Covalently Cross-Linked Chemistry of a Three-Dimensional Network Binder at Limited Dosage Enables Practical Si/C Composite Electrode Applications.

Currently, Si (or SiOx, 1 < x < 2) and graphite composite (Si/C) electrodes (e.g., Si/C450 and Si/C600 with specific capacities of 450 and 600 mAh g-1 at 0.1 C, respectively) have become the most promising alternative to traditional graphite anodes toward high-energy lithium-ion battery (LIB) applications by virtue of their higher specific capacity compared to graphite ones and improved cycle performance compared to Si (or SiOx) ones. However, such composite electrodes remain challenging to practical for implementation owing to electrode structure disintegration and interfacial instability caused by a large volume change of inner Si-based particles. Herein, we develop a covalent-bond cross-linking network binder for Si/C450 and Si/C600 electrodes via reversible addition-fragmentation chain transfer (RAFT) polymerization. The as-developed binder with a 3 mol % cross-linker of other monomers [termed P(SH-BA3%)] achieves improved mechanical and adhesive properties and decreased Si/C anode volume expansion, compared to the linear binder counterpart. Impressively, the P(SH-BA3%) binder at only 3 wt % dosage enables 83.56% capacity retention after 600 cycles at 0.5 C in Si/C450 anode based half-cells and retains 86.42% capacity retention at 0.3 C after 200 cycles and 80.95% capacity retention at 0.5 C after 300 cycles in LiNi0.8Co0.1Mn0.1O2 cathode (15 mg cm-2) based homemade soft package full cells. This work provides insight into binder cross-linking chemistry under limited dosage and enlightens cross-linking binder design toward practical Si/C electrode applications.

A Spidroin-Inspired Hierarchical-Structure Binder Achieves Highly Integrated Silicon-Based Electrodes.

As a promising component for next-generation high-energy lithium-ion batteries, silicon-based electrodes have attracted increasing attention by virtue of their ultrahigh theoretical specific capacities. Nevertheless, fast capacity fading posed by tremendous silicon-based electrode volume changes during cycling remains a huge challenge before large-scale applications. In this work, an aqueous-oil binary solution based blend (AOB) binder characterized by a spidroin-like hierarchical structure for tolerating the huge volume changes of silicon-based electrodes is developed. In the AOB binder, the polymer, containing hydrophobic tetrazole groups, denoted as PPB, and the water-soluble amorphous poly(acrylic acid), mimick the ß-sheet and α-helix structure of spidroin, respectively. Benefitting from such biomimetic design, the AOB binder enables both high tensile strength and elasticity, and strong electrode adhesion, therefore apparently stabilizing the silicon-based electrode structure and rendering prolonged electrode cycle life. Such a strategy endows 3.3 Ah soft package cells assembled with Si/C composite anode and NCM811 cathode with a discharge specific capacity of 2.92 Ah after 700 cycles. This work marks a milestone in developing state-of-the-art silicon-based electrodes toward high-energy-density lithium-battery applications.

An Endotenon Sheath-Inspired Double-Network Binder Enables Superior Cycling Performance of Silicon Electrodes.

Silicon (Si) has been regarded as an alternative anode material to traditional graphite owing to its higher theoretical capacity (4200 vs. 372 mAh g-1). However, Si anodes suffer from the inherent volume expansion and unstable solid electrolyte interphase, thus experiencing fast capacity decay, which hinders their commercial application. To address this, herein, an endotenon sheath-inspired water-soluble double-network binder (DNB) is presented for resolving the bottleneck of Si anodes. The as-developed binder shows excellent adhesion, high mechanical properties, and a considerable self-healing capability mainly benefited by its supramolecular hybrid network. Apart from these advantages, this binder also induces a Li3N/LiF-rich solid electrolyte interface layer, contributing to a superior cycle stability of Si electrodes. As expected, the DNB can achieve mechanically more stable Si electrodes than traditional polyacrylic acid and pectin binders. As a result, DNB delivers superior electrochemical performance of Si/Li half cells and LiNi0.8Co0.1Mn0.1O2/Si full cells, even with a high loading of Si electrode, to traditional polyacrylic acid and pectin binders. The bioinspired binder design provides a promising route to achieve long-life Si anode-assembled lithium batteries.

Bioinspired Antiaging Binder Additive Addressing the Challenge of Chemical Degradation of Electrolyte at Cathode/Electrolyte Interphase.

For layered transition metal oxides cathode-based lithium batteries, the chemical degradation of electrolytes leads to fast battery capacity decay, severely challenging their practical applications. This kind of chemical degradation of electrolytes is caused by the oxidation of reactive oxygen (e.g., singlet oxygen) and the attack of free radicals during cycling. To address this, we first report a biologically inspired antiaging strategy of developing the photostabilizer with singlet oxygen- and free radicals-scavenging abilities as a cathode binder additive. It is fully evidenced that this binder system consisting of the binder additive and a commercially available polyvinylidene difluoride can scavenge singlet oxygen and free radicals generated during high-voltage cycling, thus significantly restraining electrolyte decomposition. As a result, high-voltage layered transition metal oxides-based lithium batteries with reproducibly superior electrochemical performance, even under elevated temperatures, can be achieved. This bioinspired strategy to scavenge reactive oxygen and free radicals heralds a new paradigm for manipulating the cathode/electrolyte interphase chemistry of various rechargeable batteries involving layered transition metal oxides-based cathodes.

Uncovering the Chemistry of Cross-Linked Polymer Binders via Chemical Bonds for Silicon-Based Electrodes.

Great efforts have been devoted to the development of high-energy-density lithium-ion batteries (LIBs) to meet the requirements of emerging technologies such as electric cars, large-scale energy storage, and portable electronic devices. To this end, silicon-based electrodes have been increasingly regarded as promising electrode materials by virtue of their high theoretical capacity, low costs, environmental friendliness, and high natural abundance. It has been noted that during repeated cycling, severe challenges such as huge volume change remain to be solved prior to practical application, which boosts the development of advanced cross-linked binders via chemical bonds (CBCBs) beyond traditional PVDF binder. This is because CBCBs can effectively fix the electrode particles, inhibit the volume expansion of Si particles, and stabilize the solid electrolyte interface and thus can enable good cycling stability of silicon anode-based batteries. In light of these merits, CBCBs hence arouse much attention from both industry and academia. In this review, we present chemical/mechanical characteristics of CBCBs and systematically discuss the recent advancements of cross-linked binders via chemical bonding for silicon-based electrodes. Focus is placed on the cross-linking chemistries, construction methods and structure-performance relationships of CBCBs. Finally, the future development and performance optimization of CBCBs are proposed. This discussion will provide good insight into the structural design of CBCBs for silicon-based electrodes.