Graphene-Enabled Electric-Field Regulation and Ionic Redistribution Around Lithiophilic Aurum Nanoparticles Toward a Dendrite-Free and 2000-Cycle-Life Lithium Metal Battery

Lithium metal batteries (LMBs) have attracted extensive attention owing to their high energy density. However, the uncontrolled volume changes and serious dendrite growth of the Li metal anode have hindered their commercialization. Herein, a three-dimensional Cu foam decorated with Au nanoparticles and conformal graphene layer was designed to tune the Li plating/stripping behaviors. The 3D−Cu conductive host anchored by lithiophilic Au nanoparticles can effectively alleviate the volume expansion caused by the continuous plating/stripping of Li and reduce the nucleation energy barrier. Notably, the conductive graphene not only facilitates the transfer of electrons, but also acts as an ionic rectifier, thereby avoiding the aggregation of local current density and Li⁺ ions around Au nanoparticles and enabling the uniform Li⁺ flux. As a result, the G−Au@3D−Cu/Li anode ensures the non-dendritic and homogeneous Li⁺ plating/stripping. Electrochemical results show that the symmetric G−Au@3D−Cu/Li cell delivers a low voltage hysteresis of 110 mV after 1000 h at 1 mA cm⁻². Matched with a layered LiNi_0.6Co_0.2Mn_0.2O₂ cathode, the NCM622||G−Au@3D−Cu/Li full cell exhibits a long cycle life of 2000 cycles and an ultra-low capacity decay rate (0.01 % per cycle).     

锂金属负极亲锂骨架的研究进展

随着电动汽车和便携式电子产品的快速发展, 人们对于高比能二次电池的需求越来越迫切. 锂金属以其极高的理论比容量和极低的电极电势被视为下一代高比能电池理想负极材料之一. 但是, 锂枝晶的生长及体积膨胀等问题限制了金属锂负极的实际应用. 在金属锂负极中引入三维骨架可以有效抑制锂枝晶生长, 缓解体积膨胀. 其中亲锂骨架可以降低锂的形核能垒, 诱导锂的均匀成核, 更加有效地调控锂沉积行为. 本文结合国内外的研究进展总结了锂金属负极中亲锂骨架的研究成果. 根据亲锂材料的不同对亲锂骨架进行了分类, 总结了各类亲锂骨架在调控锂沉积行为和提高电池性能方面取得的成果, 并对其今后的研究和发展进行了展望.     

Lithiophilic Sites in Doped Graphene Guide Uniform Lithium Nucleation for Dendrite-Free Lithium Metal Anodes

Lithium (Li) metal is the most promising electrode for next-generation rechargeable batteries. However, the challenges induced by Li dendrites on a working Li metal anode hinder the practical applications of Li metal batteries. Herein, nitrogen (N) doped graphene was adopted as the Li plating matrix to regulate Li metal nucleation and suppress dendrite growth. The N-containing functional groups, such as pyridinic and pyrrolic nitrogen in the N-doped graphene, are lithiophilic, which guide the metallic Li nucleation causing the metal to distribute uniformly on the anode surface. As a result, the N-doped graphene modified Li metal anode exhibits a dendrite-free morphology during repeated Li plating and demonstrates a high Coulombic efficiency of 98 % for near 200 cycles.     

Lithiophilic Sites in Doped Graphene Guide Uniform Lithium Nucleation for Dendrite‐Free Lithium Metal Anodes

Lithium (Li) metal is the most promising electrode for next‐generation rechargeable batteries. However, the challenges induced by Li dendrites on a working Li metal anode hinder the practical applications of Li metal batteries. Herein, nitrogen (N) doped graphene was adopted as the Li plating matrix to regulate Li metal nucleation and suppress dendrite growth. The N‐containing functional groups, such as pyridinic and pyrrolic nitrogen in the N‐doped graphene, are lithiophilic, which guide the metallic Li nucleation causing the metal to distribute uniformly on the anode surface. As a result, the N‐doped graphene modified Li metal anode exhibits a dendrite‐free morphology during repeated Li plating and demonstrates a high Coulombic efficiency of 98 % for near 200 cycles.     

A 3D conducting scaffold with in-situ grown lithiophilic Ni_2P nanoarrays for high stability lithium metal anodes

Lithium(Li)metal is the most potential anode material for the next-generation high-energy rechargeable batteries.However,intrinsic surface unevenness and‘hostless’nature of Li metal induces infinite volume effect and uncontrollable dendrite growth.Herein,we design the in-situ grown lithiophilic Ni₂P nanoarrays inside nickel foam(PNF).Uniform Ni₂P nanoarrays coating presents a very low nucleation overpotential,which induces the homogeneous Li deposition in the entire spaces of three-dimensional(3D)metal framework.Specifically,the lithiophilic Ni₂P nanoarrays possess characteristics of electrical conductivity and structural stability,which have almost no expansion and damage during repeating Li plating/stripping.Therefore,they chronically inhibit the growth of Li dendrites.This results in an outstanding Coulombic efficiency(CE)of 98% at 3 mA cm^-2 and an ultra long cycling life over 2000 cycles with a low overpotential.Consequently,the PNF-Li||LiFePO₄ battery maintains a capacity retention of 95.3% with a stable CE of 99.9% over 500 cycles at 2 C.     

Three-Dimensional Graphene/Ag Aerogel for Durable and Stable Li Metal Anodes in Carbonate-Based Electrolytes

The use of Li metal as the anode for Li-based batteries has attracted considerable attention due to its ultrahigh energy density. However, the formation of Li dendrites, uneven deposition, and huge volume changes hinder its reliable implementation. These issues become much more severe in commercial carbonate-based electrolytes than in ether-based electrolytes. Herein, a rationally designed three-dimensional graphene/Ag aerogel (3D G-Ag aerogel) is proposed for Li metal anodes with long cycle life in carbonate-based electrolytes. The modified lithiophilic nature of G-Ag aerogel, realized through decoration with Ag NPs, effectively decreases the energy barrier for Li nucleation, regulating uniform Li deposition behavior. Moreover, the highly flexible, conductive 3D porous architecture with hierarchical mesopores and macropores can readily accommodate deposited Li and ensures the integrity of the conductive network during cycling. Consequently, high coulombic efficiency (over 93.5 %) and a significantly long cycle life (1589 h) over 200 cycles, with a relatively high cycling capacity of 2.0 mAh cm⁻², can easily be achieved, even in a carbonate-based electrolyte. Considering the intrinsic high voltage windows of carbonate-based electrolytes, matching the G-Ag aerogel Li metal anode with a high-voltage cathode can be envisaged for the fabrication of high-energy-density Li secondary batteries.     

石墨烯负载的氧配位钴单原子稳定金属锂负极

Lithium (Li)-based batteries are the dominant energy source for consumer electronics, grid storage, and electrified transportation. However, the development of batteries based on graphite anodes is hindered by their limited energy density. With its ultrahigh theoretical capacity (3860 mAh∙g⁻¹), low redox potential (−3.04 V), and satisfactorily low density (0.54 g∙cm⁻³), Li metal is the most promising anode for next-generation high-energy-density batteries. Unfortunately, the limited cycling life and safety issues raised by dendrite growth, unstable solid electrolyte interphase, and "dead Li" have inhibited their practical use. An effective strategy is to develop a suitable lithiophilic matrix for regulating initial Li nucleation behavior and controlling subsequent Li growth. Herein, single-atom cobalt coordinated to oxygen sites on graphene (Co-O-G SA) is demonstrated as a Li plating substrate to efficiently regulate Li metal nucleation and growth. Owing to its dense and more uniform lithiophilic sites than single-atom cobalt coordinated to nitrogen sites on graphene (Co-N-G SA), high electronic conductivity, and high specific surface area (519 m²∙g⁻¹), Co-O-G SA could significantly reduce the local current density and promote the reversibility of Li plating and stripping. As a result, the Co-O-G SA based Li anodes exhibited a high Coulombic efficiency of 99.9% at a current density of 1 mA∙cm⁻² with a capacity of 1 mAh∙cm⁻², and excellent rate capability (high current density of 8 mA∙cm⁻²). Even at a high plating capacity of 6 mAh∙cm⁻², the Co-O-G SA electrode could stably cycle for an ultralong lifespan of 1300 h. In the symmetric battery, the Co-O-G SA based Li anode (Co-O-G SA/Li) possessed a stable voltage profile of 18 mV for 780 h at 1 mA∙cm⁻², and even at a high current density of 3 mA∙cm⁻², its overpotential maintained a small hysteresis of approximately 24 mV for > 550 h. Density functional theory calculations showed that the surface of Co-O-G SA had a stronger interaction with Li atoms with a larger binding energy, −3.1 eV, than that of Co-N-G SA (−2.5 eV), leading to a uniform distribution of metallic Li on the Co-O-G SA surface. More importantly, when matched with a sulfur cathode, the resulting Co-O-G SA/lithium sulfur full batteries exhibited a high capacity of 1002 mAh∙g⁻¹, improved kinetics with a small polarization of 191 mV, and an ultralow capacity decay rate of 0.036% per cycle for 1000 cycles at 0.5C (1C = 1675 mA∙g⁻¹) with a steady Coulombic efficiency of nearly 100%. Therefore, this work provides novel insights into the coordination environment of single atoms for the chemistry of Li metal anodes for high-energy-density batteries.     

轻质三维多孔泡沫铝用作高性能锂金属负极骨架

将轻质、三维多孔且亲锂的泡沫铝用作锂(Li)金属负极骨架,通过简单的机械挤压方法,将泡沫铝与金属Li复合,制得Al@Li复合负极。泡沫铝自身的高亲锂性,能够为Li金属成核提供丰富且均匀的活性位点,诱导Li在泡沫铝内部的快速成核和均匀电沉积。同时,泡沫铝的三维多孔结构,可以容纳Li金属负极在充放电过程中的巨大体积应变,降低局部电流密度,从而有效抑制Li枝晶的生长。因此,与纯Li金属负极相比,所获得的Al@Li复合负极在对称电池和LiFePO₄||Al@Li半电池中,均表现出了更加优异的循环稳定性。     

轻质三维多孔泡沫铝用作高性能锂金属负极骨架

将轻质、三维多孔且亲锂的泡沫铝用作锂(Li)金属负极骨架,通过简单的机械挤压方法,将泡沫铝与金属 Li复合,制得Al@Li复合负极。泡沫铝自身的高亲锂性,能够为Li金属成核提供丰富且均匀的活性位点,诱导Li在泡沫铝内部的快速成核和均匀电沉积。同时,泡沫铝的三维多孔结构,可以容纳Li金属负极在充放电过程中的巨大体积应变,降低局部电流密度,从而有效抑制Li枝晶的生长。因此,与纯Li金属负极相比,所获得的Al@Li复合负极在对称电池和LiFePO₄||Al@Li半电池中,均表现出了更加优异的循环稳定性。     

亲锂的三维二硫化锡@碳纤维布用于稳定的锂金属负极

金属锂由于其高的比容量,低的电极电势和轻质等特点被认为是下一代高能量密度锂金属二次电池负极材料的最佳选择。然而,充放电循环中不均匀的锂沉积会导致严重的体积变化和大量的锂枝晶形成,从而影响了电池的库伦效率甚至会带来严重的安全隐患。为此,本文设计了一种亲锂的三维二硫化锡@碳纤维布复合基底材料,并作为集流体将其应用于金属锂电池上。一者,高比表面积的三维碳纤维骨架可以适应充放电过程中的体积变化并且有效地降低局部电流密度,从而确保锂的均匀沉积。二者,表面修饰的SnS2层在锂沉积过程中可以形成Li-Sn合金界面层,诱导锂的沉积并降低过电势。最终,实验结果表明:使用所制备的复合集流体与金属锂搭配组成的半电池可以在5 mA·cm^-2的高电流密度下以>98%的库伦效率稳定循环100周以上。此外,在承载10 mAh·cm^-2的金属锂后,复合的锂负极无论是在对称电池还是与磷酸铁锂组装成的实际电池中,均可以在高的电流密度下实现稳定的循环。我们相信这一复合的集流体构建策略对于设计安全稳定的锂金属电池或器件具有重要意义。     

Active‐Oxygen‐Enhanced Homogeneous Nucleation of Lithium Metal on Ultrathin Layered Double Hydroxide

The development of safe lithium‐metal anodes is crucial for the next‐generation rechargeable batteries. To stabilize Li metal anodes, pre‐planting Li nucleation seeds on lithiophilic substrates is an efficient strategy to regulate initial nucleation process of Li metal. Now, activated ultrathin layered double hydroxide (U‐LDHs) are reported as a promising lithiophilic 2D material to realize the uniform deposition of Li metal. The experimental studies and DFT calculations reveal that the active oxygen on U‐LDHs provides abundant atomic‐scale active sites for Li homogeneous nucleation and plating. Moreover, the lithiophilic properties of active oxygen is also related to its coordination environments. This work opens up an opportunity to more accurate regulation and understanding of Li nucleation from atomic‐scale based on 2D ultrathin materials.     

Catalytic Chemistry Derived Artificial Solid Electrolyte Interphase for Stable Lithium Metal Anodes Working at 20 mA cm−2 and 20 mAh cm−2

A stable solid electrolyte interphase (SEI) layer is crucial for lithium metal anode (LMA) to survive in long-term cycling. However, chaotic structures and chemical inhomogeneity of natural SEI make LMA suffering from exasperating dendrite growth and severe electrode pulverization, which hinder the practical application of LMAs. Here, we design a catalyst-derived artificial SEI layer with an ordered polyamide-lithium hydroxide (PA-LiOH) bi-phase structure to modulate ion transport and enable dendrite-free Li deposition. The PA-LiOH layer can substantially suppress the volume changes of LMA during Li plating/stripping cycles, as well as alleviate the parasitic reactions between LMA and electrolyte. The optimized LMAs demonstrate excellent stability in Li plating/stripping cycles for over 1000 hours at an ultra-high current density of 20 mA cm⁻² in Li||Li symmetric cells. A high coulombic efficiency up to 99.2 % in Li half cells in additive-free electrolytes is achieved even after 500 cycles at a current density of 1 mA cm⁻² with a capacity of 1 mAh cm⁻².     

细菌纤维素衍生的三维碳集流体用于无枝晶的锂金属负极

锂金属是下一代高能量密度电池的关键负极,然而其实用化面临着一系列问题,主要包括循环过程中体积变化大、枝晶生长等。使用三维集流体是解决这些问题的有效方法,然而现有大多数三维集流体存在重量大、体积大、表面亲锂性差、成本高等问题。针对上述问题,本文以低成本的细菌纤维素为前驱体,通过直接碳化制备出具有连通网络的轻质三维碳集流体,其表面均匀分布的含氧官能团可以促进锂离子的均匀成核和沉积,有效抑制了枝晶生长。值得注意的是,该集流体的面密度仅为0.32 mg·cm^?2,在3 mAh·cm^?2比容量的锂金属负极中质量占比仅为28.8%。电化学测试结果表明,该集流体在3 mA·cm^?2的高电流密度或4 mAh·cm^?2的高循环容量的工作条件下,稳定循环超过150次,并且在对称电池或与LiNi0.8Co0.15Al0.05匹配的全电池中也表现出良好的电化学性能。     

A Full Li–S Battery with Ultralow Excessive Li Enabled via Lithiophilic and Sulfilic W2C Modulation

The practical application of Li–S batteries demands low cell balance (Li_capacity/S_capacity), which involves uniform Li growth, restrained shuttle effect, and fast redox reaction kinetics of S species simultaneously. Herein, with the aid of W₂C nanocrystals, a freestanding 3D current collector is applied as both Li and S hosts owing to its lithiophilic and sulfilic property. On the one hand, the highly conductive W₂C can reduce Li nucleation overpotentials, thus guiding uniform Li nucleation and deposition to suppress Li dendrite growth. On the other hand, the polar W₂C with catalytic effect can enhance the chemisorption affinity to lithium polysulfides (LiPSs) and guarantee fast redox kinetics to restrain S species in cathode region and promote the utilization of S. Surprisingly, a full Li–S battery with ultralow cell balance of 1.5:1 and high sulfur loading of 6.06 mg cm⁻² shows obvious redox plateaus of S and maintains high reversible specific capacity of 1020 mAh g⁻¹ (6.2 mAh cm⁻²) after 200 cycles. This work may shed new sights on the facile design of full Li–S battery with low excessive Li supply.     

担载纳米硅的锂-碳复合微球作为锂二次电池负极

金属锂由于其极高的理论比容量(3860mAh·g~(-1),2061mAh·cm~(-3))和低的还原电势(相对于标准氢电极(SHE)为-3.04 V)等特点,成为了高能量密度锂电池负极材料的极佳选择之一。从上个世纪七十年代开始,科研工作者便开始了金属锂负极的研究,然而,由于金属锂与电解液反应严重,镀锂过程体积膨胀大,且在循环中易生成枝晶,以金属锂为负极的电池循环稳定性差,而且容易短路从而带来安全隐患。因此金属锂做为锂电池负极的商业化推广最终没有成功。在本工作中,我们在前期设计的锂-碳纳米管复合微球(Li-CNT)中引入了纳米硅颗粒制备了硅颗粒担载的锂-碳复合球(LiCNT-Si)。实验发现,纳米硅颗粒的加入不仅提高了锂-碳复合微球的载锂量(10%(质量百分含量)的硅添加量使得比容量从2000 mAh·g~(-1)提高到2600 mAh·g~(-1)),降低了锂的沉积/溶解过电势,有利于引导锂离子回到复合微球内部沉积,大大提高了材料的循环稳定性。同时,担载了纳米硅颗粒的锂-碳复合球也继承了锂-碳复合微球循环过程中体积膨胀小,不长枝晶的优点。而且添加的纳米硅颗粒还填充了Li-CNT微球中的孔隙,减少了电解液渗入复合微球内部腐蚀里面的金属锂,进一步提高了材料的库仑效率。以添加10%硅的锂碳复合材料作为负极,与商用磷酸铁锂正极组成全电池,在常规酯类电解液中1C (0.7 mA·cm~(-2))条件下能稳定循环900圈以上,库仑效率为96.7%,大大高于同样条件下测得的Li-CNT复合材料(90.1%)和金属锂片(79.3%)的库仑效率。因此,这种通过简单的熔融浸渍法即可制备的,具有高的比容量和长的循环稳定性的锂硅-碳复合材料具有较大的潜能成为高能量密度电池的负极材料,尤其适用于锂硫、锂氧这种正极不含锂源的电池体系。     

Anode-Free Lithium Metal Batteries Based on an Ultrathin and Respirable Interphase Layer

Anode-free lithium (Li) metal batteries are desirable candidates in pursuit of high-energy-density batteries. However, their poor cycling performances originated from the unsatisfactory reversibility of Li plating/stripping remains a grand challenge. Here we show a facile and scalable approach to produce high-performing anode-free Li metal batteries using a bioinspired and ultrathin (250 nm) interphase layer comprised of triethylamine germanate. The derived tertiary amine and Li_xGe alloy showed enhanced adsorption energy that significantly promoted Li-ion adsorption, nucleation and deposition, contributing to a reversible expansion/shrinkage process upon Li plating/stripping. Impressive Li plating/stripping Coulombic efficiencies (CEs) of ≈99.3 % were achieved for 250 cycles in Li/Cu cells. In addition, the anode-free LiFePO₄ full batteries demonstrated maximal energy and power densities of 527 Wh kg⁻¹ and 1554 W kg⁻¹, respectively, and remarkable cycling stability (over 250 cycles with an average CE of 99.4 %) at a practical areal capacity of ≈3 mAh cm⁻², the highest among state-of-the-art anode-free LiFePO₄ batteries. Our ultrathin and respirable interphase layer presents a promising way to fully unlock large-scale production of anode-free batteries.     

水溶液法原位构建ZnO亲锂层稳定锂-石榴石电解质界面

固态电池以其高安全性和高能量密度而备受关注。石榴石型固体电解质(LLZO)由于具有较高的离子导电性和对锂金属的稳定性,在固态电池中具有应用前景,但陶瓷与锂金属较差的界面接触会导致高的界面阻抗和可能形成的枝晶穿透。我们利用LLZO表层独特的H⁺/Li⁺交换反应,提出了一种简便有效的金属盐类水溶液诱发策略,在电解质表面原位构建ZnO亲锂层,界面处LiZn合金化实现紧密连续的接触。引入改性层后,界面阻抗可显著降低至约10Ω·cm²,对称电池能够在0.1mA·cm^-2的电流密度下实现长达1000h的长循环稳定性。匹配正极LiFePO₄(LFP)或LiNi_0.5Co_0.2Mn_0.3O₂(NCM523)的准固态电池在室温下能够稳定循环100次以上。     

A Two-Dimensional Mesoporous Polypyrrole–Graphene Oxide Heterostructure as a Dual-Functional Ion Redistributor for Dendrite-Free Lithium Metal Anodes

Guiding the lithium ion (Li-ion) transport for homogeneous, dispersive distribution is crucial for dendrite-free Li anodes with high current density and long-term cyclability, but remains challenging for the unavailable well-designed nanostructures. Herein, we propose a two-dimensional (2D) heterostructure composed of defective graphene oxide (GO) clipped on mesoporous polypyrrole (mPPy) as a dual-functional Li-ion redistributor to regulate the stepwise Li-ion distribution and Li deposition for extremely stable, dendrite-free Li anodes. Owing to the synergy between the Li-ion transport nanochannels of mPPy and the Li-ion nanosieves of defective GO, the 2D mPPy-GO heterostructure achieves ultralong cycling stability (1000 cycles), even tests at 0 and 50 °C, and an ultralow overpotential of 70 mV at a high current density of 10.0 mA cm⁻², outperforming most reported Li anodes. Furthermore, mPPy-GO-Li/LiCoO₂ full batteries demonstrate remarkably enhanced performance with a capacity retention of >90 % after 450 cycles. Therefore, this work opens many opportunities for creating 2D heterostructures for high-energy-density Li metal batteries.     

A Two‐Dimensional Mesoporous Polypyrrole–Graphene Oxide Heterostructure as a Dual‐Functional Ion Redistributor for Dendrite‐Free Lithium Metal Anodes

Guiding the lithium ion (Li‐ion) transport for homogeneous, dispersive distribution is crucial for dendrite‐free Li anodes with high current density and long‐term cyclability, but remains challenging for the unavailable well‐designed nanostructures. Herein, we propose a two‐dimensional (2D) heterostructure composed of defective graphene oxide (GO) clipped on mesoporous polypyrrole (mPPy) as a dual‐functional Li‐ion redistributor to regulate the stepwise Li‐ion distribution and Li deposition for extremely stable, dendrite‐free Li anodes. Owing to the synergy between the Li‐ion transport nanochannels of mPPy and the Li‐ion nanosieves of defective GO, the 2D mPPy‐GO heterostructure achieves ultralong cycling stability (1000 cycles), even tests at 0 and 50 °C, and an ultralow overpotential of 70 mV at a high current density of 10.0 mA cm^?2, outperforming most reported Li anodes. Furthermore, mPPy‐GO‐Li/LiCoO₂ full batteries demonstrate remarkably enhanced performance with a capacity retention of >90 % after 450 cycles. Therefore, this work opens many opportunities for creating 2D heterostructures for high‐energy‐density Li metal batteries.     

Normalized Lithium Growth from the Nucleation Stage for Dendrite‐Free Lithium Metal Anodes

Inducing uniform deposition of lithium from the stage of metal crystallization nucleation is of vital importance to achieve dendrite‐free lithium anodes. Herein, using experiments and simulation, homogenization of Li nucleation and normalization of Li growth can be achieved on PNIPAM polymer brushes with lithiophilic functional groups modified Cu substrates. The lithiophilic functional groups of amide O can homogenize ion mass transfer and induce the uniform distribution of Li nucleation sites. What is more, the ultra‐small space between each brush can act as the channels for Li transportation and normalization growth. Owing to the synergistic effect of homogenization and normalization of electrodeposited Li, the obtained planar columnar Li anode exhibits excellent cycle stability at an ultra‐high current density of 20 mA cm^?2.