Silicon has attracted ever-increasing attention as a high-capacity anode material in Li-ion batteries owing to its extremely high theoretical capacity. However, practical application of silicon anodes is seriously hindered by its fast capacity fading as a result of huge volume changes during the charge/discharge process. Here, an interpenetrated gel polymer binder for high-performance silicon anodes is created through in-situ crosslinking of water-soluble poly(acrylic acid) (PAA) and polyvinyl alcohol (PVA) precursors. This gel polymer binder with deformable polymer network and strong adhesion on silicon particles can effectively accommodate the large volume change of silicon anodes upon lithiation/delithiation, leading to an excellent cycling stability and high Coulombic efficiency even at high current densities. Moreover, high areal capacity of ∼4.3 mAh/cm2 is achieved based on the silicon anode using the gel PAA–PVA polymer binder with a high mass loading. In view of simplicity in using the water soluble gel polymer binder, it is believed that this novel binder has a great potential to be used for high capacity silicon anodes in next generation Li-ion batteries, as well as for other electrode materials with large volume change during cycling.

Interpenetrated Gel Polymer Binder for High Performance Silicon Anodes in Lithium-Ion Batteries

Owing to its high theoretical capacity, appropriate working potential, abundant resource, intrinsic safety, and low cost, zinc (Zn) metal is regarded as one of the most promising anode candidates for aqueous batteries. However, the hazards caused by dendrite growth and side reactions impede its practical applications. Herein, to solve these problems, a protective heterogeneous layer composed of electronic conductive sulfur-doped three-dimensional (3D) MXene and ionic conductive ZnS on Zn anode is designed and constructed. The sulfur doping and the creation of a 3D structure on MXene are simultaneously achieved during the generation of ZnS. The sulfur-doped 3D MXene can effectively homogenize distribution of electric field, decrease local current density, and alleviate volume change. The ZnS can inhibit side reactions, promote uniform Zn2+ distribution, and accelerate Zn2+ migration. Consequently, a stable and dendrite-free Zn anode is achieved with notable cycling stability up to 1600 h and rate performance. The relationship between structure of protective layer and performance of Zn anode is also probed. With the protected Zn anode and freestanding sulfur-doped 3D MXene@MnO2 cathode, a high-energy, long cycling life, and high-rate full cell is obtained. This work may provide a direction for the design of practical Zn anodes and other metal-based battery systems.

Rational Design of Sulfur-Doped Three-Dimensional Ti3C2Tx MXene/ZnS Heterostructure as Multifunctional Protective Layer for Dendrite-Free Zinc-Ion Batteries.

Rechargeable aqueous Zn batteries are potential for large-scale electrochemical energy storage due to their low cost and high security. However, Zn metal anode suffers from the dendritic growth and interfacial hydrogen evolution reaction (HER), resulting in the deterioration of electrode/battery performance. Here we propose that both dendrites and HER are related to the water participated Zn2+ solvation structure-Zn(H2 O)62+ and thus can be resolved by transforming Zn(H2 O)62+ to an anion-type water-free solvation structure-ZnCl42- , which is achieved in traditional ZnSO4 aqueous electrolyte after adding chloride salt with a bulky cation (1-ethyl-3-methylimidazolium chloride). The elimination of cation-water interaction suppresses HER, while the electrostatic repulsion between Zn tips and the anion solvation structure inhibits dendrite formation. As a result, the electrolyte shows uniform Zn deposition with an average Zn plating/stripping Coulombic efficiency of ≈99.9 %, enabling a capacity retention of 78.8 % after 300 cycles in anode-free Zn batteries with pre-zincificated polyaniline as the cathode. This work provides a novel electrolyte design strategy to prevent HER and realize long-lifespan metal anode.

Designing Anion-Type Water-Free Zn2+ Solvation Structure for Robust Zn Metal Anode

The rapid advance of mild aqueous zinc-ion batteries (ZIBs) is driving the development of the energy storage system market. But the thorny issues of Zn anodes, mainly including dendrite growth, hydrogen evolution, and corrosion, severely reduce the performance of ZIBs. To commercialize ZIBs, researchers must overcome formidable challenges. Research about mild aqueous ZIBs is still developing. Various technical and scientific obstacles to designing Zn anodes with high stripping efficiency and long cycling life have not been resolved. Moreover, the performance of Zn anodes is a complex scientific issue determined by various parameters, most of which are often ignored, failing to achieve the maximum performance of the cell. This review proposes a comprehensive overview of existing Zn anode issues and the corresponding strategies, frontiers, and development trends to deeply comprehend the essence and inner connection of degradation mechanism and performance. First, the formation mechanism of dendrite growth, hydrogen evolution, corrosion, and their influence on the anode are analyzed. Furthermore, various strategies for constructing stable Zn anodes are summarized and discussed in detail from multiple perspectives. These strategies are mainly divided into interface modification, structural anode, alloying anode, intercalation anode, liquid electrolyte, non-liquid electrolyte, separator design, and other strategies. Finally, research directions and prospects are put forward for Zn anodes. This contribution highlights the latest developments and provides new insights into the advanced Zn anode for future research. 

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Zinc Anode for Mild Aqueous Zinc-Ion Batteries: Challenges, Strategies, and Perspectives

Reversible zinc-based anodes enabled by zincophilic antimony engineered MXene for stable and dendrite-free aqueous zinc batteries

Stable Aqueous Anode-Free Zinc Batteries Enabled by Interfacial Engineering

Metal anodes based on a plating/stripping electrochemistry such as metallic Li, Na, K, Zn, Ca, Mg, Fe, and Al are recognized as promising anode materials for constructing next-generation high-energy-density rechargeable metal batteries owing to their low electrochemical potential, high theoretical specific capacity, superior electronic conductivity, etc. However, inherent issues such as high chemical reactivity, severe growth of dendrites, huge volume changes, and unstable interface largely impede their practical application. Covalent organic frameworks (COFs) and their derivatives as emerging multifunctional materials have already well addressed the inherent issues of metal anodes in the past several years due to their abundant metallophilic functional groups, special inner channels, and controllable structures. COFs and their derivatives can solve the issues of metal anodes by interfacial modification, homogenizing ion flux, acting as nucleation seeds, reducing the corrosion of metal anodes, and so on. Nevertheless, related reviews are still absent. Here we present a detailed review of multifunctional COFs and their derivatives in metal anodes for rechargeable metal batteries. Meanwhile, some outlooks and opinions are put forward. We believe the review can catch the eyes of relevant researchers and supply some inspiration for future research.

Covalent Organic Frameworks and Their Derivatives for Better Metal Anodes in Rechargeable Batteries.

Building stable solid electrolyte interphases (SEI) for microsized silicon anode and 5V-class cathode with salt engineered nonflammable phosphate-based lithium-ion battery electrolyte

Lithium metal anodes are promising for their high energy density and low working potential. However, high reactivity and dendrite growth of lithium metal lead to serious safety issues. Lithium dendrite may form "dead lithium" or pierce the separator, which will cause low efficiency and short-circuit inside the battery. A nonflammable phosphate-based electrolyte can effectively solve the flammability problem. Also, it shows poor compatibility with lithium metal anodes, resulting in an unstable solid electrolyte interface (SEI), which leads to dendrite growth and poor electrochemical performance. In this study, trimethyl phosphate is used to ensure the safety of lithium metal batteries. By adjusting the concentration of lithium salt and introducing fluoroethylene carbonate, a stable SEI layer is formed on the surface of the lithium metal anode and dendrite growth of the lithium metal anode is inhibited. Lithium metal batteries with a modified electrolyte achieved stable electrochemical plating/stripping, and the full cell has 93.4% capacity left and the coulombic efficiency is nearly 100%. In addition, the modified electrolyte can also enable reversible intercalation and de-intercalation of Li+ in the commercial graphite anode. This work may provide an alternative direction for the development of lithium metal batteries with high safety and high energy density.

High-Safety and Dendrite-Free Lithium Metal Batteries Enabled by Building a Stable Interface in a Nonflammable Medium-Concentration Phosphate Electrolyte.

Highly Reversible and Safe Lithium Metal Batteries enabled by Non-flammable All-fluorinated Carbonate Electrolyte Conjugated With 3D Flexible MXene-based Lithium Anode

Kai Zhang

Papers

Stable Aqueous Anode-Free Zinc Batteries Enabled by Interfacial Engineering

Covalent Organic Frameworks and Their Derivatives for Better Metal Anodes in Rechargeable Batteries.

Building stable solid electrolyte interphases (SEI) for microsized silicon anode and 5V-class cathode with salt engineered nonflammable phosphate-based lithium-ion battery electrolyte

High-Safety and Dendrite-Free Lithium Metal Batteries Enabled by Building a Stable Interface in a Nonflammable Medium-Concentration Phosphate Electrolyte.

Highly Reversible and Safe Lithium Metal Batteries enabled by Non-flammable All-fluorinated Carbonate Electrolyte Conjugated With 3D Flexible MXene-based Lithium Anode