High-performance Li Metal Batteries Research Articles

In Situ Formed Continuous and Dense Inorganic Borate-Based SEI for High-Performance Li-Metal Batteries.

The practical application of lithium metal batteries (LMBs) is largely hindered by the notorious lithium dendrite growth, low cycle efficiency associated with insufficient electrode-electrolyte interphase dynamics, and electrolyte combustion. Here, an advanced electrolyte using a combination of three kinds of salts dissolved in carbonate-based solvents is developed. The salt anions dominate a primary solvation sheath, resulting in weak interaction between Li+ and the solvents, as well as the in situ formation of an inorganic-rich bilayer solid electrolyte interface (SEI). The designed electrolyte enables high cycle stability in LMBs with a high-loading NMC cathode (approximately 20mg cm-2), exhibiting 89.89% capacity retention after 200 cycles with the cutoff voltage of 4.5V. Cryo-TEM characterization and density-functional theory (DFT) calculations reveal that the borate-based bilayer SEI, characterized by an exceptional dense structure, effectively suppresses lithium dendrite growth, and certify the crucial role of inorganic component continuity and density within the SEI, which surpasses the absorption and migration energy barrier in terms of significance. This profound understanding of SEI structure holds great potential for advancing the development of high-stable LMBs and can be expanded to other battery system.

Trace Dual-Salt Electrolyte Additive Enabling a LiF-Rich Solid Electrolyte Interphase for High-Performance Lithium Metal Batteries.

The composition and physiochemical properties of the solid electrolyte interphase (SEI) significantly impact the electrochemical cyclability of the Li metal. Here, we introduce a trace dual-salt electrolyte additive (TDEA) that accelerates LiF production from FEC decomposition and improves the LiF distribution, resulting in earlier LiF precipitation and the formation of a LiF-rich SEI on the Li anode. TDEA at a millimolar-level concentration was found to alter the morphology of deposited Li, suppress Li dendrite formation, and increase the cycling time and operating current density for Li anodes. Li∥NCM811 full cells using TDEA-based electrolytes exhibited approximately two times longer lifespan than those without additives. Additionally, the TDEA-based electrolytes enabled a high energy density of 347 Wh kg-1 for 500-mAh pouch cells, maintaining stable cycling over 180 cycles under stringent conditions (N/P = 1.26 and E/C = 2.2 g A h-1). Our findings suggest that the proposed TDEA strategy offers a promising path to achieving high-performance Li metal batteries.

Li2ZnCu3 Modified Cu Current Collector to Regulate Li Deposition.

Rationally designing a current collector that can maintain low lithium (Li) porosity and smooth morphology while enduring high-loading Li deposition is crucial for realizing the high energy density of Li metal batteries, but it is still challengeable. Herein, a Li2ZnCu3 alloy-modified Cu foil is reported as a stable current collector to fulfill the stable high-loading Li deposition. Benefiting from the in situ alloying, the generated numerous Li2ZnCu3@Cu heterojunctions induce a homogeneous Li nucleation and dense growth even at an ultrahigh capacity of 12 mAh cm-2. Such a spatial structure endows the overall Li2ZnCu3@Cu electrode with the manipulated steric hindrance and outmost surface electric potential to suppress the side reactions during Li stripping and plating. The resultant Li||Li2ZnCu3@Cu asymmetric cell preserves an ultrahigh average Coulombic efficiency of 99.2 % at 3 mA cm-2/6 mAh cm-2 over 200 cycles. Moreover, the Li-Li2ZnCu3@Cu||LiFePO4 cell maintains a cycling stability of 87.5 % after 300 cycles. After coupling with the LiCoO2 cathode (4 mAh cm-2), the cell exhibits a high energy density of 407.4 Wh kg-1 with remarkable cycling reversibility at an N/P ratio of 3. All these findings present a doable way to realize the high-capacity, dendrite-free, and dense Li deposition for high-performance Li metal batteries.

LiNO3 regulated rigid-flexible-synergistic polymer electrolyte boosting high-performance Li metal batteries

Conventional polymer electrolytes suffer from low ionic conductivity, poor interface compatibility, low mechanical strength and certain flammability. Herein, a rigid-flexible synergistic ultrastrong nonflammable polymer electrolyte (LiNO3-PPT@PI) regulated by LiNO3 is developed, which consists of rigid polyimide (PI) fiber skeleton and flexible poly pentaerythritol tetraacrylate (PPT) plasticized with LiNO3/triethyl phosphate (TEP)/fluoroethylene carbonate (FEC). PI fiber skeleton enhances tensile strength of LiNO3-PPT@PI to 21.8 MPa. TEP effectively enhances ionic conductivity to 7.57 × 10−4 S cm−1 at 30 °C and improves flame retardancy. LiNO3 is creatively utilized as the only lithium salt for LiNO3-PPT@PI to construct Li3N-rich solid electrolyte interphases (SEIs) and promote FEC to form LiF-rich SEIs/cathode-electrolyte interphases (CEIs) to improve interface stability, thereby enabling high-efficiency, long-term and dendrite-free cycling of LiFePO4 (LFP)||Li cells and LiNi0.8Mn0.1Co0.1O2 (NCM811)||Li cells, which is superior to the LiPF6-based polymer electrolytes. LFP||Li cells with LiNO3-PPT@PI exhibit excellent cycle performance over 650 cycles with 81.8 % capacity retention. This work presents a promising design strategy of safe and efficient polymer electrolytes for Li metal batteries.

Dual Li ion transport channels in a dynamical supramolecular solid electrolyte toward safety and high-performance Li metal batteries

The polymer based quasi-solid electrolyte (QSE), which combines the high ionic conductivity of the liquid electrolytes with the excellent mechanical flexibility of the polymer matrix, is highly desired and most promising for Li metal batteries (LMBs). However, the Li+ transfer pathways in QSE is not clear enough, and the practical applications in LMBs are also hindered by safety hazards arising from risks of mechanical damage, flammability and high voltage instability. Here, a dynamical supramolecular QSE with abundant hydrogen bonds to fabricate stable and safety LMBs, is reported. In this designed electrolyte, both thermal stability and superior interface stability with anode/cathode electrodes were achieved. Notably, the dual Li+ transport channels in QSE were investigated using in-situ FTIR technology and DFT calculations, providing insights into both the “wet” liquid phase and “dry” polymer chain channels. Benefiting from this design, the Li||NCM622 full batteries based on this QSE exhibit excellent long-term cycling stability.

Ti3C2Tx MXene enhanced PEO/SN-based solid electrolyte for high-performance Li metal battery

Succinonitrile has shown significant promise for application in polymer electrolytes for solid-state lithium metal batteries due to its high ionic conductivity at low-temperature. However, the use of Succinonitrile is limited due to its corrosion of Li metal. Herein, we report a solid polymer electrolyte with high ionic conductivity (2.17 × 10−3 S cm−1, 35 °C) enhanced by Ti3C2Tx. Corrosion of the Li anode is prevented due to the Succinonitrile molecules being efficiently anchored by Ti3C2Tx. Meanwhile, the coordination environment of Li+ is weakened due to the introduction of competitive coordination induction effects into the polymer electrolyte, resulting in efficient Li+ conduction. Furthermore, the mechanical properties of the electrolyte are enhanced by modulating the ratio of Ti3C2Tx to suppress the growth of Li dendrites. Therefore, Li||Li symmetric batteries deliver stable cycling up to 8000 h at 28 °C. LiFePO4||Li full batteries exhibit excellent cycling stability of 151.7 mAh g−1 with a capacity retention of 99.3% after 300 cycles. This work not only presents a new idea to suppress the corrosion of the Li anode by Succinonitrile but also provides a simple, feasible, and scalable strategy for high-performance Li metal batteries.

Low-Solvent-Coordination Solvation Structure for Lithium-Metal Batteries via Electric Dipole-Dipole Interaction.

Unveiling inherent interactions among solvents, Li+ ions, and anions are crucial in dictating solvation-desolvation kinetics at the electrode/electrolyte interface. Developing an electrolyte with a low ion-transport barrier and minimal solvent coordination in its interfacial solvation structure is essential for forming an anion-derived solid-electrolyte interface, a key component for high-performance Li-metal batteries. In this study, we harness electric dipole-dipole synergistic interactions to formulate an electrolyte with significantly reduced interfacial solvent coordination. Operando characterization and theoretical analysis reveal that 2-fluoropyridine (FPy) with high dipole preferentially adsorbs onto the Li metal surface. The adsorbed FPy molecule squeezes succinonitrile in the primary solvation sheath through steric hindrance, leading to the formation of an inorganic-rich interphase. Consequently, the introduction of FPy enhances the reversible capacity of the LiCoO2||Li cell, which maintains a capacity of 143 mAh g-1 after 500 cycles at a 1C rate. Moreover, the cycle life of LiCoO2 batteries with a limited supply of lithium extends from 120 cycles to over 200 cycles. These findings offer a strategy that can be applied broadly to design interfacial solvation structures for various metal-ion/metal-based batteries.

The Dependence of Solid Electrolyte Interphase on the Crystal Facet of Current Collector in Li Metal Battery.

The continuous electrolyte decomposition and uncontrolled dendrite growth caused by the unstable solid electrolyte interphase (SEI) have largely hindered the development of Li metal batteries. Here, we demonstrate that tuning the facet of current collector can regulate the composition of SEI and the subsequent Li deposition behavior using single-crystal Cu foils as an ideal platform. The theoretical and experimental studies reveal that the (100) facet of Cu possesses strong adsorption to anions, guiding more anions to participate preferentially in the inner Helmholtz plane and further promoting the formation of the stable inorganic-rich SEI. Consequently, the single-crystal Cu foils with a single [100] orientation (s-Cu(100)) achieve the dendrite-free Li deposition with enhanced Li plating/stripping reversibility. Moreover, the Li anode deposited on s-Cu(100) can stabilize the operation of an Ah-level pouch cell (350 Wh kg-1) with a low negative/positive capacity ratio (~2) and lean electrolyte (2.4 g Ah-1) for 150 cycles. Impressively, this strategy demonstrates universality in a series of electrolytes employed different anions. This work provides new insights into the correlation between the SEI and current collector, opening a universal avenue towards high-performance Li metal batteries.

A cation and anion dual-doping strategy in novel Li-rich Mn-based cathode materials for high-performance Li metal batteries

Lithium (Li)-rich Manganese (Mn)-based cathode materials are considered to be the most hopeful cathode materials for next-generation high-energy-density Li metal batteries. However, the rapid capacity fading and voltage decaying derived from phase transformation still hinder their practical application. Herein, we developed a cation/anion dual-doping strategy by synchronically incorporating Zr4+ cation and F− anion to boost the structural stability of the Li-rich Mn-based cathode. The strengthened transition metal-oxygen bonds raised by doping effect can inhibit the release of oxygen for enhanced electrochemical reversibility and mitigate the anisotropic lattice distortion to stabilize the layered structure. Meanwhile, dual doping strategy expands the lattice distance and increases oxygen vacancy formation energy, thereby improving ion diffusion kinetics and structural stability. As a result, the obtained cathode presents an excellent initial discharge capacity of 268.5 mAh g−1 and a prolonged cycle lifespan beyond 300 cycles. A stable cycling performance can be obtained under a high areal capacity of 5.17 mAh cm−2 with a low negative/positive electrode capacity ratio of 1.93. Our dual-doping strategy provides a valuable new idea for improving the structural stability and electrochemical properties of Li-rich Mn-based cathode materials, further promoting the development of high-energy-density Li metal batteries.

Engineering High-Performance Li Metal Batteries through Dual-Gradient Porous Cu-CuZn Host.

Porous copper (Cu) current collectors show promise in stabilizing Li metal anodes (LMAs). However, insufficient lithiophilicity of pure Cu and limited porosity in three-dimensional (3D) porous Cu structures led to an inefficient Li-Cu composite preparation and poor electrochemical performance of Li-Cu composite anodes. Herein, we propose a porous Cu-CuZn (DG-CCZ) host for Li composite anodes to tackle these issues. This architecture features a pore size distribution and lithiophilic-lithiophobic characteristics designed in a gradient distribution from the inside to the outside of the anode structure. This dual-gradient porous Cu-CuZn exhibits exceptional capillary wettability to molten Li and provides a high porosity of up to 66.05%. This design promotes preferential Li deposition in the interior of the porous structure during battery operation, effectively inhibiting Li dendrite formation. Consequently, all cell systems achieve significantly improved cycling stability, including Li half-cells, Li-Li symmetric cells, and Li-LFP full cells. When paired synergistically with the double-coated LiFePO4 cathode, the pouch cell configured with multiple electrodes demonstrates an impressive discharge capacity of 159.3 mAh g-1 at 1C. We believe this study can inspire the design of future 3D Li anodes with enhanced Li utilization efficiency and facilitate the development of future high-energy Li metal batteries.

Cation-Loaded Porous Mg2+-Zeolite Layer Direct Dendrite-Free Deposition toward Long-Life Lithium Metal Anodes.

Lithium metal, with ultrahigh theoretical specific capacity, is considered as an ideal anode material for the lithium-ion batteries. However, its practical application is severely plagued by the uncontrolled formation of dendritic Li. Here, a cation-loaded porous Mg2+-Zeolite layer is proposed to enable the dendrite-free deposition on the surface of Li metal anode. The skeleton channels of zeolite provide the low coordinated Li+-solvation groups, leading to the faster desolvation process at the interface. Meanwhile, anions-involved solvation sheath induces a stable, inorganic-rich SEI, contributing to the uniform Li+ flux through the interface. Furthermore, the co-deposition of sustained release Mg2+ realizes a new faster migration pathway, which proactively facilitates the uniform diffusion of Li on the lithium substrate. The synergistic modulation of these kinetic processes facilitates the homogeneous Li plating/stripping behavior. Based on this synergistic mechanism, the high-efficiency deposition with cyclic longevity exceeding 2100h is observed in the symmetric Li/Li cell with Mg2+-Zeolite modified anode at 1mA cm-2. The pouch cell matched with LiFePO4 cathode fulfills a capacity retention of 88.4% after 100 cycles at a severe current density of 1 C charge/discharge. This synergistic protective mechanism can give new guidance for realizing the safe and high-performance Li metal batteries.

Stabilizing Lithium-Metal Host Anodes by Covalently Binding MgF2 Nanodots to Honeycomb Carbon Nanofibers.

Constructing lithiophilic carbon hosts has been regarded as an effective strategy for inhibiting Li dendrite formation and mitigating the volume expansion of Li metal anodes. However, the limitation of lithiophilic carbon hosts by conventional surface decoration methods over long-term cycling hinders their practical application. In this work, a robust host composed of ultrafine MgF2 nanodots covalently bonded to honeycomb carbon nanofibers (MgF2/HCNFs) is created through an in situ solid-state reaction. The composite exhibits ultralight weight, excellent lithiophilicity, and structural stability, contributing to a significantly enhanced energy efficiency and lifespan of the battery. Specifically, the strong covalent bond not only prevents MgF2 nanodots from migrating and aggregating but also enhances the binding energy between Mg and Li during the molten Li infusion process. This allows for the effective and stable regulation of repeated Li plating/stripping. As a result, the MgF2/HCNF-Li electrode delivers a high Coulombic efficiency of 97% after 200 cycles, cycling stably for more than 2000 h. Furthermore, the full cells with a LiFePO4 cathode achieve a capacity retention of 85% after 500 cycles at 0.5C. This work provides a strategy to guide dendrite-free Li deposition patterns toward the development of high-performance Li metal batteries.

Adjusting Li+ Solvation Structures via Dipole-Dipole Interaction to Construct Inorganic-Rich Interphase for High-Performance Li Metal Batteries.

Practical applications of lithium metal batteries are limited by unstable solid electrolyte interphase (SEI) and uncontrollable dendrite Li deposition. Regulating the solvation structure of Li+ via modifying electrolyte components enables optimizing the structure of the SEI and realizing dendrite-free Li deposition. In this work, it is found that the ionic-dipole interactions between the electron-deficient B atoms in lithium oxalyldifluoro borate (LiDFOB) and the O atoms in the DME solvent molecule can weaken the interaction between the DME molecule and Li+, accelerating the desolvation of Li+. On this basis, the ionic-dipole interactions facilitate the entry of abundant anions into the inner solvation sheath of Li+, which promotes the formation of inorganic-rich SEI. In addition, the interaction between DFOB- and DME molecules reduces the highest occupied molecular orbital energy level of DME molecules in electrolytes, which improves the oxidative stability of the electrolytes system. As a result, the Li||Li cells in LiDFOB-containing electrolytes exhibit an excellent cyclability of over 1800h with a low overpotential of 18.2mV, and the Li||LiFePO4 full cells display a high-capacity retention of 93.4% after 100 cycles with a high Coulombic efficiency of 99.3%.

High-Performance Lithium Metal Batteries

The success of rechargeable lithium-ion batteries (LIBs) has brought evident convenience to human society, but state-of-the-art LIBs with a graphite anode are approaching their energy density limits. Li metal is considered the ultimate anode material due to its ultra-high theoretical specific capacity of 3860 mAh g-1, which is more than 10 times higher than lithiated graphite. Nonetheless, Li metal anode suffers from poor safety and low cycling efficiency due to its high reactivity. Electrolytes that work with Li anode should possess excellent stability against Li metal or form a highly passivating interface. It is also critical to control the amount of Li in the cell, preferably having no excess Li at the anode side. In this talk next-generation solid state and hybrid electrolytes based on Li-stuffed garnets that enable high-performance Li metal batteries will be discussed.

Self-supported 3D current collector modified with in-situ formed lithiophilic [Cu(NH3)2]Cl for high-performance Li-metal batteries

Li-metal batteries (LMBs) are regarded as some of the most promising energy storage systems owing to their superior theoretical specific capacity and lowest electrochemical potential. However, the application of LMBs has been severely hindered by the uncontrollable dendrite growth and volume expansion of metal anodes during Li plating. Herein, we construct a three-dimensional (3D) porous CuZn current collector decorated with a lithiophilic [Cu(NH3)2]Cl compound (3D 1H3N), in which [Cu(NH3)2]Cl offers nucleation sites and guides fast Li+ deposition in the pores and tunnels. The 3D framework accommodates volume expansion and disperses deposition current. Together, these two functions contribute to low-barrier and dendrite-free Li plating/stripping with enhanced Coulombic efficiency (CE) and excellent stability. The half-cell utilizing the as-fabricated 3D 1H3N current collector exhibited a CE of 98 % for over 270 cycles at 0.5 mA·cm–2 and 97 % for over 220 cycles at 1 mA·cm–2. The Li@3D 1H3N anode stabilized over 270 cycles (1100 h) at 0.5C in symmetric cells and delivered a capacity retention of 92.5 % after 450 cycles at 1C (1C = 170 mAh·g–1) in full cells. This study sheds light on the multifunction modification of self-supported anode current collectors for advanced LMBs to promote their practical application.

Uniform Li-metal growth on renewable lignin with lithiophilic functional groups derived from wood for high-performance Li-metal batteries

Lithium metal batteries (LMBs) are promising energy storage devices with high energy density owing to their high theoretical capacity (3860 mAh g−1) and low reduction potential of lithium (Li)-metal anodes. However, their practical application is limited by poor Coulombic efficiency (CE) and safety issues due to Li dendrite growth during Li plating/stripping. Herein, a three-dimensional (3D) structure of lignin with a lithiophilic functional group derived from waste wood is suggested as an additional functional layer of LMBs, i.e., a lignosulfonic acid sodium salt (LASS) with a negatively charged sulfonate group (SO3−) in its chemical structure. The SO3− group enhances the Li-ion (Li+) affinity and enables Li+-flux control, supplying homogeneous Li growth sites. It induces stable electrochemical dendrite-free Li growth. Consequently, in the LASS-Cu||Li half-cell, a high CE of 96.7 % at 210 cycles and stable operation is achieved without a short circuit and, symmetric-cell with LASS layers shows stable cycling over 2000 h. Moreover, full-cells with LiFePO4 (LFP) and LiNi0.8Co0.1Mn0.1O2 (NCM 811) cathodes exhibit enhanced electrochemical performance. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) reveal that the LASS layer suppressed dendritic Li growth and stimulated densely packed Li growth. This work suggests an effective strategy for improving the performance of LMBs using renewable lignin materials.

Electronegative graphene film based interface-chemistry regulation for stable lithium metal batteries

To achieve practical application of lithium (Li) metal anodes for high-energy–density batteries, the primary challenges of the inhomogeneous solid electrolyte interphase (SEI) and irregular Li electrochemical stripping/depositing behaviors should been surmounted. So as to homogenize Li+ distribution and stabilize the SEI layer, herein, we reported a partially reduced graphene oxide (PrGO) film with a manageable electronegativity as an ideal Li host to construct composite electrode (PrGO@Li). The fabricated PrGO with tunable oxygen amount and negatively charge can achieve controllable Li capacity avoiding excess Li. More importantly, the electronegative PrGO film matrix can cause an electrostatic force and thereby regulate the Li+ distribution pattern and diffusion kinetics, which induces a homogeneous and stable LiF-rich SEI and highly conformal Li+ stripping/deposition behaviors without Li dendrites. As a result, the optimal PrGO@Li electrode delivers long-term reversible Li+ stripping/depositing processes with an extremely low overpotential (7 mV) after 2000 h cycling at 20 mA cm−2 and 10 mAh cm−2. Moreover, the full battery based on this anode paired with LiFePO4 cathode exhibits outstanding cycling stability, high rate capacity and excellent flexibility characters. Meanwhile, the controllable PrGO films can also be loading with sulfur as cathodes for satisfactory Li/sulfur batteries. This research deeply analyzes the intermediation mechanism between the graphene host and Li+ on the electrochemical behaviors, and offers universal guidance for the development of high-performance Li-metal batteries.

Towards high performance Li metal batteries: Surface functionalized graphene separator with improved electrochemical kinetics and stability

Lithium (Li) metal is a promising anode for next-generation batteries owing to its ultrahigh theoretical capacity (3,860 mAh g−1) and the lowest reduction potential (−3.04 vs SHE at RT). However, the development of Li-metal batteries (LMBs) is still in the research stage due to the inherent problems related to the growth of Li dendrites and unlimited volume change in Li metal. Among diverse approaches, the introduction of functional separators is regarded as an effective strategy for improving the safety and electrochemical performance of LMBs. Herein, we deposited two different graphene layers onto the separators to explore the influence of surface functionalized graphene layer on the electrochemical performance and cycle stability of LMBs. When a surface functionalized graphene separator (SFGS) was used in the LMBs, it exhibited superior electrolyte wettability than a graphene separator (GS), contributing to the improved ionic conductivity and homogeneous Li-ion flux. Due to the improved electrochemical kinetics and reversible electrochemical reactions, Li/Cu cells with the SFGS exhibited the most stable cycle performance with a high Coulombic efficiency of 98 % over 200 cycles compared with other Li/Cu cells. Our strategy would resolve many issues related to the poor electrochemical reversibility of Li-metal anodes and advance the development of practical surface-modified separators for high-performance LMBs.

Fine-tuned molecular design toward a stable solid electrolyte interphase on a lithium metal anode from in silico simulation

Electrolyte engineering has emerged as a promising approach for enhancing the performance of lithium (Li) metal batteries, with recent advancements in novel electrolytes contributing to improved battery performance. Nevertheless, the intricate electrochemical interface poses significant challenges for experimental studies, resulting in a limited fundamental understanding of interface phenomena. To address this issue, we utilize hybrid ab initio and reactive molecular dynamics (HAIR) simulations to examine the solid electrolyte interphase (SEI) formation process and chemical composition at the atomic level in a series of fluorinated pseudo-localized high-concentration electrolytes (LHCEs). Our detailed analysis uncovers that ionic conductivity, the abundance of LiF, and oligomer length are three pivotal factors influencing cell performance. The simulations not only corroborate the –CF2- fluorinated backbone scheme, aligning with experimental findings but also reveal new opportunities for enhancing performance through the introduction of –CHF– moieties based on the concept of incremental design. Consequently, we propose a novel solvent molecule, fluorinated 1,2,3,4,5,6-hexa-1,6-dimethoxylhexane (FHDH), and demonstrate that FHDH maintains desirable physicochemical properties and high F concentration while exhibiting superior SEI physicochemical properties in terms of ionic conductivity, relative amount of LiF, and long-chain oligomers. Our findings offer a rational explanation for experimental design strategies and suggest further electrolyte optimization based on these insights, paving the way for the development of high-performance Li metal batteries.

(Invited) High-Performance Lithium Metal Batteries

The success of rechargeable lithium-ion batteries (LIBs) has brought evident convenience to human society, but state-of-the-art LIBs with a carbon anode are approaching their energy density limits. Li metal is considered the ultimate anode material due to its ultra-high theoretical specific capacity of 3860 mAh g-1, which is more than 10 times higher than lithiated graphite. Nonetheless, Li anode suffers from poor safety and low cycling efficiency due to its high reactivity. Electrolytes that work with Li anode should possess excellent stability against Li metal or form a highly passivating interface. It is also critical to control the amount of Li in the cell, preferably having no excess Li at the anode side.1 In this presentation, next-generation electrolytes that enable such types of high-performance Li metal batteries will be discussed, including advanced liquid electrolytes,2 garnet-type ceramic electrolytes3–5 and hybrid electrolytes.6,7 References C. Zhou, A. J. Samson, M. A. Garakani, and V. Thangadurai, J. Electrochem. Soc., 168, 060532 (2021).C. Zhou et al., Energy Storage Mater., 42, 295–306 (2021) https://doi.org/10.1016/j.ensm.2021.07.043.S. P. Kammampata, R. H. Basappa, T. Ito, H. Yamada, and V. Thangadurai, ACS Appl. Energy Mater., 2, 1765–1773 (2019).S. P. Kammampata, H. Yamada, T. Ito, R. Paul, and V. Thangadurai, J. Mater. Chem. A, 8, 2581–2590 (2020).C. Zhou, A. J. Samson, K. Hofstetter, and V. Thangadurai, Sustain. Energy Fuels, 2, 2165–2170 (2018).S. Bag, C. Zhou, P. J. Kim, V. G. Pol, and V. Thangadurai, Energy Storage Mater., 24, 198–207 (2019) https://doi.org/10.1016/j.ensm.2019.08.019.C. Zhou, S. Bag, T. He, B. Lv, and V. Thangadurai, Appl. Mater. Today, 19, 100585 (2020) https://doi.org/10.1016/j.apmt.2020.100585.