artificial nitrogen fixation has been pivotal in escalating agricultural productivity and sustaining exponential human population growth. Nonetheless, these practices have concurrently perturbed the natural nitrogen cycle, engendering a plethora of environmental challenges. The advent of electrochemical nitrogen transformation techniques represents a burgeoning avenue for rectifying the nitrogen cycle's imbalance and for synthesizing value-added nitrogenous products from atmospheric nitrogen. In this review, we delve into the recent progress concerning the electrocatalytic interconversion among key nitrogen species, namely N2, NOx(-), and NH3. Our examination encompasses a multifaceted analysis, including the elucidation of reaction mechanisms and a critical evaluation of the intrinsic challenges behind each reaction and the strategies to boost their translation to practical applications. Extending beyond primary nitrogen transformations, we also assess a spectrum of emergent and promising directions. These include lithium-mediated nitrogen fixation, carbon-nitrogen coupling reactions, and the development of electrochemical batteries harnessing nitrogen transformation chemistry. This review aims to offer a critical and forward-looking perspective on the role of electrocatalysis in modulating the nitrogen cycle and to highlight untapped opportunities for its application in a myriad of innovative domains.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":null,"pages":null},"PeriodicalIF":32.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452590","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}
Yang Ding, Erming Feng, Siyuan Lu, Jianhui Chang, Caoyu Long, S.C. Tong, Hengyue Li, Junliang Yang
Residual stresses generated within perovskite films during the high-temperature annealing and cooling process are the key contributors to reduce device performance and lifespan deterioration. Herein, a strategy of surface micro-etching and reconstruction is developed to regulate the stresses in triple-cation (formamidine, methylamine, cesium) perovskite film. Precise stoichiometric mixture of L-lactic acid (LA) and isopropanol (IPA) is used to controllably dissolve the surface of perovskite film, followed by octylammonium iodide (OAI) post-treatment, enabling a sinking reconstruction of 2D perovskite from surface to bulk phase and achieving a benign transition from surface tensile stress to compressive stress, as well as a more matchable interface energy level. As a result, the target perovskite solar cells (PSCs) yield an obviously enhanced power conversion efficiency (PCE) of 25.54%, which is the highest reported PCE for triple-cation PSCs. Meanwhile, PSC modules with 10.4 cm2 achieve a PCE of 21.02%. Furthermore, the surface micro-etched and reconstructed PSCs exhibit superior stability, and the PSC devices without encapsulation can maintain 83% of original efficiency after 500 hours illumination at maximum power point (MPPT) tracking in N2 atmosphere. The research provides a valuable avenue to improve PSC stability and efficiency by regulating residual stresses through surface micro-etching and reconstruction.
{"title":"Stress Regulation via Surface Micro-etching and Reconstruction for Enhancing Triple-Cation Perovskite Solar Cells with the Efficiency of 25.54%","authors":"Yang Ding, Erming Feng, Siyuan Lu, Jianhui Chang, Caoyu Long, S.C. Tong, Hengyue Li, Junliang Yang","doi":"10.1039/d4ee04248d","DOIUrl":"https://doi.org/10.1039/d4ee04248d","url":null,"abstract":"Residual stresses generated within perovskite films during the high-temperature annealing and cooling process are the key contributors to reduce device performance and lifespan deterioration. Herein, a strategy of surface micro-etching and reconstruction is developed to regulate the stresses in triple-cation (formamidine, methylamine, cesium) perovskite film. Precise stoichiometric mixture of L-lactic acid (LA) and isopropanol (IPA) is used to controllably dissolve the surface of perovskite film, followed by octylammonium iodide (OAI) post-treatment, enabling a sinking reconstruction of 2D perovskite from surface to bulk phase and achieving a benign transition from surface tensile stress to compressive stress, as well as a more matchable interface energy level. As a result, the target perovskite solar cells (PSCs) yield an obviously enhanced power conversion efficiency (PCE) of 25.54%, which is the highest reported PCE for triple-cation PSCs. Meanwhile, PSC modules with 10.4 cm2 achieve a PCE of 21.02%. Furthermore, the surface micro-etched and reconstructed PSCs exhibit superior stability, and the PSC devices without encapsulation can maintain 83% of original efficiency after 500 hours illumination at maximum power point (MPPT) tracking in N2 atmosphere. The research provides a valuable avenue to improve PSC stability and efficiency by regulating residual stresses through surface micro-etching and reconstruction.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":null,"pages":null},"PeriodicalIF":32.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452627","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}
Hong-Bo Zhang, Yu Meng, Lingzhe Fang, Fei Yang, Shangqian Zhu, Tao Li, Xiaohua Yu, Ju Rong, Weiwei Chen, Dong Su, Yi Mei, Peng-Xiang Hou, Chang Liu, Minhua Shao, Jin-Cheng Li
Great efforts have been devoted to the development of bifunctional electrocatalysts to accelerate the sluggish kinetics of cathodic oxygen reduction/evolution reactions (ORR/OER) in zinc–air batteries (ZABs). Here we report a thermal evaporating-trapping synergistic strategy to fabricate bifunctional electrocatalyst of flexible N-doped carbon fiber cloth loaded with both CoFe-oxide nanoparticles and single-atom Co/Fe-Nx sites, in which the thermal evaporation process functions in both downsizing CoFe-oxide nanoparticles and trapping the evaporated Co/Fe species to generate Co/Fe-Nx sites. The obtained flexible electrocatalyst, directly served as an oxygen electrode, displays a small potential gap of 0.542 V for OER/ORR, large peak power densities (liquid-state ZAB: 237.4 mW cm–2; solid-state ZAB: 141.1 mW cm-2), and excellent charge-discharge cycling stability without decay after 1000 cycles. Furthermore, in situ Raman spectroscopy characterization reveals that CoFe2O4 species is responsible for the OER catalysis.
{"title":"Thermal Evaporating-Trapping Strategy to Synthesize Flexible and Robust Oxygen Electrocatalysts for Rechargeable Zinc-Air Batteries","authors":"Hong-Bo Zhang, Yu Meng, Lingzhe Fang, Fei Yang, Shangqian Zhu, Tao Li, Xiaohua Yu, Ju Rong, Weiwei Chen, Dong Su, Yi Mei, Peng-Xiang Hou, Chang Liu, Minhua Shao, Jin-Cheng Li","doi":"10.1039/d4ee03005b","DOIUrl":"https://doi.org/10.1039/d4ee03005b","url":null,"abstract":"Great efforts have been devoted to the development of bifunctional electrocatalysts to accelerate the sluggish kinetics of cathodic oxygen reduction/evolution reactions (ORR/OER) in zinc–air batteries (ZABs). Here we report a thermal evaporating-trapping synergistic strategy to fabricate bifunctional electrocatalyst of flexible N-doped carbon fiber cloth loaded with both CoFe-oxide nanoparticles and single-atom Co/Fe-Nx sites, in which the thermal evaporation process functions in both downsizing CoFe-oxide nanoparticles and trapping the evaporated Co/Fe species to generate Co/Fe-Nx sites. The obtained flexible electrocatalyst, directly served as an oxygen electrode, displays a small potential gap of 0.542 V for OER/ORR, large peak power densities (liquid-state ZAB: 237.4 mW cm–2; solid-state ZAB: 141.1 mW cm-2), and excellent charge-discharge cycling stability without decay after 1000 cycles. Furthermore, in situ Raman spectroscopy characterization reveals that CoFe2O4 species is responsible for the OER catalysis.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":null,"pages":null},"PeriodicalIF":32.5,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142450109","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}
Jingyu Shi, Pengfei Ding, Jintao Zhu, Zhenyu Chen, Shuangjiao Gao, Xueliang Yu, Xiaochun Liao, Quan Liu, Ziyi Ge
The well-defined structures featured giant-molecule acceptors (GMAs) can exhibit unique properties of small-molecule acceptors and polymers simultaneously, and the consecutive innovations in materials design have enabled GMAs-based organic solar cells (OSCs) to possess outstanding devices power conversion efficiency (PCE) over 19% and extended long-term stability. Here, through systematically selecting the numbers and positions of selenium atom, π-spacer linking units and the outermost conjugate ring of central core of monomers, four novel GMAs are successfully synthesized, GMA-SSS, GMA-SSeS, GMA-SeSSe and GMA-SeSeSe. Surprisingly, PM6:GMA-SSeS-based OSC yields the highest PCE of 19.37% with remarkably open current voltage of 0.917 V with reduced voltage loss (ΔE3 = 0.246 eV), and excellent fill factor of 77.12%. Furthermore, when devices annealed at 100 °C, the PM6:GMA-SSeS and PM6:GMA-SSS-based OSCs exhibit remarkably extended t80% lifetimes of 5600 and 5250 h, respectively. Our work indicates that the selenium substituted regulation of GMAs structures in linking units and monomers is a valuable approach to obtain high-performance and long-term stability devices at the same time, shedding light on the further development of GMAs-based OSCs.
{"title":"Well-regulated Structures Featured Giant-molecule Acceptors Enable Long-term Stability and High-Performance Binary Organic Solar Cells","authors":"Jingyu Shi, Pengfei Ding, Jintao Zhu, Zhenyu Chen, Shuangjiao Gao, Xueliang Yu, Xiaochun Liao, Quan Liu, Ziyi Ge","doi":"10.1039/d4ee03754e","DOIUrl":"https://doi.org/10.1039/d4ee03754e","url":null,"abstract":"The well-defined structures featured giant-molecule acceptors (GMAs) can exhibit unique properties of small-molecule acceptors and polymers simultaneously, and the consecutive innovations in materials design have enabled GMAs-based organic solar cells (OSCs) to possess outstanding devices power conversion efficiency (PCE) over 19% and extended long-term stability. Here, through systematically selecting the numbers and positions of selenium atom, π-spacer linking units and the outermost conjugate ring of central core of monomers, four novel GMAs are successfully synthesized, GMA-SSS, GMA-SSeS, GMA-SeSSe and GMA-SeSeSe. Surprisingly, PM6:GMA-SSeS-based OSC yields the highest PCE of 19.37% with remarkably open current voltage of 0.917 V with reduced voltage loss (ΔE3 = 0.246 eV), and excellent fill factor of 77.12%. Furthermore, when devices annealed at 100 °C, the PM6:GMA-SSeS and PM6:GMA-SSS-based OSCs exhibit remarkably extended t80% lifetimes of 5600 and 5250 h, respectively. Our work indicates that the selenium substituted regulation of GMAs structures in linking units and monomers is a valuable approach to obtain high-performance and long-term stability devices at the same time, shedding light on the further development of GMAs-based OSCs.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":null,"pages":null},"PeriodicalIF":32.5,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448186","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}
High-performance thermoelectric materials at room temperature are eagerly pursued due to their promising applications in the Internet of Things for sustainable power supply. Reducing sound velocity by softening chemical bonds is considered an effective approach to lowering thermal conductivity and enhancing thermoelectric performance. Here, different from softening chemical bonds at the atomic scale, we introduce a global softening strategy, which macroscopically softens the overall material to manipulate its sound velocity. This is demonstrated in MgAgSb, one of the most promising p-type thermoelectric materials at room temperature to replace (Bi,Sb)2Te3, that the addition of inherently soft organic compounds can easily lower its sound velocity, leading to an obvious reduction in lattice thermal conductivity. Despite a simultaneous reduction of the power factor, the overall thermoelectric quality factor B is enhanced, enabling softened MgAgSb by C18H36O2 addition to achieve a figure of merit zT value of ∼0.88 at 300 K and a peak zT value of ∼1.30. Consequently, an impressive average zT of ∼1.17 over a wide temperature range has been realized. Moreover, this high-performance MgAgSb is verified to be highly repeatable and stable. With this MgAgSb, a decent conversion efficiency of 8.6% for a single thermoelectric leg and ∼7% for a two-pair module have been achieved under a temperature difference of ∼276 K, indicating its great potential for low-grade heat harvesting. This work will not only advance MgAgSb for low-grade power generation, but also inspire the development of high-performance thermoelectrics with global softening in the future.
室温下的高性能热电材料在可持续供电的物联网中有着广阔的应用前景，因此受到热切追捧。通过软化化学键降低声速被认为是降低热导率和提高热电性能的有效方法。在这里，与在原子尺度上软化化学键不同，我们引入了一种全局软化策略，从宏观上软化整体材料，从而操纵其声速。MgAgSb 是室温下最有希望取代 (Bi,Sb)2Te3 的 p 型热电材料之一，我们在 MgAgSb 中证明，添加固有的软有机化合物可以轻松降低其声速，从而明显降低晶格热导率。尽管同时降低了功率因数，但整体热电品质因数 B 却得到了提高，这使得通过添加 C18H36O2 而软化的 MgAgSb 在 300 K 时的性能系数 zT 值达到了∼0.88，峰值 zT 值达到了∼1.30。因此，在很宽的温度范围内，平均 zT 值达到了惊人的 ∼ 1.17。此外，这种高性能 MgAgSb 的可重复性和稳定性也得到了验证。在温度差为 ∼276 K 的条件下，这种 MgAgSb 的单热电腿转换效率达到了 8.6%，双对模块转换效率达到了 ∼7%，这表明它在低品位热收集方面具有巨大潜力。这项工作不仅推动了 MgAgSb 在低品位发电领域的应用，还为未来开发全局软化的高性能热电半导体器件提供了灵感。
{"title":"Global softening to manipulate sound velocity for reliable high-performance MgAgSb thermoelectrics","authors":"Airan Li, Longquan Wang, Jiankang Li, Takao Mori","doi":"10.1039/d4ee03521f","DOIUrl":"https://doi.org/10.1039/d4ee03521f","url":null,"abstract":"High-performance thermoelectric materials at room temperature are eagerly pursued due to their promising applications in the Internet of Things for sustainable power supply. Reducing sound velocity by softening chemical bonds is considered an effective approach to lowering thermal conductivity and enhancing thermoelectric performance. Here, different from softening chemical bonds at the atomic scale, we introduce a global softening strategy, which macroscopically softens the overall material to manipulate its sound velocity. This is demonstrated in MgAgSb, one of the most promising p-type thermoelectric materials at room temperature to replace (Bi,Sb)<small><sub>2</sub></small>Te<small><sub>3</sub></small>, that the addition of inherently soft organic compounds can easily lower its sound velocity, leading to an obvious reduction in lattice thermal conductivity. Despite a simultaneous reduction of the power factor, the overall thermoelectric quality factor <em>B</em> is enhanced, enabling softened MgAgSb by C<small><sub>18</sub></small>H<small><sub>36</sub></small>O<small><sub>2</sub></small> addition to achieve a figure of merit <em>zT</em> value of ∼0.88 at 300 K and a peak <em>zT</em> value of ∼1.30. Consequently, an impressive average <em>zT</em> of ∼1.17 over a wide temperature range has been realized. Moreover, this high-performance MgAgSb is verified to be highly repeatable and stable. With this MgAgSb, a decent conversion efficiency of 8.6% for a single thermoelectric leg and ∼7% for a two-pair module have been achieved under a temperature difference of ∼276 K, indicating its great potential for low-grade heat harvesting. This work will not only advance MgAgSb for low-grade power generation, but also inspire the development of high-performance thermoelectrics with global softening in the future.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":null,"pages":null},"PeriodicalIF":32.5,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448184","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}
Xinpeng Han, Jinpeng Han, Kang Ma, Jiaqi Wen, Lianpeng Li, Daliang Han, Jie Sun
Manipulating ion solvation sheath behaviour is of great significance for alleviating dendritic growth, hydrogen production, and metal corrosion, thus achieving long-term stability of zinc ion batteries. Herein, we rationally design a Zn2+·O=C group-derived contact ion pair (CIP)/aggregate (AGG)-rich electrolyte with Zn-philic and H2O-phobic features through in situ polymerization of 3-methacryloxypropyl trimethoxysilane monomers. Being attributed with this unique electrolyte design, this "skin" enables the generation of gradient fluoride, Zn-salt-rich hydrophobic solid electrolyte interface (SEI) layer through increasing the ratios of ZnF2/ZnO in SEI layer. Moreover, the amounts of ZnF2 in inner SEI are higher than those in outer SEI. Considering the higher dendrite-suppressing and desolvation ability of ZnF2 instead of ZnO, the SEI exhibits excellent capability in suppressing the growth of Zn dendrite and restraining H2O-related side reactions. Owing to its unprecedented average modulus (71.25 GPa), the SEI effectively inhibits the external stress originating from dendritic growth, the undesirable volume expansion of Zn and the long-lasting anode/electrolyte side reactions. Consequently, at high depth of discharge of 34.2%, the symmetric cell maintains long-term stability for over 1000 h, and anode-free battery delivers superior performance with a high-capacity retention of 99.2% after 110 cycles.
{"title":"Gradient fluoride, Zn-salt-rich hydrophobic interphase enabled by Zn-philic, H2O-phobic, anion-philic polymer 'skin' for anode-free solid Zn battery","authors":"Xinpeng Han, Jinpeng Han, Kang Ma, Jiaqi Wen, Lianpeng Li, Daliang Han, Jie Sun","doi":"10.1039/d4ee01978d","DOIUrl":"https://doi.org/10.1039/d4ee01978d","url":null,"abstract":"Manipulating ion solvation sheath behaviour is of great significance for alleviating dendritic growth, hydrogen production, and metal corrosion, thus achieving long-term stability of zinc ion batteries. Herein, we rationally design a Zn2+·O=C group-derived contact ion pair (CIP)/aggregate (AGG)-rich electrolyte with Zn-philic and H2O-phobic features through in situ polymerization of 3-methacryloxypropyl trimethoxysilane monomers. Being attributed with this unique electrolyte design, this \"skin\" enables the generation of gradient fluoride, Zn-salt-rich hydrophobic solid electrolyte interface (SEI) layer through increasing the ratios of ZnF2/ZnO in SEI layer. Moreover, the amounts of ZnF2 in inner SEI are higher than those in outer SEI. Considering the higher dendrite-suppressing and desolvation ability of ZnF2 instead of ZnO, the SEI exhibits excellent capability in suppressing the growth of Zn dendrite and restraining H2O-related side reactions. Owing to its unprecedented average modulus (71.25 GPa), the SEI effectively inhibits the external stress originating from dendritic growth, the undesirable volume expansion of Zn and the long-lasting anode/electrolyte side reactions. Consequently, at high depth of discharge of 34.2%, the symmetric cell maintains long-term stability for over 1000 h, and anode-free battery delivers superior performance with a high-capacity retention of 99.2% after 110 cycles.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":null,"pages":null},"PeriodicalIF":32.5,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448187","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}
Tao Zhou, Jinze Wang, Ling Lv, Ruhong Li, Long Chen, Shuoqing Zhang, Haikuo Zhang, Baochen Ma, Jiajie Huang, Bing Wu, Lixin Chen, Tao Deng, Xiulin Fan
Extending the charging cutoff voltage of lithium cobalt oxide (LCO) cathode is an effective strategy to enhance energy density of lithium-ion batteries (LIBs), while the formation of poor cathode electrolyte interphase (CEI) has limited its widespread application. Various electrolyte additives, particularly nitrile compounds, have shown promise in addressing these interfacial issues, though the fundamental design principles remain unclear. Herein, we introduce an interfacial leverage mechanism utilizing nitriles adsorbed on LCO surface to fine-tune the CEI composition. A nitrile additive's suitability for high-voltage LCO is determined by the repulsive interaction with the solvent (Esol) and the attractive interaction with the anion (Eanion). The former inhibits solvent decomposition, while the latter facilitates the anion decomposition during CEI construction. These interactions can be tailored through the functional design of nitrile compounds, as demonstrated using 3,5-bis(trifluoromethyl)benzonitrile (BFBN) in a commercial carbonate electrolyte. The BFBN molecules adsorb onto the LCO surface through coordination between cyano groups (-CN) and cobalt (Co) atoms. Exhibiting repulsive interactions with the solvent and attractive interactions with the anion through anion-π interaction, BFBN suppresses carbonate solvent dehydrogenation while promoting PF6- anions decomposition to form an inorganic-rich CEI. A 1 wt.% addition of BFBN enables 4.55 V-graphite||LCO pouch cells to achieve over 550 cycles at 25 °C and more than 145 cycles at 45 °C, significantly surpassing the lifespan of around 110 and 50 cycles observed in the baseline electrolyte. This work provides new insights into the design of high-voltage electrolyte additives for high-energy-density LIBs.
延长锂钴氧化物（LCO）阴极的充电截止电压是提高锂离子电池（LIB）能量密度的有效策略，但形成不良阴极电解质相（CEI）限制了其广泛应用。各种电解质添加剂，尤其是腈化合物，在解决这些界面问题方面已显示出前景，但其基本设计原理仍不清楚。在此，我们介绍一种界面杠杆机制，利用吸附在 LCO 表面的腈类化合物来微调 CEI 成分。腈类添加剂对高压 LCO 的适用性取决于与溶剂（Esol）的排斥作用和与阴离子（Eanion）的吸引作用。前者抑制溶剂的分解，而后者则促进阴离子在 CEI 构建过程中的分解。正如在商用碳酸盐电解液中使用 3,5-双（三氟甲基）苯甲腈（BFBN）所证明的那样，这些相互作用可以通过腈化合物的功能设计进行定制。BFBN 分子通过氰基（-CN）和钴（Co）原子之间的配位吸附到 LCO 表面。BFBN 与溶剂发生排斥作用，并通过阴离子-π 相互作用与阴离子发生吸引作用，从而抑制碳酸盐溶剂的脱氢，同时促进 PF6-阴离子的分解，形成富含无机物的 CEI。添加 1 wt.% 的 BFBN 可使 4.55 V 石墨||LCO 袋式电池在 25 °C 下循环 550 次以上，在 45 °C 下循环 145 次以上，大大超过了在基线电解液中观察到的大约 110 次和 50 次循环的寿命。这项研究为高能量密度 LIB 的高压电解质添加剂设计提供了新的见解。
{"title":"Anion-π Interaction and Solvent Dehydrogenation Control Enable High-Voltage Lithium-ion Batteries","authors":"Tao Zhou, Jinze Wang, Ling Lv, Ruhong Li, Long Chen, Shuoqing Zhang, Haikuo Zhang, Baochen Ma, Jiajie Huang, Bing Wu, Lixin Chen, Tao Deng, Xiulin Fan","doi":"10.1039/d4ee03027c","DOIUrl":"https://doi.org/10.1039/d4ee03027c","url":null,"abstract":"Extending the charging cutoff voltage of lithium cobalt oxide (LCO) cathode is an effective strategy to enhance energy density of lithium-ion batteries (LIBs), while the formation of poor cathode electrolyte interphase (CEI) has limited its widespread application. Various electrolyte additives, particularly nitrile compounds, have shown promise in addressing these interfacial issues, though the fundamental design principles remain unclear. Herein, we introduce an interfacial leverage mechanism utilizing nitriles adsorbed on LCO surface to fine-tune the CEI composition. A nitrile additive's suitability for high-voltage LCO is determined by the repulsive interaction with the solvent (<em>E</em><small><sub>sol</sub></small>) and the attractive interaction with the anion (<em>E</em><small><sub>anion</sub></small>). The former inhibits solvent decomposition, while the latter facilitates the anion decomposition during CEI construction. These interactions can be tailored through the functional design of nitrile compounds, as demonstrated using 3,5-bis(trifluoromethyl)benzonitrile (BFBN) in a commercial carbonate electrolyte. The BFBN molecules adsorb onto the LCO surface through coordination between cyano groups (-CN) and cobalt (Co) atoms. Exhibiting repulsive interactions with the solvent and attractive interactions with the anion through anion-π interaction, BFBN suppresses carbonate solvent dehydrogenation while promoting PF<small><sub>6</sub></small><small><sup>-</sup></small> anions decomposition to form an inorganic-rich CEI. A 1 wt.% addition of BFBN enables 4.55 V-graphite||LCO pouch cells to achieve over 550 cycles at 25 °C and more than 145 cycles at 45 °C, significantly surpassing the lifespan of around 110 and 50 cycles observed in the baseline electrolyte. This work provides new insights into the design of high-voltage electrolyte additives for high-energy-density LIBs.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":null,"pages":null},"PeriodicalIF":32.5,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448185","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}
Jinyu Guo, Matthew J. Liu, Chloe Laguna, Dean M. Miller, Kindle S. Williams, Brandon D. Clark, Carolina Muñoz, Sarah J. Blair, Adam C. Nielander, Thomas F. Jaramillo, William A. Tarpeh
Underutilized wastewaters containing dilute levels of reactive nitrogen (Nr) can help rebalance the nitrogen cycle. This study describes electrodialysis and nitrate reduction (EDNR), a reactive electrochemical separation architecture that combines catalysis and separations to remediate nitrate and ammonium-polluted wastewaters while recovering ammonia. By engineering operating parameters (e.g., background electrolyte, applied potential, electrolyte flow rate), we achieved high recovery and conversion of Nr in both simulated and real wastewaters. The EDNR process demonstrated long-term robustness and up-concentration that recovered >100 mM ammonium fertilizer solution from agricultural runoff that contained 8.2 mM Nr. EDNR is the first reported process to our knowledge that remediates dilute real wastewater and recovers ammonia from multiple Nr pollutants, with an energy consumption (245 MJ per kg NH3–N in simulated wastewater, 920 MJ per kg NH3–N in agricultural runoff) on par with the state-of-the-art. Demonstrated first at proof-of-concept and engineered to technology readiness level (TRL) 4–5, EDNR shows great promise for distributed wastewater treatment and sustainable ammonia manufacturing.
含有稀释活性氮 (Nr) 的未充分利用废水有助于重新平衡氮循环。本研究介绍了电渗析和硝酸盐还原 (EDNR)，这是一种反应型电化学分离结构，它将催化和分离相结合，在回收氨的同时修复硝酸盐和铵污染废水。通过设计操作参数（如背景电解质、应用电位、电解质流速），我们在模拟废水和实际废水中都实现了较高的硝酸回收率和转化率。EDNR 工艺具有长期稳定性和高浓缩性，可从含有 8.2 mM Nr 的农业径流中回收 100 mM 氨肥溶液。据我们所知，EDNR 是首个报告的工艺，可修复稀释的实际废水并从多种 Nr 污染物中回收氨，能耗（模拟废水中每千克 NH3-N 245 兆焦耳，农业径流中每千克 NH3-N 920 兆焦耳）与最先进的工艺相当。EDNR 首先进行了概念验证，其工程设计达到了技术就绪水平 (TRL) 4-5，为分布式废水处理和可持续合成氨生产带来了巨大希望。
{"title":"Electrodialysis and nitrate reduction (EDNR) to enable distributed ammonia manufacturing from wastewaters","authors":"Jinyu Guo, Matthew J. Liu, Chloe Laguna, Dean M. Miller, Kindle S. Williams, Brandon D. Clark, Carolina Muñoz, Sarah J. Blair, Adam C. Nielander, Thomas F. Jaramillo, William A. Tarpeh","doi":"10.1039/d4ee03002h","DOIUrl":"https://doi.org/10.1039/d4ee03002h","url":null,"abstract":"Underutilized wastewaters containing dilute levels of reactive nitrogen (Nr) can help rebalance the nitrogen cycle. This study describes electrodialysis and nitrate reduction (EDNR), a reactive electrochemical separation architecture that combines catalysis and separations to remediate nitrate and ammonium-polluted wastewaters while recovering ammonia. By engineering operating parameters (<em>e.g.</em>, background electrolyte, applied potential, electrolyte flow rate), we achieved high recovery and conversion of Nr in both simulated and real wastewaters. The EDNR process demonstrated long-term robustness and up-concentration that recovered >100 mM ammonium fertilizer solution from agricultural runoff that contained 8.2 mM Nr. EDNR is the first reported process to our knowledge that remediates dilute real wastewater and recovers ammonia from multiple Nr pollutants, with an energy consumption (245 MJ per kg NH<small><sub>3</sub></small>–N in simulated wastewater, 920 MJ per kg NH<small><sub>3</sub></small>–N in agricultural runoff) on par with the state-of-the-art. Demonstrated first at proof-of-concept and engineered to technology readiness level (TRL) 4–5, EDNR shows great promise for distributed wastewater treatment and sustainable ammonia manufacturing.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":null,"pages":null},"PeriodicalIF":32.5,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448188","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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