Lightweight 3D Lithiophilic Graphene Aerogel Current Collectors for Lithium Metal Anodes.

Constructing three-dimensional (3D) current collectors is an effective strategy to solve the hindrance of the development of lithium metal anodes (LMAs). However, the excessive mass of the metallic scaffold structure leads to a decrease in energy density. Herein, lithiophilic graphene aerogels comprising reduced graphene oxide aerogels and silver nanowires (rGO-AgNW) are synthesized through chemical reduction and freeze-drying techniques. The rGO aerogels with large specific surface areas effectively mitigate local current density and delay the formation of lithium dendrites, and the lithiophilic silver nanowires can provide sites for the uniform deposition of lithium. The rGO-AgNW/Li symmetric cell presents a stable cycle of about 2000 h at 1 mA cm-2. When coupled with the LiFePO4 cathode, the assembled full cells exhibit outstanding cycle stability and rate performance. Lightweight rGO-AgNW aerogels, as the host for lithium metal, can significantly improve the energy density of lithium metal anodes.

In Situ Formed Tribofilms as Efficient Organic/Inorganic Hybrid Interlayers for Stabilizing Lithium Metal Anodes.

The practical application of Li metal anodes (LMAs) is limited by uncontrolled dendrite growth and side reactions. Herein, we propose a new friction-induced strategy to produce high-performance thin Li anode (Li@CFO). By virtue of the in situ friction reaction between fluoropolymer grease and Li strips during rolling, a robust organic/inorganic hybrid interlayer (lithiophilic LiF/LiC6 framework hybridized -CF2-O-CF2- chains) was formed atop Li metal. The derived interface contributes to reversible Li plating/stripping behaviors by mitigating side reactions and decreasing the solvation degree at the interface. The Li@CFO||Li@CFO symmetrical cell exhibits a remarkable lifespan for 5,600 h (1.0 mA cm-2 and 1.0 mAh cm-2) and 1,350 cycles even at a harsh condition (18.0 mA cm-2 and 3.0 mAh cm-2). When paired with high-loading LiFePO4 cathodes, the full cell lasts over 450 cycles at 1C with a high-capacity retention of 99.9%. This work provides a new friction-induced strategy for producing high-performance thin LMAs.

Stabilizing Lithium Metal Batteries by Synergistic Effect of High Ionic Transfer Separator and Lithium-Boron Composite Material Anode.

The development of lithium (Li) metal batteries (LMBs) has been limited by problems, such as severe dendrite growth, drastic interfacial reactions, and large volume change. Herein, an LMB (8AP@LiB) combining agraphene oxide-poly(ethylene oxide) (PEO) functionalized polypropylene separator (8AP) with a lithium-boron (LiB) anode is designed to overcome these problems. Raman results demonstrate that the PEO chain on 8AP can influence the Li+ solvation structure in the electrolyte, resulting in Li+ homogeneous diffusion and Li+ deposition barrier reduction. 8AP exhibits good ionic conductivity (4.9 × 10-4 S cm-1), a high Li+ migration number (0.88), and a significant electrolyte uptake (293%). The 3D LiB skeleton can significantly reduce the anode volume changes and local current density during the charging/discharging process. Therefore, 8AP@LiB effectively regulates the Li+ flux and promotes the uniform Li deposition without dendrites. The Li||Li symmetrical cells of 8AP@LiB exhibit a high electrochemical stability of up to 1000 h at 1 mA cm-2 and 5 mAh cm-2. Importantly, the Li||LiFePO4 full cells of 8AP@LiB achieve an impressive 2000 cycles at 2C, while maintaining a high-capacity retention of 86%. The synergistic effect of the functionalized separator and LiB anode might provide a direction for the development of high-performance LMBs.

Interfacial friction enabling ≤ 20 µm thin free-standing lithium strips for lithium metal batteries.

A practical high-specific-energy Li metal battery requires thin (≤20 µm) and free-standing Li metal anodes, but the low melting point and strong diffusion creep of lithium metal impede their scalable processing towards thin-thickness and free-standing architecture. In this paper, thin (5 to 50 µm) and free-standing lithium strips were achieved by mechanical rolling, which is determined by the in situ tribochemical reaction between lithium and zinc dialkyldithiophosphate (ZDDP). A friction-induced organic/inorganic hybrid interface (~450 nm) was formed on Li with an ultra-high hardness (0.84 GPa) and Young's modulus (25.90 GPa), which not only enables the scalable process mechanics of thin lithium strips but also facilitates dendrite-free lithium metal anodes by inhibiting dendrite growth. The rolled lithium anode exhibits a prolonged cycle lifespan and high-rate cycle stability (in excess of more than 1700 cycles even at 18.0 mA cm-2 and 1.5 mA cm-2 at 25 °C). Meanwhile, the LiFePO4 (with single-sided load 10 mg/cm2) ||Li@ZDDP full cell can last over 350 cycles with a high-capacity retention of 82% after the formation cycles at 5 C (1 C = 170 mA/g) and 25 °C. This work provides a scalable approach concerning tribology design for producing practical thin free-standing lithium metal anodes.

Reactive Polymer as Artificial Solid Electrolyte Interface for Stable Lithium Metal Batteries.

Lithium (Li) metal anodes have the highest theoretical capacity and lowest electrochemical potential making them ideal for Li metal batteries (LMBs). However, Li dendrite formation on the anode impedes the proper discharge capacity and practical cycle life of LMBs, particularly in carbonate electrolytes. Herein, we developed a reactive alternative polymer named P(St-MaI) containing carboxylic acid and cyclic ether moieties which would in situ form artificial polymeric solid electrolyte interface (SEI) with Li. This SEI can accommodate volume changes and maintain good interfacial contact. The presence of carboxylic acid and cyclic ether pendant groups greatly contribute to the induction of uniform Li ion deposition. In addition, the presence of benzyl rings makes the polymer have a certain mechanical strength and plays a key role in inhibiting the growth of Li dendrites. As a result, the symmetric Li||Li cell with P(St-MaI)@Li layer can stably cycle for over 900 h under 1 mA cm-2 without polarization voltage increasing, while their Li||LiFePO4 full batteries maintain high capacity retention of 96 % after 930 cycles at 1C in carbonate electrolytes. The innovative strategy of artificial SEI is broadly applicable in designing new materials to inhibit Li dendrite growth on Li metal anodes.

Highly Reversible Lithium Metal Anode Enabled by 3D Lithiophilic-Lithiophobic Dual-Skeletons.

Lithium metal is a promising anode for high-energy-density lithium batteries, but its practical application is still hindered by intrinsic defects such as infinite volume expansion and uncontrollable dendrite growth. Herein, a dendrite-free 3D composite Li anode (Li-B@SSM) is prepared by mechanical rolling of lithiophilic LiB nanofibers supported by Li-B composite and lithiophobic stainless-steel mesh (SSM). Featuring hierarchical lithiophilic-lithiophobic dual-skeletons, the Li-B@SSM anode shows an ultrahigh Coulombic efficiency of 99.95% and a long lifespan of 900 h under 2 mA cm-2 /1 mAh cm-2 . It is demonstrated that the abnormally reversible Li stripping/plating processes should be closely related to the site-selective plating behavior and spatial confinement effect induced by the robust lithiophilic-lithiophobic dual-skeletons, which alleviates the volume changes, suppresses the growth of Li dendrites, and reduces the accumulation of "dead" Li. More importantly, the application feasibility of the Li-B@SSM anode is also confirmed in full batteries, of which the Li-B@SSM|LiFePO4 full cell shows a high capacity retention of 97.5% after 400 cycles while the Li-B@SSM|S pouch battery exhibits good cycle stability even under practically harsh conditions. This work paves the way for the facile and efficient fabrication of high-efficiency Li metal anodes toward practical applications.

Mg Doped Li-LiB Alloy with In Situ Formed Lithiophilic LiB Skeleton for Lithium Metal Batteries.

High energy density lithium metal batteries (LMBs) are promising next-generation energy storage devices. However, the uncontrollable dendrite growth and huge volume change limit their practical applications. Here, a new Mg doped Li-LiB alloy with in situ formed lithiophilic 3D LiB skeleton (hereinafter called Li-B-Mg composite) is presented to suppress Li dendrite and mitigate volume change. The LiB skeleton exhibits superior lithiophilic and conductive characteristics, which contributes to the reduction of the local current density and homogenization of incoming Li+ flux. With the introduction of Mg, the composite achieves an ultralong lithium deposition/dissolution lifespan (500 h, at 0.5 mA cm-2) without short circuit in the symmetrical battery. In addition, the electrochemical performance is superior in full batteries assembled with LiCoO2 cathode and the manufactured composite. The currently proposed 3D Li-B-Mg composite anode may significantly propel the advancement of LMB technology from laboratory research to industrial commercialization.