Energy Storage Materials最新文献

Utilizing lithium metal anodes with solid-state electrolytes (SSEs) to construct all-solid-state lithium batteries (ASSLBs) is a promising approach, which offers high energy density and safety. The SSEs play an integral role in ASSLBs, and the oxide garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is widely used as electrolyte material due to its high Li⁺ conductivity and wide electrochemical window. However, many issues in LLZO still need to be addressed, like the formation of Li₂CO₃ in air, interface contact with electrodes, and the growth of Li dendrites. We approach this review from the perspective that “structure determines performance”, elucidating the relationship between multi-scale microstructures (doping defects, grain boundary, surface and interface) and four key performances in batteries (Li⁺ conductivity, air stability, Li dendrites and cathode compatibility), analyzing the mechanisms of performances degradation induced by microstructures and summarizing various microstructures modification strategies that enhance performances, with the aim of constructing high-performance LLZO-based ASSLBs. Finally, we outline future research directions for LLZO, including the development of high-entropy LLZO SSEs, in-depth studies of grain boundary, advanced characterization and extra performance testing for LLZO evaluation, and feasible strategies in applications of LLZO-based ASSLBs.

The investigation of sustainable and renewable energy sources, coupled with the advancement of innovative energy storage technologies, represents a vital strategy for mitigating the present-day energy crisis. Among various techniques, supercapacitors (SCs) own great potential for future energy storage given their high-power density and long cycle life. However, conventional SCs are generally constructed based on fossil-derived products, which calls for sustainable materials in functionalization. Wood-derived materials, known for their hierarchically porous structures, robust mechanical strength, and tunable multifunctionality, are considered as ideal candidates for integration into SCs. While existing literature reviews have shed light on the advanced applications of wood or cellulose-based materials in SCs, there remains a notable gap in comprehensively exploring wood-derived materials across multiple scales − from macro (bulk wood) to micro (cellulose microfibers) and nano (cellulose nanofibers and cellulose nanocrystals). This review, therefore, undertakes a thorough investigation into the design and characteristics of multiscale wood-derived materials for advanced SCs. Initially, we provide a concise overview of the energy storage mechanism, the structural composition of SCs, the key factors influencing the properties of electrode materials in SCs, and the structural properties and constituents of wood. Subsequent sections uncover the latest advancements in the fabrication of electrode materials from wood, including carbonized wood, modified wood-derived carbon, and binary and ternary composite electrode involving cellulose and its derivatives. Furthermore, we address the challenges encountered in these processes and outline prospective directions for future research in electrode and device design, thus contributing to the advancement of SC applications in the field of energy storage.

The inability to effectively inhibit the lithium (Li) dendrite growth is identified as the real culprit hindering the practical application of polyethylene oxide (PEO)-based electrolytes. Herein, a novel PEO composite electrolyte with ion rectifier is developed based on the cross-scale synergistic rectification strategy. At the micro-scale, the array structure of the ion rectifier suppresses the growth of PEO crystals and their distribution in the non-ionic conduction direction through space confinement, alleviating ion-migration crosstalk and enabling polymer chain rectification. Furthermore, the matrix contains abundant copper ions and oxygen-containing groups that inhibit anion conduction and accelerate Li⁺ migration at the nanoscale, respectively, to achieve ion flow rectification. Implementing this strategy results in a uniform, fast, and stable Li⁺ migration/diffusion behavior from the electrolyte to anode interface. The critical current density of the PEO electrolyte is increased to 2.5 mA cm⁻², indicating a significant improvement in dendrite growth inhibition. Impressively, the composite electrolytes exhibit long-term stability (>4000 h at 0.2 mA cm⁻²) and ultra-high current-density tolerance (>200 h at 1 mA cm⁻²). Moreover, the composite electrolytes enable stable cycling of high-area-capacity (3.11 mAh cm⁻², 20 mg cm⁻²) LiFePO₄/Li pouch cells, highlighting the importance of this strategy for the practical application of PEO electrolytes.

Manganese dioxide (MnO₂) stands out as a prospective cathode material for calcium ion batteries (CIBs) owing to its elevated theoretical capacity and high operating voltage. Nevertheless, MnO₂ with Jahn-Teller (J-T) twisted MnO₆ octahedra experiences severe Mn dissolution during cycling, leading to the destabilization of the transition metal layer and resulting in poor cycling performance. In this work, Mo-substitution is purposely proposed to suppress the J-T effect in MnO₂ for CIBs. The local charge of Mn is regulated by Mo doping, which enhances the electrical conductivity of MnO₂ and suppresses the J-T distortion of the MnO₆ octahedron. Meanwhile, density-functional theory (DFT) calculations manifest that Mo doping enhances the structural integrity of MnO₂, making it difficult for Mn to escape from the MnO₆ structure and inhibiting the dissolution of Mn. Accordingly, Mo-MnO₂ demonstrates impressive rate capability (112 mAh g⁻¹ at 1 A g⁻¹) and excellent cycling stability, maintaining approximately 93.9 % capacity after 900 cycles at 1 A g⁻¹. As a result, the introduction of heteroatoms through doping offers a novel design approach for the advancement of cathode materials for advanced CIBs.

Seawater batteries (SWBs), which utilize sodium ions instead of lithium ions, hold significant promise due to the abundance and cost-effectiveness of raw materials. Additionally, SWBs can achieve high theoretical capacities with Na metal anode, and the introduction of redox-active electrolytes enhances the reversibility during Na metal plating and stripping. However, under certain conditions, such as high current density and extended distance between the solid electrolyte and current collector, the redox-active electrolyte can result in inferior cycling performance due to issues with Na metal plating on the solid electrolyte surface. In this study, we investigated the mechanism of Na metal deposition on solid electrolyte surfaces using redox-active electrolytes owning electronic conductivity. Through electrochemical analyses, we elucidated the factors that influence Na metal plating: electronic conductivity, distance, and current density. By controlling the concentration and electronic conductivity of redox-active electrolytes, we established operational parameters to mitigate solid electrolyte cracking and ensure stable cycling, even under conditions of long distance and high current density. Given that instances of Na metal plating on solid electrolytes in battery systems are rarely reported, our research provides new insights and suggests innovative approaches to understanding the mechanisms of Na metal plating and cracking in solid electrolytes.

Due to the uniform distribution of sodium in the crust, the increasing demand for high specific energy and long life in terms of energy storage is placing higher requests on sodium-ion battery technology. The activation of multi-electron reactions in NASICON sodium-ion battery cathode materials can not only reduce the use of vanadium, but also effectively increase the specific energy, therefore, it has received enormous attention from researchers. In this report, the importance of the covalent proportion of metal-oxygen bond in activating the V⁴⁺/V⁵⁺ redox with higher discharge voltage in Na₃V₂(PO₄)₃ has been extensively studied. Advanced characterization methods and theoretical calculations comprehensively explain the effects of Zn²⁺, Mg²⁺, and Cu²⁺ on V³⁺ substitution and the corresponding electrochemical behavior and structural change behavior. Moreover, a complete two-phase reaction in the high voltage reaction region (3.88 V) was observed in Na₃V_1.5Cu_0.5(PO₄)₃. Our results highlight the importance of the covalent proportion of metal-oxygen bonds in activating multi-electron reactions in NASICON structures.

The real-world commercial application of aqueous zinc-ion batteries (AZIBs) is retarded by the poor stability of Zn anode in aqueous solutions, resulting in annoying dendrite growth and intricate side reactions. Herein, the KI-CHOP polymer with rich hydroxyl groups is decorated on the Zn anode surface to rationally construct a solid-state ion-regulating interface. Combing with elaborate experiments and theoretical calculations, the tremendous zincophilic nucleation sites exposed on the KI-CHOP layer could homogenize the Zn²⁺ flux passing through the interface and decrease the desolvation barrier of hydrated Zn²⁺, thus speeding up deposition kinetics. Furthermore, the KI-CHOP coating could serve as a hydrogen-bond breaker to construct a lean-water interface thereby suppressing the parasitic side reactions. As expected, as-obtained KI-CHOP@Zn symmetric cells could deliver ultra-long cyclability for over 2200 h at 1.0 mA cm⁻² with an area capacity of 1.0 mAh cm⁻² as well as excellent reversibility of repeated plating/stripping of Zn²⁺. Moreover, the KI-CHOP@Zn//MnO₂ full cells also exhibit exceptional long-term durability under 1.0 A g⁻¹ for 2000 cycles and rate performance. The KI-CHOP protective layer in this work paves an inspiration for multifunctional polymer coating and takes a step towards the real-world application for AZIBs.

On the strength of the low-temperature tolerance, sodium-ion batteries (SIBs) are considered a promising complementary to lithium-ion batteries for applications in high-latitude, high-cold, deep-space, and deep-earth environments. However, the low-temperature performance of SIBs remains a challenge due to the sluggish Na⁺ diffusion kinetics in electrode materials and unstable electrode-electrolyte interface reactions. Therefore, the sound strategies of electrodes and electrolytes designed to optimize the low-temperature performance of SIBs are of great significance. In this review, the research and challenges of electrolytes, anode and cathode materials for low-temperature SIBs are critical emphasized focusing on the Na⁺ storage mechanism in electrode materials and the composition of electrolytes. In addition, the related strategies to improve low-temperature performance are summarized, including the selection of sodium salt anions, the use of multi-solvent components, and the incorporation of additives in electrolytes; as well as defect, interface, and nanostructure engineering for cathodes; and morphology engineering, elements doping, pore structure for anodes. Finally, the review provides an in-depth analysis of the solvated Na⁺ structure and the electrode/electrolyte interface mechanism and offers insights to the design of electrode materials, with the aim of facilitating the commercialization and large-scale deployment of SIBs in low-temperature conditions.

Quasi-solid state electrolytes (QSSEs) combine the benefits of both solid and liquid electrolytes, making them promising for high-performance lithium metal batteries (LMBs). However, developing QSSEs that achieve high ionic conductivity, a continuous electrode/electrolyte interface, and significant mechanical robustness remains challenging. Plant cell walls provide mechanical strength, while the cell membrane offers excellent material transport capabilities, making them effective models for quasi-solid electrolytes. However, using plant cells as a model can result in poor interface contacts due to the rigid components on the exterior. To address this, a “reverse” plant cell QSSE with a multifunctional bilayer architecture has been proposed. The outer layer acts as a functional reaction interface to enhance Li⁺ transmission, improve interfacial contact, and significantly reduce interfacial impedance. Meanwhile, the inner layer is designed to provide mechanical robustness and shorten ion transport distances. The QSSE inspired by “reverse” plant cells has an ionic conductivity of 4.26 × 10⁻³ S cm⁻¹, a Li⁺ transference number (t_Li+) of 0.91, and an electrochemical stability window (ESW) of 4.83 V. Li−LiFePO₄ (LFP) full cells based on the “reverse” plant cell QSSE can maintain a cycling capacity of 137 mAh g⁻¹ after 500 cycles at 1 C, with 95 % retention.

Aqueous Zn-ion batteries show superior development prospects and competitiveness with high theoretical capacity, abundant reserves and low potential. However, the inhomogeneous electrodeposition of zinc anodes and zinc dendrite growth highly limit their commercialization. To address these issues, multifunctional hybridized interfaces consisting of layered double hydroxide (LDH) and graphene quantum dots (GQDs) are constructed on the surface of zinc metal anodes. LDH with hydrophobicity will effectively shield the corrosion of aqueous electrolyte on the zinc anode, and simultaneously serve as a mechanical skeleton for zinc deposition. The hydrophilic GQDs will control the coordination environment of solvated Zn²⁺, reduce the reactivity of water and promote the uniform deposition of zinc ions along the (002) crystal surface. The interfacially modified Zn anode achieves more than 1000 h and 1200 h of stable cycling at 1 and 2 mA cm⁻², respectively. Moreover, the assembled Zn@LDH@GQDs//NH₄V₄O₁₀ full cells achieve 2000 stable cycles at a high current density of 10 A g⁻¹. The present work reveals the intrinsic mechanism of inhibiting zinc dendrites by the protective layer of multifunctional hybrid materials, which provides an important idea for stabilizing zinc anodes.