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1. Biomimetic composite architecture achieves ultrahigh rate capability and cycling life of sodium ion battery cathodes

   https://doi.org/10.1063/5.0020805  

   Shin, Kang_Ho; Park, Sul_Ki; Nakhanivej, Puritut; Wang, Yixian; Liu, Pengcheng; Bak, Seong-Min; Choi, Min_Sung; Mitlin, David; Park, Ho_Seok (December 2020, Applied Physics Reviews)

   Sodium ion batteries are an emerging candidate to replace lithium ion batteries in large-scale electrical energy storage systems due to the abundance and widespread distribution of sodium. Despite the growing interest, the development of high-performance sodium cathode materials remains a challenge. In particular, polyanionic compounds are considered as a strong cathode candidate owing to their better cycling stability, a flatter voltage profile, and stronger thermal stability compared to other cathode materials. Here, we report the rational design of a biomimetic bone-inspired polyanionic Na3V2(PO4)3-reduced graphene oxide composite (BI-NVP) cathode that achieves ultrahigh rate charging and ultralong cycling life in a sodium ion battery. At a charging rate of 1 C, BI-NVP delivers 97% of its theoretical capacity and is able to retain a voltage plateau even at the ultra-high rate of 200 C. It also shows long cycling life with capacity retention of 91% after 10 000 cycles at 50 C. The sodium ion battery cells with a BI-NVP cathode and Na metal anode were able to deliver a maximum specific energy of 350 W h kg−1 and maximum specific power of 154 kW kg−1. In situ and postmortem analyses of cycled BI-NVP (including by Raman and XRD spectra) HRTEM, and STEM-EELS, indicate highly reversible dilation–contraction, negligible electrode pulverization, and a stable NVP-reduced graphene oxide layer interface. The results presented here provide a rational and biomimetic material design for the electrode architecture for ultrahigh power and ultralong cyclability of the sodium ion battery full cells when paired with a sodium metal anode. 

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2. The Evolution of MXenes Conductivity and Optical Properties Upon Heating in Air

   https://doi.org/10.1002/smtd.202300568  

   Shamsabadi, Ahmad A.; Fang, Hui; Zhang, Danzhen; Thakur, Anupma; Chen, Cindy Y.; Zhang, Aixi; Wang, Haonan; Anasori, Babak; Soroush, Masoud; Gogotsi, Yury; et al (July 2023, Small Methods)

   Abstract MXenes, a family of 2D transition‐metal carbides and nitrides, have excellent electrical conductivity and unique optical properties. However, MXenes oxidize in ambient conditions, which is accelerated upon heating. Intercalation of water also causes hydrolysis accelerating oxidation. Developing new tools to readily characterize MXenes’ thermal stability can enable deeper insights into their structure–property relationships. Here, in situ spectroscopic ellipsometry (SE) is employed to characterize the optical properties of three types of MXenes (Ti₃C₂T_x, Mo₂TiC₂T_x, and Ti₂CT_x) with varied composition and atomistic structures to investigate their thermal degradation upon heating under ambient environment. It is demonstrated that changes in MXene extinction and optical conductivity in the visible and near‐IR regions correlate well with the amount of intercalated water and hydroxyl termination groups and the degree of oxidation, measured using thermogravimetric analysis. Among the three MXenes, Ti₃C₂T_xand Ti₂CT_x, respectively, have the highest and lowest thermal stability, indicating the role of transition‐metal type, synthesis route, and the number of atomic layers in MXene flakes. These findings demonstrate the utility of SE as a powerful in situ technique for rapid structure–property relationship studies paving the way for the further design, fabrication, and property optimization of novel MXene materials. 

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3. Ultrasmall Cu Nanoparticles Supported on Crystalline, Mesoporous ZnO for Selective CO ₂ Hydrogenation

   https://doi.org/10.1002/cctc.202301077  

   Hu, Mingzhen; Lu, Xingxu; Zhu, Chunxiang; Yang, Tiangang; Tan, Haiyan; Jin, Lei; Kerns, Peter; Meng, Michael; Suib, Steven_L; Gao, Puxian; et al (December 2023, ChemCatChem)

   Abstract Converting CO₂to value‐added chemicals,e. g., CH₃OH, is highly desirable in terms of the carbon cycling while reducing CO₂emission from fossil fuel combustion. Cu‐based nanocatalysts are among the most efficient for selective CO₂‐to‐CH₃OH transformation; this conversion, however, suffers from low reactivity especially in the thermodynamically favored low temperature range. We herein report ultrasmall copper (Cu) nanocatalysts supported on crystalline, mesoporous zinc oxide nanoplate (Cu@mZnO) with notable activity and selectivity of CO₂‐to‐CH₃OH in the low temperature range of 200–250 °C. Cu@mZnO nanoplates are prepared based on the crystal‐crystal transition of mixed Cu and Zn basic carbonates to mesoporous metal oxides and subsequent hydrogen reduction. Under the nanoconfinement of mesopores in crystalline ZnO frameworks, ultrasmall Cu nanoparticles with an average diameter of 2.5 nm are produced. Cu@mZnO catalysts have a peak CH₃OH formation rate of 1.13 mol h⁻¹per 1 kg under ambient pressure at 246 °C, about 25 °C lower as compared to that of the benchmark catalyst of Cu−Zn−Al oxides. Our new synthetic strategy sheds some valuable insights into the design of porous catalysts for the important conversion of CO₂‐to‐CH₃OH. 

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4. Physical Origin of Negative Differential Resistance in V ₃ O ₅ and Its Application as a Solid‐State Oscillator

   https://doi.org/10.1002/adma.202208477  

   Das, Sujan_Kumar; Nandi, Sanjoy_Kumar; Marquez, Camilo_Verbel; Rúa, Armando; Uenuma, Mutsunori; Puyoo, Etienne; Nath, Shimul_Kanti; Albertini, David; Baboux, Nicolas; Lu, Teng; et al (December 2022, Advanced Materials)

   Abstract Oxides that exhibit an insulator–metal transition can be used to fabricate energy‐efficient relaxation oscillators for use in hardware‐based neural networks but there are very few oxides with transition temperatures above room temperature. Here the structural, electrical, and thermal properties of V₃O₅thin films and their application as the functional oxide in metal/oxide/metal relaxation oscillators are reported. The V₃O₅devices show electroforming‐free volatile threshold switching and negative differential resistance (NDR) with stable (<3% variation) cycle‐to‐cycle operation. The physical mechanisms underpinning these characteristics are investigated using a combination of electrical measurements, in situ thermal imaging, and device modeling. This shows that conduction is confined to a narrow filamentary path due to self‐confinement of the current distribution and that the NDR response is initiated at temperatures well below the insulator–metal transition temperature where it is dominated by the temperature‐dependent conductivity of the insulating phase. Finally, the dynamics of individual and coupled V₃O₅‐based relaxation oscillators is reported, showing that capacitively coupled devices exhibit rich non‐linear dynamics, including frequency and phase synchronization. These results establish V₃O₅as a new functional material for volatile threshold switching and advance the development of robust solid‐state neurons for neuromorphic computing. 

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5. Concentrated ternary ether electrolyte allows for stable cycling of a lithium metal battery with commercial mass loading high‐nickel NMC and thin anodes

   https://doi.org/10.1002/cey2.275  

   Yang, Jun; Li, Xing; Qu, Ke; Wang, Yixian; Shen, Kangqi; Jiang, Changhuan; Yu, Bo; Luo, Pan; Li, Zhuangzhi; Chen, Mingyang; et al (March 2023, Carbon Energy)

   Abstract A new concentrated ternary salt ether‐based electrolyte enables stable cycling of lithium metal battery (LMB) cells with high‐mass‐loading (13.8 mg cm⁻², 2.5 mAh cm⁻²) NMC622 (LiNi_0.6Co_0.2Mn_0.2O₂) cathodes and 50 μm Li anodes. Termed “CETHER‐3,” this electrolyte is based on LiTFSI, LiDFOB, and LiBF₄with 5 vol% fluorinated ethylene carbonate in 1,2‐dimethoxyethane. Commercial carbonate and state‐of‐the‐art binary salt ether electrolytes were also tested as baselines. With CETHER‐3, the electrochemical performance of the full‐cell battery is among the most favorably reported in terms of high‐voltage cycling stability. For example, LiNi_xMn_yCo_1–x–yO₂(NMC)‐Li metal cells retain 80% capacity at 430 cycles with a 4.4 V cut‐off and 83% capacity at 100 cycles with a 4.5 V cut‐off (charge at C/5, discharge at C/2). According to simulation by density functional theory and molecular dynamics, this favorable performance is an outcome of enhanced coordination between Li⁺and the solvent/salt molecules. Combining advanced microscopy (high‐resolution transmission electron microscopy, scanning electron microscopy) and surface science (X‐ray photoelectron spectroscopy, time‐of‐fight secondary ion mass spectroscopy, Fourier‐transform infrared spectroscopy, Raman spectroscopy), it is demonstrated that a thinner and more stable cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) are formed. The CEI is rich in lithium sulfide (Li₂SO₃), while the SEI is rich in Li₃N and LiF. During cycling, the CEI/SEI suppresses both the deleterious transformation of the cathode R‐3m layered near‐surface structure into disordered rock salt and the growth of lithium metal dendrites. 

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