A 3D Lithiophilic Host for Dendrite-Free Lithium Metal Anode via One-Step Carbonization of an Energetic Metal-Organic Framework.

Low Coulombic efficiency (CE) and safety issues are huge problems that hinder the practical application of Li metal anodes. Constructing Li host structures decorated with functional species can restrain the growth of Li dendrites and alleviate the great volume change. Here, a 3D porous carbonaceous skeleton modified with rich lithiophilic groups (Zn, ZnO, and Zn(CN)2 ) is synthesized as a Li host via one-step carbonization of a triazole-containing metal-organic framework. The nano lithiophilic groups serve as preferred sites for Li nucleation and growth, regulating a uniform Li+ flux and uniform current density distribution. In addition, the 3D porous network functions as a Li reservoir that provides rich internal space to store Li, thus alleviating the volumetric expansion during Li plating/stripping process. Thanks to these component and structural merits, an ultra-low overpotential for Li deposition is achieved, together with high CE of over 99.5% for more than 500 cycles at 1 mA cm-2 and 1 mAh cm-2 in half cells. The symmetric cells exhibit a prolonged cycling of 900 h at 1 mA cm-2 . The full cells by coupling Zn/ZnO/Zn(CN)2 @C-Li anode with LiFePO4 cathode deliver a high capacity retention of 94.3% after 200 cycles at 1 C.

Built-In Stable Lithiophilic Sites in 3D Current Collectors for Dendrite Free Li Metal Electrode.

Stable lithiophilic sites in 3D current collectors are the key to guiding the uniform Li deposition and thus suppressing the Li dendrite growth, but such sites created by the conventional surface decoration method are easy to be consumed along with cycling. In this work, carbon fiber (CF)-based 3D porous networks with built-in lithiophilic sites that are stable upon cycling are demonstrated. Such heterostructured architecture is constructed by the introduction of zeolitic imidazolate framework-8-based nanoparticles during the formation of the 3D fibrous carbonaceous network and the following annealing. The introduced Zn species are found to be re-distributed along the entire individual CF in the 3D network, and function as lithiophilic sites that favor the homogenous lithium nucleation and growth. The 3D network also presents a multi-scale porous structure that improves the space utilization of the host. The corresponding symmetric cells adopting such 3D anode demonstrate excellent cycling performance, especially at a high rate (300 cycles at 10 mA cm-2 with a capacity of 5 mA h cm-2 ). A full cell with LiFePO4 cathode shows a capacity retention of 98% after cycling at 1C for 300 cycles. This method provides an effective design strategy for 3D hosting electrodes in dendrite-free alkali metal anode applications.

Self-Healing Nucleation Seeds Induced Long-Term Dendrite-Free Lithium Metal Anode.

Seeded lithium (Li) nucleation has been considered as a promising strategy to achieve uniform Li deposition. However, problems of agglomeration and pulverization quickly invalidate the nucleation seeds, resulting in Li dendrite growth during repeated charge/discharge processes. Herein, liquid gallium-indium (GaIn) nanoparticles with structural self-healing properties are utilized to guide uniform metallic Li nucleation and deposition. Ultrafine GaIn nanoparticles (∼25 nm) uniformly decorated on the surface of carbon layers effectively homogenize the lithium-ion flux. After fully Li stripping, lithiophilic GaIn nanoparticles return to the liquid binary eutectic phase, thereby healing the deformed structure and enabling them to continuously guide dendrite-free Li deposition. Li metal anodes with such nucleation seeds exhibit nearly zero nucleation overpotential even after hundreds of cycles and a high average Coulombic efficiency of 99.03% for more than 400 cycles. The design of self-healing nucleation seeds provides important insights for obtaining high-performance lithium metal anodes.

Nitrogen-Doped Amorphous Zn-Carbon Multichannel Fibers for Stable Lithium Metal Anodes.

The application of lithium metal anodes for practical batteries is still impeded by safety issues and low Coulombic efficiency caused mainly by the uncontrollable growth of lithium dendrites. Herein, two types of free-standing nitrogen-doped amorphous Zn-carbon multichannel fibers are synthesized as multifunctional hosts for lithium accommodation. The 3D macroporous structures endow effectively reduced local current density, and the lithiophilic nitrogen-doped carbon and functional Zn nanoparticles serve as preferred deposition sites with low nucleation barriers to guide uniform lithium deposition. As a result, the developed anodes exhibit remarkable electrochemical properties in terms of high Coulombic efficiency for more than 500 cycles at various current densities from 1 to 5 mA cm-2 , and symmetric cells show long-term cycling duration over 2000 h. Moreover, full cells based on the developed anode and a LiFePO4 cathode also demonstrate superior rate capability and stable cycle life.

MXene Aerogel Scaffolds for High-Rate Lithium Metal Anodes.

Li metal is considered to be an ultimate anode for metal batteries owing to its extremely high theoretical capacity and lowest potential. However, numerous issues such as short lifespan and infinite volume expansion caused by the dendrite growth during Li plating/stripping hinder its practical usage. These challenges become more grievous under high current densities. Herein, 3D porous MXene aerogels are proposed as scaffolds for high-rate Li metal anodes using Ti3 C2 as an example. With high metallic electron conductivity, fast Li ion transport capability, and abundant Li nucleation sites, such scaffolds could deliver high cycling stability and low overpotential at current density up to 10 mA cm-2 . High rate performance is also demonstrated in full cells with LiFePO4 as cathodes. This work provides a new type of scaffolds for Li metal anodes and paves the way for the application of non-graphene 2D materials toward high energy density Li metal batteries.

A Stable Lithium Metal Anode Enabled by the Site-Directed Lithium Deposition of ZnO-Nanosheet-Modified Carbon Cloth.

Uneven lithium (Li) metal deposition typically results in uncontrollable dendrite growth, which renders an unsatisfactory cycling stability and coulombic efficiency (CE) of Li metal batteries (LMBs), preventing their practical application. Herein, a novel carbon cloth with the modification of ZnO nanosheets (ZnO@CC) is fabricated for LMBs. The as-prepared ZnO@CC with a cross-linked network significantly reduces the local current density, and the design of ZnO nanosheets can promote the uniform deposition of Li metal as lithiophilic sites. As a result, the Li metal anodes (LMAs) based on ZnO@CC (ZnO@CC@Li) enables a long cycle life over 640 hours with a low overpotential of 65 mV at a current density of 4 mA cm-2 with a capacity of 1 mAh cm-2 in the symmetric cell. Moreover, when coupling the ZnO@CC@Li with a LiFePO4 cathode, the assembled full cell exhibits excellent long cycle and rate performance, highlighting its promising practical application prospect.

Regulation of Dendrite-Free Li Plating via Lithiophilic Sites on Lithium-Alloy Surface.

Lithium (Li) deposition behavior plays an important role in dendrite formation and the subsequent performance of lithium metal batteries. This work reveals the impact of the lithiophilic sites of lithium-alloy on the Li plating process via the first-principles calculations. We find that the Li deposition mechanisms on the Li metal and Li22Sn5 surface are different due to the lithiophilic sites. We first propose that Li plating on the Li metal surface goes through the "adsorption-reduction-desorption-heterogeneous nucleation-cluster drop" process, while it undergoes the "adsorption-reduction-growth" process on the Li22Sn5 surface. The lower adsorption energy contributes to the easy adsorption of Li on the lithiophilic sites of the Li22Sn5 surface. The lower Li reduction energy on the Li metal surface indicates that it is easy for Li to be reduced on the Li metal surface, attributed to its higher Fermi energy level. Furthermore, the faster Li diffusion on the Li22Sn5 surface results in smooth Li deposition, which is based on a "two-Li synergy diffusion" mechanism. However, Li diffuses more slowly on the Li metal surface than on the Li22Sn5 surface due to the "single Li diffusion" mechanism. This work provides a fundamental understanding on the impact of lithiophilic sites of Li alloy on the Li plating process and points out that the future design of 3D Li-alloy substrates decorated with multilithiophilic sites can prevent dendrite formation on the lithium-alloy substrate by guiding uniform Li deposition.

Facile Replacement Reaction Enables Nano-Ag-Decorated Three-Dimensional Cu Foam as High-Rate Lithium Metal Anode.

In developing advanced lithium (Li) metal batteries with high-energy density, excellent cycle stability, and high-rate capability, it is imperative to resolve dendrite growth and volume expansion during repeated Li plating/stripping. 3D hosts featuring lithiophilic sites are expected to realize both spatial control and dendrite inhibition over Li nucleation. Herein, this work prepares silver (Ag) nanoparticle-decorated 3D copper (Cu) foam via a facile replacement reaction. The 3D host provides rigid skeleton to accommodate volume expansion during cycling. Ag nanoparticles show micro-structural affinity to guide efficient nucleation of Li, leading to reduced overpotential and enhanced electrochemical kinetics. As the result, under an ultrahigh current density of 10 mA cm-2, Cu@Ag foam/Li half cells demonstrate outstanding Coulombic efficiency (CE) of 97.2% more than 100 cycles. Also, Cu@Ag foam-Li symmetric cells sustain preeminent cycling over 900 h with a small voltage hysteresis of 32.8 mV at 3 mA cm-2. Moreover, the Cu@Ag foam-Li||LiFePO4 full cell demonstrates a high discharge capacity of 2.33 mAh cm-2 over 200 cycles with an excellent CE up to 99.9% at 0.6C under practical conditions (N/P = 1.3, 17.4 mg cm-2 LiFePO4). Notably, the full cell with LiFePO4 exhibits a higher areal capacity of 1 mAh cm-2 over 700 cycles under a high rate of 5C, corresponding to capacity retention up to 100% (N/P = 3, 17.4 mg cm-2 LiFePO4). This study provides a novel and simple strategy for constructing high-rate and long-life Li metal batteries.

Single-Atom Iron as Lithiophilic Site To Minimize Lithium Nucleation Overpotential for Stable Lithium Metal Full Battery.

High lithium nucleation overpotential on a lithiophobic matrix results in uncontrollable growth of lithium dendrites and thus restricts the wide application of lithium-metal batteries. Herein, the single-atom iron in a N-doped carbon matrix (FeSA-N-C) is first reported as a lithiophilic site to minimize Li nucleation overpotential from 18.6 mV to a very low value of 0.8 mV. Molecular dynamics simulations quantitatively confirmed the excellent affinity between Li ions and FeSA-N-C in the atomic level. Induced by the homogeneously distributed FeSA-N in the carbon substrate, uniform and stable metallic Li plating/stripping behaviors are realized and lithium dendrite growth is greatly suppressed. The proposed strategy of using single-atom iron as a lithiophilic site to minimize lithium nucleation overpotential opens a promising avenue for solving intrinsic problems of Li-metal-based batteries.