Constructing An Oxyhalide Interface for 4.8†V-Tolerant High-Nickel Cathodes in All-Solid-State Lithium-Ion Batteries.

All-solid-state lithium batteries (ASSBs) have received increasing attentions as one promising candidate for the next-generation energy storage devices. Among various solid electrolytes, sulfide-based ASSBs combined with layered oxide cathodes have emerged due to the high energy density and safety performance, even at high-voltage conditions. However, the interface compatibility issues remain to be solved at the interface between the oxide cathode and sulfide electrolyte. To circumvent this issue, we propose a simple but effective approach to magic the adverse surface alkali into a uniform oxyhalide coating on LiNi0.8Co0.1Mn0.1O2 (NCM811) via a controllable gas-solid reaction. Due to the enhancement of the close contact at interface, the ASSBs exhibit improved kinetic performance across a broad temperature range, especially at the freezing point. Besides, owing to the high-voltage tolerance of the protective layer, ASSBs demonstrate excellent cyclic stability under high cutoff voltages (500 cycles~94.0 % at 4.5 V, 200 cycles~80.4 % at 4.8 V). This work provides insights into using a high voltage stable oxyhalide coating strategy to enhance the development of high energy density ASSBs.

Achieving a Deeply Desodiated Stabilized Cathode Material by the High Entropy Strategy for Sodium-ion Batteries.

Manganese-based layered oxides are currently of significant interest as cathode materials for sodium-ion batteries due to their low toxicity and high specific capacity. However, the practical applications are impeded by sluggish intrinsic Na+ migration and poor structure stability as a result of Jahn-Teller distortion and complicated phase transition. In this study, a high-entropy strategy is proposed to enhance the high-voltage capacity and cycling stability. The designed P2-Na0.67Mn0.6Cu0.08Ni0.09Fe0.18Ti0.05O2 achieves a deeply desodiation and delivers charging capacity of 158.1 mAh g-1 corresponding to 0.61 Na with a high initial Coulombic efficiency of 98.2 %. The charge compensation is attributed to the cationic and anionic redox reactions conjunctively. Moreover, the crystal structure is effectively stabilized, leading to a slight variation of lattice parameters. This research carries implications for the expedited development of low-cost, high-energy-density cathode materials for sodium-ion batteries.

Atomic-Resolution In Situ Exploration of the Phase Transition Triggered Failure in a Single-Crystalline Ni-Rich Cathode.

Single-crystalline cathode materials LiNixCoyMn1-y-zO2 (x ≥ 0.6) are important candidates for obtaining better cyclic stability and achieving high energy densities of Li-ion batteries. However, it is liable to initiate phase transitions inside the grains during electrochemical cycling, and the processes and regions of these phase transitions have remained unknown. In this research, we conducted an intrinsic study, investigating the chemicals and microstructural evolution of single-crystalline LiNi0.83Co0.11Mn0.06O2 using in situ biasing transmission electron microscopy at an atomic scale. We observed that the layered structure on the surface of the single-crystalline material was degraded during the charging process, resulting in continuous phase transitions and the formation of surface oxygen vacancies, which can reduce both the structural and thermal stability of the material. Uneven delithiation led to the formation of high-density defects and discontinuous inactive electrochemical phases, such as local antiphase boundaries and the rock salt phase, in the bulk of the material. The non-uniformity of the structure and the coexistence of active and inactive phases introduce significant tensile stress, which can lead to intragranular cracks inside the grains. As the number of cycles increases, the structural degradation caused by the intragranular phase transition will further increase, ultimately affecting the cycling capacity and stability of the battery. This work has broad implications for creating lithium-ion batteries that are effective and long-lasting.

From Oxygen Redox to Sulfur Redox: A Paradigm for Li-Rich Layered Cathodes.

The utilization of anionic redox chemistry provides an opportunity to further improve the energy density of Li-ion batteries, particularly for Li-rich layered oxides. However, oxygen-based hosts still suffer from unfavorable structural rearrangement, including the oxygen release and transition metal (TM)-ion migration, in association with the tenuous framework rooted in the ionicity of the TM-O bonding. An intrinsic solution, by using a sulfur-based host with strong TM-S covalency, is proposed here to buffer the lattice distortion upon the highly activating sulfur redox process, and it achieves howling success in stabilizing the host frameworks. Experimental results demonstrate the prolonged preservation of the layered sulfur lattice, especially the honeycomb superlattice, during the Li+ extraction/insertion process in contrast to the large structural degeneration in Li-rich oxides. Moreover, the Li-rich sulfide cathodes exhibited a negligible overpotential of 0.08 V and a voltage drop of 0.13 mV/cycle, while maintaining a substantial reversible capacity upon cycling. These superior electrochemical performances can be unambiguously ascribed to the much shorter trajectories of sulfur in comparison to those of oxygen revealed by molecular dynamics simulations at a large scale (∼30 nm) and a long time scale (∼300 ps) via high-dimensional neural network potentials during the delithiation process. Our findings highlight the importance of stabilizing host frameworks and establish general guidance for designing Li-rich cathodes with durable anionic redox chemistry.

Molecular Engineering toward Robust Solid Electrolyte Interphase for Lithium Metal Batteries.

Lithium-metal batteries (LMBs) with high energy density are becoming increasingly important in global sustainability initiatives. However, uncontrollable dendrite seeds, inscrutable interfacial chemistry, and repetitively formed solid electrolyte interphase (SEI) have severely hindered the advancement of LMBs. Organic molecules have been ingeniously engineered to construct targeted SEI and effectively minimize the above issues. In this review, multiple organic molecules, including polymer, fluorinated molecules, and organosulfur, are comprehensively summarized and insights into how to construct the corresponding elastic, fluorine-rich, and organosulfur-containing SEIs are provided. A variety of meticulously selected cases are analyzed in depth to support the arguments of molecular design in SEI. Specifically, the evolution of organic molecules-derived SEI is discussed and corresponding design principles are proposed, which are beneficial in guiding researchers to understand and architect SEI based on organic molecules. This review provides a design guideline for constructing organic molecule-derived SEI and will inspire more researchers to concentrate on the exploitation of LMBs.

A prototype of dual-ion conductor for all-solid-state lithium batteries.

All-solid-state batteries (ASSBs) represent a promising battery strategy to achieve high energy density with great safety. However, inadequate kinetic property and poor interfacial compatibility remain great challenges, which impede their practical application. A prototype of dual-ion conductor of Li+ synchronized with Cu+ unlocks a four-electron redox reaction with high reversibility and fast kinetics. As a result, the constructed ASSB exhibited a high reversible capacity of 603.0 mA·hour g-1 and an excellent cycling retention of 93.2% over 1500 cycles. Moreover, because of the ion highway connecting active materials and catholytes constructed by dual-ion conductor, remarkable temperature tolerance (-60°C) and excellent rate performance (231.6 mA·hour g-1 at 20 mA cm-2) were achieved. The superior electrochemical performance can be ascribed to the migration pathway with small energy barrier and low tortuosity once the Cu+ introduced into Li6PS5Cl. This work creates a unique perspective of ASSBs with dual-ion conducting strategy, thus inspiring a potential developing strategy of state-of-the-art ASSBs.

A new Li-rich layered cathode with low lattice strain for lithium-ion batteries.

A new layered C2/m oxide, Li2Ni0.2Mn0.4Ru0.4O3 (LNMR), is introduced as a cathode for lithium-ion batteries, which undergoes a low volume variation of 1.5% in the voltage window of 2.0-4.6 V studied via in situ X-ray diffraction. Compared with the contrast sample Li2MnO3, LNMR displays superior capacity, a more stable capacity retention rate, and higher energy density and average discharge voltage.

Cyclic enrichment of chromium based on valence state transformation in metal-free photocatalytic reductive imprinted composite hydrogel.

Cr (VI) exists in anion form and can be reduced to positive charged Cr (III) under certain conditions. Can positive charged Cr (III) be continually used for absorbing Cr (VI) to achieve cyclic accumulation of chromium? In this paper, an ion imprinting material for adsorption of Cr (VI) was prepared by dispersing polypyrrole (PPy) in a gelatin/chitosan (Gel/CS) hydrogel network, named Gel/CS/PPy. Based on the conversion of Cr (VI) to Cr (III), a cyclic enrichment process including adsorption-photoreduction-fixation-readsorption of Cr (VI) was established in Gel/CS/PPy hydrogel. The composition and structure of the Gel/CS/PPy were analyzed by scanning electron microscopy (SEM), Fourier transform-infrared spectroscopy (FT-IR), thermogravimetric (TGA), texture analyzer (Universal TA), zeta potential and ultraviolet-visible-near infrared spectra (UV-vis-NIR). The conversion of Cr (VI) and Cr (III) and its promoting effect on readsorption were verified by XPS. The results showed that Gel/CS/PPy has good adsorption capacity for Cr (VI) and excellent photocatalytic ability to reduce Cr (VI) to Cr (III). Cr (III)-loaded Gel/CS/PPy can be further used to adsorb Cr (VI) and showed good adsorption efficiency even after four cycles. The optimal operating condition for Cr (VI) adsorption is pH = 3; 2 g/L dose of Gel/CS/PPy; and the adsorption capacity of Cr (VI) was about 106.8 mg/g after six adsorption cycles. Since Gel/CS/PPy is composed of organic components, high purity chromium can be recovered by simple calcination method later. Therefore, the synthesized Gel/CS/PPy has great potential in the practical application of low concentration Cr (VI) treatment in water.

Photo/thermal response of polypyrrole-modified calcium alginate/gelatin microspheres based on helix-coil structural transition and the controlled release of agrochemicals.

Responsive controlled-release systems can not only improve the efficiency of agrochemical utilization but also increase crop yield and reduce environmental pollution caused by excessive use of agrochemicals. In this paper, the helix-coil structural transition of gelatin was adopted to construct a novel stimuli-responsive controlled-release system called polypyrrole/Ca-alginate/gelatin (PPy/Ca-alginate/Gel). In PPy/Ca-alginate/Gel, Ca-alginate and gelatin form a semi-interpenetrating network in which uncross-linked gelatin can undergo a free helix-coil structural transition due to the photothermal effect of PPy. The structural transition of gelatin will lead to changes in the functional groups and microstructure of semi-interpenetrating hydrogels and furthermore achieve the release of template agrochemical molecules embedded in hydrogels. By using carbendazim as a template molecule, the photothermal conversion and controlled release of PPy/Ca-alginate/Gel were systematically studied. After 600 s of light irradiation, its temperature could be increased by 17 ℃. The release of carbendazim in microspheres reached 91.8 % after 8 h of light irradiation, while it was only 13.3 % in the dark. The results indicated that PPy/Ca-alginate/Gel have excellent controlled-release and sustained-release properties and broad application potential in agriculture.

High-Performance Flexible In-Plane Micro-Supercapacitors Based on Vertically Aligned CuSe@Ni(OH)2 Hybrid Nanosheet Films.

The orientation and hybridization of ultrathin two-dimensional (2D) nanostructures on interdigital electrodes is vital for developing high-performance flexible in-plane micro-supercapacitors (MSCs). Despite great progress has been achieved, integrating CuSe and Ni(OH)2 nanosheets to generate advanced nanohybrids with oriented arrangement of each component and formation of porous frameworks remains a challenge, and their application for in-plane MSCs has not been explored. Herein, the vertically aligned CuSe@Ni(OH)2 hybrid nanosheet films with hierarchical open channels are skillfully deposited on Au interdigital electrodes/polyethylene terephthalate substrate via a template-free sequential electrodeposition approach, and directly employed to construct in-plane MSCs by choosing polyvinyl alcohol-LiCl gel as both the separator and the solid electrolyte. Because of the unique geometrical structure and combination of intrinsically conductive CuSe and battery-type Ni(OH)2 components, such hybrid nanosheet films can not only resolve the poor conductivity and re-stacking problems of Ni(OH)2 nanosheets but also create the 3D electrons or ions transport pathway. Thus, the in-plane MSCs device fabricated by such hybrid nanosheet films exhibits high volumetric specific capacitance (38.9 F cm-3). Moreover, its maximal energy and power density can reach 5.4 mW h cm-3 and 833.2 mW cm-3, superior to pure CuSe nanosheets, and most of reported carbon materials and metal hydroxides/oxides/sulfides based in-plane MSCs ones. Also, the hybrid nanosheet films device shows excellent cycling performance, good flexibility, and mechanical stability. This work may shed some light on optimizing 2D electrode materials and promote the development of flexible in-plane MSCs or other energy storage systems.