Modulating the Inner Helmholtz Plane towards Stable Solid Electrolyte Interphase by Anion-π Interactions for High-Performance Anode-Free Lithium Metal Batteries.

Anode-free lithium (Li) metal batteries (AFLBs) featured high energy density are viewed as the viable future energy storage technology. However, the irregular Li deposition and unstable solid electrolyte interphase (SEI) on anode current collectors reduce their cycling performance. Here, we propose a concept of anion-recognition electrodes enabled by anion-π interactions to regulate the inner Helmholtz plane (IHP) and electrolyte solvation chemistry for high-performance AFLBs. By engineering the electrodes with electron-deficient aromatic-π systems that possess high permanent quadrupole moment (Qzz), the anion-π interactions can be generated to concentrate the anions on the electrode surface and tune the IHP structure to construct a stable anion-derived SEI layer, thus achieving highly reversible Li plating/stripping process. Through designing various current collectors with different Qzz values, the intimate correlations among the surface charge of the electrode, competitive adsorption of the IHP, and SEI structures are demonstrated. Particularly, the modified carbon cloth current collector with a high Qzz value (+35.1) delivers a high average Li stripping/plating Coulombic efficiency of 99.1 % over 230 cycles in the carbonated electrolyte, enabling a long lifespan and high capacity retention of LiNi0.8Co0.1Mn0.1O2-based AFLBs with a commercial-level areal capacity (4.1 mAh cm-2).

An Ion-Pumping Quasi-Solid Electrolyte Enabled by Electrokinetic Effects for Stable Aqueous Zinc Metal Batteries.

The practical application of aqueous zinc (Zn) metal batteries (ZMBs) is hindered by the complicated hydrogen evolution, passivation reactions, and dendrite growth of Zn metal anodes. Here, an ion-pumping quasi-solid electrolyte (IPQSE) with high Zn2+ transport kinetics enabled by the electrokinetic phenomena to realize high-performance quasi-solid state Zn metal batteries (QSSZMBs) is reported. The IPQSE is prepared through the in situ ring-opening polymerization of tetramethylolmethane-tri-ß-aziridinylpropionate in the aqueous electrolyte. The porous polymer framework with high zeta potential provides the IPQSE with an electrokinetic ion-pumping feature enabled by the electrokinetic effects (electro-osmosis and electrokinetic surface conduction), which significantly accelerates the Zn2+ transport, reduces the concentration polarization and overcomes the diffusion-limited current. Moreover, the Zn2+ affinity of the polymer and hydrogen bonding interactions in the IPQSE changes the Zn2+ coordination environment and reduces the amount of free H2O, which lowers the H2O activity and inhibits H2O-induced side reactions. Consequently, the highly reversible and stable Zn metal anodes are achieved. The assembled QSSZMBs based on the IPQSE display excellent cycling stability with high capacity retention and Coulombic efficiency. The high-performance quasi-solid state Zn metal pouch cells are demonstrated, showing great promise for the practical application of the IPQSE.

Breaking Mass Transport Limitations by Iodized Polyacrylonitrile Anodes for Extremely Fast-Charging Lithium-Ion Batteries.

The fast-charging capability of rechargeable batteries is greatly limited by the sluggish ion transport kinetics in anode materials. Here we develop an iodized polyacrylonitrile (I-PAN) anode that can boost the bulk/interphase lithium (Li)-ion diffusion kinetics and accelerate Li-ion desolvation process to realize high-performance fast-charging Li-ion batteries. The iodine immobilized in I-PAN framework expands ion transport channels, compresses the electric double layer, and changes the inner Helmholtz plane to form LiF/LiI-rich solid electrolyte interphase layer. The dissolved iodine ions in the electrolyte self-induced by the interfacial nucleophilic substitution of PF6 - not only promote the Li-ion desolvation process, but also reuse the plated/dead Li formed on the anode under fast-charging conditions. Consequently, the I-PAN anode exhibits a high capacity of 228.5 mAh g-1 (39 % of capacity at 0.5 A g-1 delivered in 18 seconds) and negligible capacity decay for 10000 cycles at 20 A g-1 . The I-PAN||LiNi0.8 Co0.1 Mn0.1 O2 full cell shows excellent fast-charging performance with attractive capacities and negligible capacity decay for 1000 cycles at extremely high rates of 5 C and 10 C (1 C=180 mA g-1 ). We also demonstrate high-performance fast-charging sodium-ion batteries using I-PAN anodes.

Post-synthetic Fully π-Conjugated Three-Dimensional Covalent Organic Frameworks for High-Performance Lithium Storage.

A fully π-conjugated nitrogen-rich three-dimensional covalent organic framework (PYTRI-COF-2) containing both pyrazine and triazine units was prepared through a post-synthetic strategy. The imine linkages in the pre-prepared PYTRI-COF-1 were converted into heterocyclic quinoline by the Povarov reaction. The obtained PYTRI-COF-2 displayed high Li-ion storage capacity and excellent cycling stability when it was used as the lithium (Li)-ion battery electrode.

Fast-Charging Strategies for Lithium-Ion Batteries: Advances and Perspectives.

Rapid development of high-energy-density lithium-ion batteries (LIBs) enables the sufficient driving range of electric vehicles (EVs). However, the slow charging speed restricts the popularization of EVs. Commitment to fast-charging research is considered to be the key to advance the EVs strategy. This Review discusses the kinetic factors limiting the fast-charging capability at the material aspects, and summarizes the recent research strategies to achieve fast-charging performance of high-energy-density LIBs through electrode engineering, electrolyte design, and interface optimization. The increasingly important role of computational tools and advanced characterization techniques in fundamentally understanding the failure mechanism of LIBs is emphasized, and the analysis of the thermal runaway problem in the fast-charging process and the corresponding thermal optimization scheme is also involved to give the guidance for the more rational battery design. In view of these factors and strategies, some future perspectives for realizing high-performance fast-charging LIBs are proposed, which are expected to facilitate the large-scale application of fast-charging LIBs in EVs.