Advanced Composite Solid Electrolytes for Lithium Batteries: Filler Dimensional Design and Ion Path Optimization

Composite solid electrolytes are considered to be the crucial components of all-solid-state lithium batteries, which are viewed as the next-generation energy storage devices for high energy density and long working life. Numerous studies have shown that fillers in composite solid electrolytes can effectively improve the ion-transport behavior, the essence of which lies in the optimization of the ion-transport path in the electrolyte. The performance is closely related to the structure of the fillers and the interaction between fillers and other electrolyte components including polymer matrices and lithium salts. In this review, the dimensional design of fillers in advanced composite solid electrolytes involving 0D–2D nanofillers, and 3D continuous frameworks are focused on. The ion-transport mechanism and the interaction between fillers and other electrolyte components are highlighted. In addition, sandwich-structured composite solid electrolytes with fillers are also discussed. Strategies for the design of composite solid electrolytes with high room temperature ionic conductivity are summarized, aiming to assist target-oriented research for high-performance composite solid electrolytes.     

Composition Modulation and Structure Design of Inorganic‐in‐Polymer Composite Solid Electrolytes for Advanced Lithium Batteries

Owing to their safety, high energy density, and long cycling life, all‐solid‐state lithium batteries (ASSLBs) have been identified as promising systems to power portable electronic devices and electric vehicles. Developing high‐performance solid‐state electrolytes is vital for the successful commercialization of ASSLBs. In particular, polymer‐based composite solid electrolytes (PCSEs), derived from the incorporation of inorganic fillers into polymer solid electrolytes, have emerged as one of the most promising electrolyte candidates for ASSLBs because they can synergistically integrate many merits from their components. The development of PCSEs is summarized. Their major components, including typical polymer matrices and diverse inorganic fillers, are reviewed in detail. The effects of fillers on their ionic conductivity, mechanical strength, thermal/interfacial stability and possible Li⁺‐conductive mechanisms are discussed. Recent progress in a number of rationally constructed PCSEs by compositional and structural modulation based on different design concepts is introduced. Successful applications of PCSEs in various lithium‐battery systems including lithium–sulfur and lithium–gas batteries are evaluated. Finally, the challenges and future perspectives for developing high‐performance PCSEs are proposed.     

Self‐Suppression of Lithium Dendrite in All‐Solid‐State Lithium Metal Batteries with Poly(vinylidene difluoride)‐Based Solid Electrolytes

Polymer‐based electrolytes have attracted ever‐increasing attention for all‐solid‐state lithium (Li) metal batteries due to their ionic conductivity, flexibility, and easy assembling into batteries, and are expected to overcome safety issues by replacing flammable liquid electrolytes. However, it is still a critical challenge to effectively block Li dendrite growth and improve the long‐term cycling stability of all‐solid‐state batteries with polymer electrolytes. Here, the interface between novel poly(vinylidene difluoride) (PVDF)‐based solid electrolytes and the Li anode is explored via systematical experiments in combination with first‐principles calculations, and it is found that an in situ formed nanoscale interface layer with a stable and uniform mosaic structure can suppress Li dendrite growth. Unlike the typical short‐circuiting that often occurs in most studied poly(ethylene oxide) systems, this interface layer in the PVDF‐based system causes an open‐circuiting feature at high current density and thus avoids the risk of over‐current. The effective self‐suppression of the Li dendrite observed in the PVDF–LiN(SO₂F)₂ (LiFSI) system enables over 2000 h cycling of repeated Li plating–stripping at 0.1 mA cm^?2 and excellent cycling performance in an all‐solid‐state LiCoO₂||Li cell with almost no capacity fade after 200 cycles at 0.15 mA cm^?2 at 25 °C. These findings will promote the development of safe all‐solid‐state Li metal batteries.     

Dendrite‐Free Lithium Deposition via Flexible‐Rigid Coupling Composite Network for LiNi0.5Mn1.5O4/Li Metal Batteries

Notorious lithium dendrite causes severe capacity fade and harsh safety issues of lithium metal batteries, which hinder the practical applications of lithium metal electrodes in higher energy rechargeable batteries. Here, a kind of 3D‐cross‐linked composite network is successfully employed as a flexible‐rigid coupling protective layer on a lithium metal electrode. During the plating/stripping process, the composite protective layer would enable uniform distribution of lithium ions in the adjacent regions of the lithium electrode, resulting in a dendrite‐free deposition at a current density of 2 mA cm^?2. The LiNi_0.5Mn_1.5O₄‐based lithium metal battery presents an excellent cycling stability at a voltage range of 3.5–5.0 V with the induction of 3D‐cross‐linked composite protective layer. From an industrial field application of view, thin lithium metal electrodes (40 µm, with 4 times excess lithium) can be used in LiNi_0.5Mn_1.5O₄ (with industrially significant loading of 18 mg cm^?2 and 2.6 mAh cm^?2)‐based lithium metal batteries, which reveals a promising opportunity for practical applicability in high energy lithium metal batteries.     

Optimized Solid Electrolyte Interphase and Solvation Structure of Potassium Ions in Carbonate Electrolytes for High-Performance Potassium Metal Batteries

The introduction of electrolyte additives is one of the most potential strategies to improve the performance of potassium metal batteries (PMBs). However, designing an additive that can alter the K⁺ solvation shell and essentially inhibit K dendrite remains a challenge. Herein, the amyl-triphenyl-phosphonium bromide was introduced as an additive to build a stable solid electrolyte interphase layer. The amyl-TPP cations can form a cation shielding layer on the metal surface during the nucleation stage, preventing K⁺ from gathering at the tip to form K dendrites. Besides, the cations can be preferentially reduced to form K_xP_y with fast K⁺ transport kinetics. The Br⁻ anions, as Lewis bases with strong electronegativity, can not only coordinate the Lewis acid pentafluoride to inhibit the formation of HF, but also change the K⁺ solvation structure to reduce solvent molecules in the first solvation structure. Therefore, the symmetrical battery exhibits a low deposition overpotential of 123 mV at 0.1 mA cm⁻² over 4200 h cycle life. The full battery, paried with a perylene-tetracarboxylic dianhydride (PTCDA) cathode, possesses a cycle life of 250 cycles at 2 C and 81.9% capacity retention. This work offers a reasonable electrolyte design to obtain PMBs with long-term stablity and safety.     

Developing Outstanding Bifunctional Electrocatalysts for Rechargeable Zn-Air Batteries Using High-Purity Spinel-Type ZnCo2Se4 Nanoparticles

Zinc-air batteries are gaining popularity as viable energy sources for green energy storage technologies. The cost and performance of Zn-air batteries are mostly determined by the air electrodes in combination with an oxygen electrocatalyst. This research aims at the particular innovations and challenges relating to air electrodes and related materials. Here, a nanocomposite of ZnCo₂Se₄@rGO that exhibits excellent electrocatalytic activity for the oxygen reduction reaction, ORR (E_1/2 = 0.802 V), and oxygen evolution reaction, OER (η₁₀ = 298 mV@10 mA cm⁻²) is synthesized. In addition, a rechargeable zinc-air battery with ZnCo₂Se₄@rGO as the cathode showed a high open circuit voltage (OCV) of 1.38 V, a peak power density of 210.4 mW cm⁻², and outstanding long-term cycling stability. The electronic structure and oxygen reduction/evolution reaction mechanism of the catalysts ZnCo₂Se₄ and Co₃Se₄ are further investigated using density functional theory calculations. Finally, a perspective for designing, preparing, and assembling air electrodes is suggested for the future developments of high-performance Zn-air batteries.     

A Mesoporous Tungsten Oxynitride Nanofibers/Graphite Felt Composite Electrode with High Catalytic Activity for the Cathode in Zn-Br Flow Battery

High electrochemical polarization during a redox reaction in the electrode of aqueous zinc–bromine flow batteries largely limits its practical implementation as an effective energy storage system. This study demonstrates a rationally-designed composite electrode that exhibits a lower electrochemical polarization by providing a higher number of catalytically-active sites for faster bromine reaction, compared to a conventional graphite felt cathode. The composite electrode is composed of electrically-conductive graphite felt (GF) and highly active mesoporous tungsten oxynitride nanofibers (mWONNFs) that are prepared by electrospinning and simple heat treatments. Addition of the 1D mWONNFs to porous GF produces a web-like structure that significantly facilitates the reaction kinetics and ion diffusion. The cell performance achieves in this study demonstrated high energy efficiencies of 89% and 80% at current densities of 20 and 80 mA cm⁻², respectively. Furthermore, the cell can also be operated at a very high current density of 160 mA cm⁻², demonstrating an energy efficiency of 62%. These results demonstrate the effectiveness of the mWONNF/GF composite as the electrode material in zinc–bromine flow batteries.     

Advances in piezoelectric thin films for acoustic biosensors,acoustofluidics and lab-on-chip applications

Recently, piezoelectric thin films including zinc oxide (ZnO) and aluminium nitride (AlN) have found a broad range of lab-on-chip applications such as biosensing, particle/cell concentrating, sorting/patterning, pumping, mixing, nebulisation and jetting. Integrated acoustic wave sensing/microfluidic devices have been fabricated by depositing these piezoelectric films onto a number of substrates such as silicon, ceramics, diamond, quartz, glass, and more recently also polymer, metallic foils and bendable glass/silicon for making flexible devices. Such thin film acoustic wave devices have great potential for implementing integrated, disposable, or bendable/flexible lab-on-a-chip devices into various sensing and actuating applications. This paper discusses the recent development in engineering high performance piezoelectric thin films, and highlights the critical issues such as film deposition, MEMS processing techniques, control of deposition/processing parametres, film texture, doping, dispersion effects, film stress, multilayer design, electrode materials/designs and substrate selections. Finally, advances in using thin film devices for lab-on-chip applications are summarised and future development trends are identified.     

Recent breakthroughs and perspectives of high-energy layered oxide cathode materials for lithium ion batteries

Ni-rich layered oxides (NRLOs) and Li-rich layered oxides (LRLOs) have been considered as promising next-generation cathode materials for lithium ion batteries (LIBs) due to their high energy density, low cost, and environmental friendliness. However, these two layered oxides suffer from similar problems like capacity fading and different obstacles such as thermal runaway for NRLOs and voltage decay for LRLOs. Understanding the similarities and differences of their challenges and strategies at multiple scales plays a paramount role in the cathode development of advanced LIBs. Herein, we provide a comprehensive review of state-of-the-art progress made in NRLOs and LRLOs based on multi-scale insights into electrons/ions, crystals, particles, electrodes and cells. For NRLOs, issues like structure disorder, cracks, interfacial degradation and thermal runaway are elaborately discussed. Superexchange interaction and magnetic frustration are blamed for structure disorder while strains induced by universal structural collapse result in issues like cracks. For LRLOs, we present an overview of the origin of high capacity followed by local crystal structure, and the root of voltage hysteresis/decay, which are ascribed to reduced valence of transition metal ions, phase transformation, strains, and microstructure degradation. We then discuss failure mechanism in full cells with NRLO cathode and commercial challenges of LRLOs. Moreover, strategies to improve the performance of NRLOs and LRLOs from different scales such as ion-doping, microstructure designs, particle modifications, and electrode/electrolyte interface engineering are summarized. Dopants like Na, Mg and Zr, delicate gradient concentration design, coatings like spinel LiNi_0.5Mn_1.5O₄ or Li₃PO₄ and novel electrolyte formulas are highly desired. Developing single crystals for NRLOs and new crystallographic structure or heterostructure for LRLOs are also emphasized. Finally, remaining challenges and perspectives are outlined for the development of NRLOs and LRLOs. This review offers fundamental understanding and future perspectives towards high-performance cathodes for next-generation LIBs.