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1. High‐Entropy and Superstructure‐Stabilized Layered Oxide Cathodes for Sodium‐Ion Batteries

   https://doi.org/10.1002/aenm.202201989  

   Yao, Libing ; Zou, Peichao ; Wang, Chunyang ; Jiang, Jiahao ; Ma, Lu ; Tan, Sha ; Beyer, Kevin A. ; Xu, Feng ; Hu, Enyuan ; Xin, Huolin L. ( September 2022 , Advanced Energy Materials)

   Layered transition metal oxides are appealing cathodes for sodium‐ion batteries due to their overall advantages in energy density and cost. But their stabilities are usually compromised by the complicated phase transition and the oxygen redox, particularly when operating at high voltages, leading to poor structural stability and substantial capacity loss. Here an integrated strategy combing the high‐entropy design with the superlattice‐stabilization to extend the cycle life and enhance the rate capability of layered cathodes is reported. It is shown that the as‐prepared high‐entropy Na_2/3Li_1/6Fe_1/6Co_1/6Ni_1/6Mn_1/3O₂cathode enables a superlattice structure with Li/transition metal ordering and delivers excellent electrochemical performance that is not affected by the presence of phase transition and oxygen redox. It achieves a high reversible capacity (171.2 mAh g⁻¹at 0.1 C), a high energy density (531 Wh kg⁻¹), extended cycling stability (89.3% capacity retention at 1 C for 90 cycles and 63.7% capacity retention at 5 C after 300 cycles), and excellent fast‐charging capability (78 mAh g⁻¹at 10 C). This strategy would inspire more rational designs that can be leveraged to improve the reliability of layered cathodes for secondary‐ion batteries.

    

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2. Ultrahigh‐Capacity Rocksalt Cathodes Enabled by Cycling‐Activated Structural Changes

   https://doi.org/10.1002/aenm.202300221  

   Ahn, Juhyeon ; Giovine, Raynald ; Wu, Vincent C. ; Koirala, Krishna Prasad ; Wang, Chongmin ; Clément, Raphaële J. ; Chen, Guoying ( May 2023 , Advanced Energy Materials)

   Mn‐redox‐based oxides and oxyfluorides are considered the most promising earth‐abundant high‐energy cathode materials for next‐generation lithium‐ion batteries. While high capacities are obtained in high‐Mn content cathodes such as Li‐ and Mn‐rich layered and spinel‐type materials, local structure changes and structural distortions ( often lead to voltage fade, capacity decay, and impedance rise, resulting in unacceptable electrochemical performance upon cycling. In the present study, structural transformations that exploit the high capacity of Mn‐rich oxyfluorides while enabling stable cycling, in stark contrast to commonly observed structural changes that result in rapid performance degradation, are reported. It is shown that upon cycling of a cation‐disordered rocksalt (DRX) cathode (Li_1.1Mn_0.8Ti_0.1O_1.9F_0.1, an ultrahigh capacity of ≈320 mAh g⁻¹(energy density of ≈900 Wh kg⁻¹) can be obtained through dynamic structural rearrangements upon cycling , along with a unique voltage profile evolution and capacity rise. At high voltage, the presence of Mn⁴⁺and Li⁺vacancies promotes local cation ordering, leading to the formation of domains of a “δphase” within the disordered framework. On deep discharge, Mn⁴⁺reduction, along with Li⁺insertion transform the structure to a partially ordered DRX phase with aβ′‐LiFeO₂‐type arrangement. At the nanoscale, domains of the in situ formed phases are randomly oriented, allowing highly reversible structural changes and stable electrochemical cycling. These new insights not only help explain the superior electrochemical performance of high‐Mn DRXbut also provide guidance for the future development of Mn‐based, high‐energy density oxide, and oxyfluoride cathode materials.

    

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3. (Digital Presentation) Ultrathin Stabilized Zn Metal Anode for Highly Reversible Aqueous Zn-Ion Batteries

   https://doi.org/10.1149/MA2022-024439mtgabs  

   Zhang, Yuxuan ; Song, Han Wook ; Lee, Sunghwan ( October 2022 , ECS Meeting Abstracts)

   Ever-increasing demands for energy, particularly being environmentally friendly have promoted the transition from fossil fuels to renewable energy.¹Lithium-ion batteries (LIBs), arguably the most well-studied energy storage system, have dominated the energy market since their advent in the 1990s.²However, challenging issues regarding safety, supply of lithium, and high price of lithium resources limit the further advancement of LIBs for large-scale energy storage applications.³Therefore, attention is being concentrated on an alternative electrochemical energy storage device that features high safety, low cost, and long cycle life. Rechargeable aqueous zinc-ion batteries (ZIBs) is considered one of the most promising alternative energy storage systems due to the high theoretical energy and power densities where the multiple electrons (Zn²⁺) . In addition, aqueous ZIBs are safer due to non-flammable electrolyte (e.g., typically aqueous solution) and can be manufactured since they can be assembled in ambient air conditions.⁴As an essential component in aqueous Zn-based batteries, the Zn metal anode generally suffers from the growth of dendrites, which would affect battery performance in several ways. Second, the led by the loose structure of Zn dendrite may reduce the coulombic efficiency and shorten the battery lifespan.⁵

   Several approaches were suggested to improve the electrochemical stability of ZIBs, such as implementing an interfacial buffer layer that separates the active Zn from the bulk electrolyte.⁶However, the and thick thickness of the conventional Zn metal foils remain a critical challenge in this field, which may diminish the energy density of the battery drastically. According to a theretical calculation, the thickness of a Zn metal anode with an areal capacity of 1 mAh cm^-2is about 1.7 μm. However, existing extrusion-based fabrication technologies are not capable of downscaling the thickness Zn metal foils below 20 μm.

   Herein, we demonstrate a thickness controllable coating approach to fabricate an ultrathin Zn metal anode as well as a thin dielectric oxide separator. First, a 1.7 μm Zn layer was uniformly thermally evaporated onto a Cu foil. Then, Al₂O₃, the separator was deposited through sputtering on the Zn layer to a thickness of 10 nm. The inert and high hardness Al₂O₃layer is expected to lower the polarization and restrain the growth of Zn dendrites. Atomic force microscopy was employed to evaluate the roughness of the surface of the deposited Zn and Al₂O₃/Zn anode structures. Long-term cycling stability was gauged under the symmetrical cells at 0.5 mA cm^-2for 1 mAh cm^-2. Then the fabricated Zn anode was paired with MnO₂as a full cell for further electrochemical performance testing. To investigate the evolution of the interface between the Zn anode and the electrolyte, a home-developed in-situ optical observation battery cage was employed to record and compare the process of Zn deposition on the anodes of the Al₂O₃/Zn (demonstrated in this study) and the procured thick Zn anode. The surface morphology of the two Zn anodes after circulation was characterized and compared through scanning electron microscopy. The tunable ultrathin Zn metal anode with enhanced anode stability provides a pathway for future high-energy-density Zn-ion batteries.

   Obama, B., The irreversible momentum of clean energy.Science2017,355(6321), 126-129.

   Goodenough, J. B.; Park, K. S., The Li-ion rechargeable battery: a perspective.J Am Chem Soc2013,135(4), 1167-76.

   Li, C.; Xie, X.; Liang, S.; Zhou, J., Issues and Future Perspective on Zinc Metal Anode for Rechargeable Aqueous Zinc‐ion Batteries.Energy & Environmental Materials2020,3(2), 146-159.

   Jia, H.; Wang, Z.; Tawiah, B.; Wang, Y.; Chan, C.-Y.; Fei, B.; Pan, F., Recent advances in zinc anodes for high-performance aqueous Zn-ion batteries.Nano Energy2020,70.

   Yang, J.; Yin, B.; Sun, Y.; Pan, H.; Sun, W.; Jia, B.; Zhang, S.; Ma, T., Zinc Anode for Mild Aqueous Zinc-Ion Batteries: Challenges, Strategies, and Perspectives.Nanomicro Lett2022,14(1), 42.

   Yang, Q.; Li, Q.; Liu, Z.; Wang, D.; Guo, Y.; Li, X.; Tang, Y.; Li, H.; Dong, B.; Zhi, C., Dendrites in Zn-Based Batteries.Adv Mater2020,32(48), e2001854.

   Acknowledgment

   This work was partially supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 22011044) by KRISS.

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4. A New Type of Li‐Rich Rock‐Salt Oxide Li 2 Ni 1/3 Ru 2/3 O 3 with Reversible Anionic Redox Chemistry

   https://doi.org/10.1002/adma.201807825  

   Li, Xiang ; Qiao, Yu ; Guo, Shaohua ; Jiang, Kezhu ; Ishida, Masayoshi ; Zhou, Haoshen ( January 2019 , Advanced Materials)

   Li‐rich oxide cathodes are of prime importance for the development of high‐energy lithium‐ion batteries (LIBs). Li‐rich layered oxides, however, always undergo irreversible structural evolution, leading to inevitable capacity and voltage decay during cycling. Meanwhile, Li‐rich cation‐disordered rock‐salt oxides usually exhibit sluggish kinetics and inferior cycling stability, despite their firm structure and stable voltage output. Herein, a new Li‐rich rock‐salt oxide Li₂Ni_1/3Ru_2/3O₃withFd‐3mspace group, where partial cation‐ordering arrangement exists in cationic sites, is reported. Results demonstrate that a cathode fabricated from Li₂Ni_1/3Ru_2/3O₃delivers a large capacity, outstanding rate capability as well as good cycling performance with negligible voltage decay, in contrast to the common cations disordered oxides with space groupFm‐3m. First principle calculations also indicate that rock‐salt oxide with space groupFd‐3mpossesses oxygen activity potential at the state of delithiation, and good kinetics with more 0‐TM (TM = transition metals) percolation networks. In situ Raman results confirm the reversible anionic redox chemistry, confirming O²⁻/O⁻evolution during cycles in Li‐rich rock‐salt cathode for the first time. These findings open up the opportunity to design high‐performance oxide cathodes and promote the development of high‐energy LIBs.

    

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5. Oxygen‐Induced Structural Disruption for Improved Li + Transport and Electrochemical Stability of Li 3 PS 4

   https://doi.org/10.1002/aenm.202302785  

   Deck, Michael J. ; Chien, Po‐Hsiu ; Poudel, Tej P. ; Jin, Yongkang ; Liu, Haoyu ; Hu, Yan‐Yan ( December 2023 , Advanced Energy Materials)

   The performance of all‐solid‐state batteries (ASSBs) relies on the Li⁺transport and stability characteristics of solid electrolytes (SEs). Li₃PS₄is notable for its stability against lithium metal, yet its ionic conductivity remains a limiting factor. This study leverages local structural disorder via O substitution to achieve an ionic conductivity of 1.38 mS cm⁻¹with an activation energy of 0.34 eV for Li₃PS_4−xO_x(x = 0.31). Optimal O substitution transforms Li⁺transport from 2D to 3D pathways with increased ion mobility. Li₃PS_3.69O_0.31exhibits improvements in the critical current density and stability against Li metal and retains its electrochemical stability window compared with Li₃PS₄. The practical implementation of Li₃PS_3.69O_0.31in ASSBs half‐cells, particularly when coupled with TiS₂as the cathode active material, demonstrates substantially enhanced capacity and rate performance. This work elucidates the utility of introducing local structural disorder to ameliorate SE properties and highlights the benefits of strategically combining the inherent strengths of sulfides and oxides via creating oxysulfide SEs.

    

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