@article{18853, abstract = {Electrolyte additives are extensively validated effective in mitigating dendrite growth and parasitic reactions in aqueous zinc-ion batteries (AZIBs). Nonetheless, the mechanisms by which additives influence the formation and characteristics of the inorganic solid–electrolyte interphase (SEI) are not yet fully elucidated. Herein, we investigate how Zn(CF3COO)2 additives influence solvation structure and elucidate the mechanism by which these additives promote the dual reduction of anions. Through cryo-transmission electron microscopy analysis, we identified the SEI as a highly amorphous ZnS/ZnF2 phase. This amorphous hybrid SEI demonstrates exceptional stability, mechanical robustness, and high Zn2+ conductivity, effectively mitigating parasitic reactions and enhancing Zn plating/stripping reversibility. Even under elevated current densities, the Zn anode exhibits ultra-stable longevity and ultra-high reversibility. This study provides a comprehensive understanding of the intrinsic mechanisms governing solvation structure modulation that lead to the formation of amorphous hybrid SEI, underscoring their efficacy in enhancing the performance and durability of AZIBs.}, author = {Zeng, Guifang and Sun, Qing and Horta, Sharona and Martínez-Alanis, Paulina R. and Wu, Peng and Li, Jing and Wang, Shang and Ibáñez, Maria and Tian, Yanhong and Ci, Lijie and Cabot, Andreu}, issn = {1754-5706}, journal = {Energy and Environmental Science}, number = {4}, pages = {1683--1695}, publisher = {Royal Society of Chemistry}, title = {{Modulating the solvation structure to enhance amorphous solid electrolyte interface formation for ultra-stable aqueous zinc anode}}, doi = {10.1039/d4ee03750b}, volume = {18}, year = {2025}, } @article{17897, abstract = {High-entropy materials (HEMs) offer a quasi-continuous spectrum of active sites and have generated great expectations in fields such as electrocatalysis and energy storage. Despite their potential, the complex composition and associated surface phenomena of HEMs pose challenges to their rational design and development. In this context, we have synthesized FeCoNiPdWP high entropy phosphide (HEP) nanoparticles using a low-temperature colloidal method, and explored their application as bifunctional electrocatalysts for the oxygen evolution and reduction reactions (OER/ORR). Our analysis provides a detailed understanding of the individual roles and transformations of each element during OER/ORR operation. Notably, the HEPs exhibit an exceptionally low OER overpotential of 227 mV at 10 mA cm−2, attributed to the reconstructed HEP surface into a FeCoNiPdW high entropy oxyhydroxide with high oxidation states of Fe, Co, and Ni serving as the active sites. Additionally, Pd and W play crucial roles in modulating the electronic structure to optimize the adsorption energy of oxygen intermediates. For the ORR, Pd emerges as the most active component. In the reconstructed catalyst, the strong d–d orbital coupling of especially Pd, Co, and W fine-tunes ORR electron transfer pathways, delivering an ORR half-wave potential of 0.81 V with a pure four-electron reduction mechanism. The practicality of these HEPs catalysts is showcased through the assembly of aqueous zinc–air batteries. These batteries demonstrate a superior specific capacity of 886 mA h gZn−1 and maintain excellent stability over more than 700 hours of continuous operation. Overall, this study not only elucidates the role of each element in HEMs but also establishes a foundational framework for the design and development of next-generation bifunctional oxygen catalysts, broadening the potential applications of these complex materials in advanced energy systems.}, author = {He, Ren and Wang, Shiqi and Yang, Linlin and Horta, Sharona and Ding, Yang and Di, Chong and Zhang, Xuesong and Xu, Ying and Ibáñez, Maria and Zhou, Yingtang and Mebs, Stefan and Dau, Holger and Hausmann, Jan Niklas and Huo, Wenyi and Menezes, Prashanth W. and Cabot, Andreu}, issn = {1754-5706}, journal = {Energy and Environmental Science}, number = {19}, pages = {7193--7208}, publisher = {Royal Society of Chemistry}, title = {{Active site switching on high entropy phosphides as bifunctional oxygen electrocatalysts for rechargeable/robust Zn-air battery}}, doi = {10.1039/d4ee01912a}, volume = {17}, year = {2024}, } @article{12155, abstract = {The growing demand of thermal management in various fields such as miniaturized 5G chips has motivated researchers to develop new and high-performance solid-state refrigeration technologies, typically including multicaloric and thermoelectric (TE) cooling. Among them, TE cooling has attracted huge attention owing to its advantages of rapid response, large cooling temperature difference, high stability, and tunable device size. Bi2Te3-based alloys have long been the only commercialized TE cooling materials, while novel systems SnSe and Mg3(Bi,Sb)2 have recently been discovered as potential candidates. However, challenges and problems still require to be summarized and further resolved for realizing better cooling performance. In this review, we systematically investigate TE cooling from its internal mechanism, crucial parameters, to device design and applications. Furthermore, we summarize the current optimization strategies for existing TE cooling materials, and finally provide some personal prospects especially the material-planification concept on future research on establishing better TE cooling.}, author = {Qin, Yongxin and Qin, Bingchao and Wang, Dongyang and Chang, Cheng and Zhao, Li-Dong}, issn = {1754-5706}, journal = {Energy & Environmental Science}, keywords = {Pollution, Nuclear Energy and Engineering, Renewable Energy, Sustainability and the Environment, Environmental Chemistry}, number = {11}, pages = {4527--4541}, publisher = {Royal Society of Chemistry}, title = {{Solid-state cooling: Thermoelectrics}}, doi = {10.1039/d2ee02408j}, volume = {15}, year = {2022}, } @article{7275, abstract = {Aprotic alkali metal–oxygen batteries require reversible formation of metal superoxide or peroxide on cycling. Severe parasitic reactions cause poor rechargeability, efficiency, and cycle life and have been shown to be caused by singlet oxygen (1O2) that forms at all stages of cycling. However, its formation mechanism remains unclear. We show that disproportionation of superoxide, the product or intermediate on discharge and charge, to peroxide and oxygen is responsible for 1O2 formation. While the overall reaction is driven by the stability of peroxide and thus favored by stronger Lewis acidic cations such as Li+, the 1O2 fraction is enhanced by weak Lewis acids such as organic cations. Concurrently, the metal peroxide yield drops with increasing 1O2. The results explain a major parasitic pathway during cell cycling and the growing severity in K–, Na–, and Li–O2 cells based on the growing propensity for disproportionation. High capacities and rates with peroxides are now realized to require solution processes, which form peroxide or release O2via disproportionation. The results therefore establish the central dilemma that disproportionation is required for high capacity but also responsible for irreversible reactions. Highly reversible cell operation requires hence finding reaction routes that avoid disproportionation.}, author = {Mourad, Eléonore and Petit, Yann K. and Spezia, Riccardo and Samojlov, Aleksej and Summa, Francesco F. and Prehal, Christian and Leypold, Christian and Mahne, Nika and Slugovc, Christian and Fontaine, Olivier and Brutti, Sergio and Freunberger, Stefan Alexander}, issn = {1754-5692}, journal = {Energy & Environmental Science}, number = {8}, pages = {2559--2568}, publisher = {RSC}, title = {{Singlet oxygen from cation driven superoxide disproportionation and consequences for aprotic metal–O2 batteries}}, doi = {10.1039/c9ee01453e}, volume = {12}, year = {2019}, } @article{7302, abstract = {Understanding charge carrier transport in Li2O2, the storage material in the non-aqueous Li-O2 battery, is key to the development of this high-energy battery. Here, we studied ionic transport properties and Li self-diffusion in nanocrystalline Li2O2 by conductivity and temperature variable 7Li NMR spectroscopy. Nanostructured Li2O2, characterized by a mean crystallite size of less than 50 nm as estimated from X-ray diffraction peak broadening, was prepared by high-energy ball milling of microcrystalline lithium peroxide with μm sized crystallites. At room temperature the overall conductivity σ of the microcrystalline reference sample turned out to be very low (3.4 × 10−13 S cm−1) which is in agreement with results from temperature-variable 7Li NMR line shape measurements. Ball-milling, however, leads to an increase of σ by approximately two orders of magnitude (1.1 × 10−10 S cm−1); correspondingly, the activation energy decreases from 0.89 eV to 0.82 eV. The electronic contribution σeon, however, is in the order of 9 × 10−12 S cm−1 which makes less than 10% of the total value. Interestingly, 7Li NMR lines of nano-Li2O2 undergo pronounced heterogeneous motional narrowing which manifests in a two-component line shape emerging with increasing temperatures. Most likely, the enhancement in σ can be traced back to the generation of a spin reservoir with highly mobile Li ions; these are expected to reside in the nearest neighbourhood of defects generated or near the structurally disordered and defect-rich interfacial regions formed during mechanical treatment.}, author = {Dunst, A. and Epp, V. and Hanzu, I. and Freunberger, Stefan Alexander and Wilkening, M.}, issn = {1754-5692}, journal = {Energy & Environmental Science}, number = {8}, pages = {2739--2752}, publisher = {RSC}, title = {{Short-range Li diffusion vs. long-range ionic conduction in nanocrystalline lithium peroxide Li2O2—the discharge product in lithium-air batteries}}, doi = {10.1039/c4ee00496e}, volume = {7}, year = {2014}, }