Electrolytes Enriched by Crown Ethers for Lithium Metal Batteries

Lithium (Li) metal battery is considered the most promising next-generation battery due to its low potential and high theoretical capacity. However, Li dendrite growth causes serious safety problems. Herein, the 15-Crown-5 (15-C-5) is reported as an electrolyte additive based on solvation shell regulation. The strong complex effect between Li⁺ ion and 15-C-5 can reduce the concentration of Li ions on the electrode surface, thus changing the nucleation, and repressing the growth of Li dendrites in the plating process. Significantly, the strong coordination of Li⁺/15-C-5 would be able to make them aggregate around the Li crystal surface, which could form a protective layer and favor the formation of a smooth and dense solid electrolyte interphase with high toughness and Li⁺ ion conductivity. Therefore, the electrolyte system with 2.0 wt% 15-C-5 achieves excellent electrochemical performance with 170 cycles at 1.0 mA cm⁻² with capacity of 0.5 mA h cm⁻² in symmetric Li|Li cells. The obviously enhanced cycle and rate performance are also achieved in Li|LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) full cells. The 15-C-5 demonstrates to be a promising additive for the electrolytes toward safe and efficient Li metal batteries.     

Non-Flammable Electrolyte with Lithium Nitrate as the Only Lithium Salt for Boosting Ultra-Stable Cycling and Fire-Safety Lithium Metal Batteries

Lithium metal batteries (LMBs) attract considerable attention for their incomparable energy density. However, safety issues caused by uncontrollable lithium dendrites and highly flammable electrolyte limit large-scale LMBs applications. Herein, a low-cost, thermally stable, and low environmentally-sensitive lithium nitrate (LiNO₃) is proposed as the only lithium salt to incorporate with nonflammable triethyl phosphate and fluoroethylene carbonate (FEC) co-solvent as the electrolyte anticipated to enhance the performance of LMBs. Benefiting from the presence of NO₃⁻ and FEC with strong solvation effect and easily reduced ability, a Li₃N–LiF-rich stable solid electrolyte interphase is constructed. Compared to commercial electrolytes, the proposed electrolyte has a high Coulombic efficiency of 98.31% in Li-Cu test at 1 mA cm⁻² of 1.0 mAh cm⁻² with dendrite-free morphology. Additionally, the electrolyte system shows high voltage stability and cathode electrolyte interphase film-forming properties with stable cycling performances, which exhibit outstanding capacity retention rates of 96.39% and 83.74% after 1000 cycles for LFP//Li and NCM811//Li, respectively. Importantly, the non-flammable electrolyte delays the onset of combustion in lithium metal soft pack batteries by 255 s and reduces the peak heat release by 21.02% under the continuous external high-temperature heating condition. The novel electrolyte can contribute immensely to developing high-electrochemical-performance and high-safety LMBs.     

An Intrinsically Nonflammable Electrolyte for Prominent-Safety Lithium Metal Batteries with High Energy Density and Cycling Stability

Nex-generation high-energy-density storage battery, assembled with lithium (Li)-metal anode and nickel-rich cathode, puts forward urgent demand for advanced electrolytes that simultaneously possess high security, wide electrochemical window, and good compatibility with electrode materials. Herein an intrinsically nonflammable electrolyte is designed by using 1 M lithium difluoro(oxalato)borate (LiDFOB) in triethyl phosphate (TEP) and N-methyl-N-propyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr₁₃][TFSI] ionic liquid (IL) solvents. The introduction of IL can bring plentiful organic cations and anions, which provides a cation shielding effect and regulates the Li⁺ solvation structure with plentiful Li⁺-DFOB⁻ and Li⁺-TFSI⁻ complexes. The unique Li⁺ solvation structure can induce stable anion-derived electrolyte/electrode interphases, which effectively inhibit Li dendrite growth and suppress side reactions between TEP and electrodes. Therefore, the LiNi_0.9Co_0.05Mn_0.05O₂ (NCM90)/Li coin cell with this electrolyte can deliver stable cycling even under 4.5 V and 60 °C. Moreover, a Li-metal battery with thick NCM90 cathode (≈ 15 mg cm⁻²) and thin Li-metal anode (≈ 50 µm) (N/P ≈ 3), also reveals stable cycling performance under 4.4 V. And a 2.2 Ah NCM90/Li pouch cell can simultaneously possess prominent safety with stably passing the nail penetration test, and high gravimetric energy density of 470 Wh kg⁻¹ at 4.4 V.     

Fluoroethylene Carbonate Additives to Render Uniform Li Deposits in Lithium Metal Batteries

Lithium (Li) metal has been considered as an important substitute for the graphite anode to further boost the energy density of Li‐ion batteries. However, Li dendrite growth during Li plating/stripping causes safety concern and poor lifespan of Li metal batteries (LMB). Herein, fluoroethylene carbonate (FEC) additives are used to form a LiF‐rich solid electrolyte interphase (SEI). The FEC‐induced SEI layer is compact and stable, and thus beneficial to obtain a uniform morphology of Li deposits. This uniform and dendrite‐free morphology renders a significantly improved Coulombic efficiency of 98% within 100 cycles in a Li | Cu half‐cell. When the FEC‐protected Li metal anode matches a high‐loading LiNi_0.5Co_0.2Mn_0.3O₂ (NMC) cathode (12 mg cm^?2), a high initial capacity of 154 mAh g^?1 (1.9 mAh cm^?2) at 180.0 mA g^?1 is obtained. This LMB with conversion‐type Li metal anode and intercalation‐type NMC cathode affords an emerging energy storage system to probe the energy chemistry of Li metal protection and demonstrates the material engineering of batteries with very high energy density.     

Strategies in Structure and Electrolyte Design for High-Performance Lithium Metal Batteries

Lithium metal is the “holy grail” anode for next-generation high-energy rechargeable batteries due to its high capacity and lowest redox potential among all reported anodes. However, the practical application of lithium metal batteries (LMBs) is hindered by safety concerns arising from uncontrollable Li dendrite growth and infinite volume change during the lithium plating and stripping process. The formation of stable solid electrolyte interphase (SEI) and the construction of robust 3D porous current collectors are effective approaches to overcoming the challenges of Li metal anode and promoting the practical application of LMBs. In this review, four strategies in structure and electrolyte design for high-performance Li metal anode, including surface coating, porous current collector, liquid electrolyte, and solid-state electrolyte are summarized. The challenges, opportunities, perspectives on future directions, and outlook for practical applications of Li metal anode, are also discussed.     

Phosphonium Bromides Regulating Solid Electrolyte Interphase Components and Optimizing Solvation Sheath Structure for Suppressing Lithium Dendrite Growth

Electrolyte additives play important roles in suppressing lithium dendrite growth and improving the electrochemical performance of long-life lithium metal batteries (LMBs), however, it is still challenging to design individual additive for adjusting the solid electrolyte interphase (SEI) components and changing lithium ion solvation sheath in the electrolyte at the same time for optimizing electrochemical performance. Herein, alkyl-triphenyl-phosphonium bromides (alkyl-TPPB) are designed as the electrolyte additive to enhance the stability of metallic Li anode under the guidance of multi-factor principle for electrolyte additive molecule design (EDMD). Both alkyl-TPP cations and Br⁻ anions produce positive influences on suppressing Li dendrite growth and stabilizing the unstable interphase between metallic Li anode/electrolyte. As expected, the optimized solvation sheath structure, and the stable SEI suppress Li dendrite growth. As a result, the Li||Li₄Ti₅O₁₂ cell reveals a long stable life over 1000 cycles with high Coulombic efficiency (99.9%). This work provides an insight on stabilizing SEI and optimizing solvation sheath structure with novel approach to develop long-term stability and safety LMBs.     

Juggling Formation of HF and LiF to Reduce Crossover Effects in Carbonate Electrolyte with Fluorinated Cosolvents for High-Voltage Lithium Metal Batteries

Fluorinated solvents emerge as a promising strategy to improve performance of lithium metal batteries (LMBs). However, most of them are prone to produce corrosive HF and deteriorate electrode interface, inducing cathode-to-anode detrimental crossover of transition metal-ions. Here, fluorinated aromatic hydrocarbons in dimethyl carbonate (DMC)-based diluted highly concentrated electrolyte (DHCE) are employed to juggle formation of HF and LiF, enabling stable cycling of high-voltage LiNi_0.7Co_0.1Mn_0.2O₂ (NCM712) and LiCoO₂ (LCO). The nature of aromatics in this carbonate-based DHCE makes them difficult to undergo β-hydrogen assisted defluorination, evidencing by the high energy barrier and high bond energy of β-sites hydrogen. The advanced DHCE restrains HF formation but strengthens LiF formation, which not only suppresses impedance growth, transition-metal dissolution, and stress crack on the cathode, but achieves highly reversible Li stripping/plating with an outstanding average Coulombic efficiency up to 99.3%. The Li||NCM712 cell and Li||LCO cell both exhibits superior cycling stability at high operation voltage. Even under stringent conditions, the 4.4 V Li||NCM712 full battery retains >95% of the initial capacity over 100 cycles, advancing practical high-voltage LMBs. This study designs an efficient electrolyte that generates robust electrode/electrolyte interphases and restrains by-products formation spontaneously, thus shedding new light on electrolyte toward applicable LMBs.     

Regulating Na-ion Solvation in Quasi-Solid Electrolyte to Stabilize Na Metal Anode

Sodium metal batteries are promising for cost-effective energy storage, however, the sluggish ion transport in electrolytes and detrimental sodium-dendrite growth stall their practical applications. Herein, a cross-linking quasi-solid electrolyte with a high ionic conductivity of 1.4 mS cm⁻¹ at 25 °C is developed by in-situ polymerizing poly (ethylene glycol) diacrylate-based monomer. Benefiting from the refined solvation structure of Na⁺ with a much lower desolvation barrier, random Na⁺ diffusion on the Na surface is restrained, so that the Na dendrite formation is suppressed. Consequently, symmetrical Na||Na cells employing the electrolyte can be cycled >2000 h at 0.1 mA cm⁻². Na₃V₂(PO₄)₃||Na batteries reveal a high discharge specific capacity of 66.1 mAh g⁻¹ at 15 C and demonstrate stable cycling over 1000 cycles with a capacity retention of 83% at a fast rate of 5 C.     

Dynamic Ion Sieve as the Buffer Layer for Regulating Li+ Flow in Lithium Metal Batteries

How to realize uniform Li⁺ flow is the key to achieve even Li deposition for lithium metal batteries (LMBs). In this study, a concept of dynamic ion sieve is proposed to design the buffer layer nearby Li anode surface to regulate Li⁺ spatial arrangement by introducing tributylmethylphosphonium bis(trifluoromethanesulfonyl)imide (TMPB) into the carbonate electrolyte. The buffer layer induced by TMP⁺ can adjust the velocity of arriving solvated Li⁺ that gives solvated Li⁺ sufficient time to redistribute and accumulate on Li anode surface, resulting in a uniform and higher concentrated Li⁺ flow. Besides, TFSI⁻ can participate in the generation of inorganic component-rich solid electrolyte interphase (SEI) with Li₃N, which can facilitate the Li⁺ conductivity of SEI. Consequently, the stable and uniform Li deposition can be obtained, achieving the excellent cycling performance up to 1000 h at 0.5 mA cm⁻² in the Li||Li symmetric cell. Besides, the Li||NCM622 full cell also possesses excellent cycling stability with a high-capacity retention rate of 66.7% after 300 cycles.     

A Self-Limited Free-Standing Sulfide Electrolyte Thin Film for All-Solid-State Lithium Metal Batteries

All-solid-state (ASS) lithium metal batteries (LMBs) are considered the most promising next-generation batteries due to their superior safety and high projected energy density. To access the practically desired high energy density of ASS LMBs, an ultrathin solid-state electrolyte (SSE) film with fast ion-transport capability presents as an irreplaceable component to reduce the proportion of inactive materials in ASS batteries. In this contribution, an ultrathin (60  µ m), flexible, and free-standing argyrodite (Li₆PS₅Cl) SSE film is designed through a self-limited strategy. A chemically compatible cellulose membrane is employed as the self-limiting skeleton that not only defined the thinness of the sulfide SSE film but also strengthened its mechanical properties. The ionic conductivity of the SSE film reaches up to 6.3 × 10⁻³ S cm⁻¹ at room temperature, enabling rapid lithium-ion transportation. The self-limited SSE thin films are evaluated in various ASS LMBs with different types of cathode (sulfur and lithium titanate) and anode materials (lithium and lithium-indium alloy) at both mold-cell and pouch-cell levels, demonstrating a stable performance and high-rate capability. This study provides a general strategy for the rational design of an SSE thin film towards high-energy-density ASS batteries.     

Composite Lithium Metal Anodes with Lithiophilic and Low-Tortuosity Scaffold Enabling Ultrahigh Currents and Capacities in Carbonate Electrolytes

The practical application of lithium metal anode has been hindered by safety and cyclability issues due to the uncontrollable dendrite growth, especially during fast cycling and deep plating/stripping process. Here, a composite Li metal anode supported by periodic, perpendicular, and lithiophilic TiO₂/poly(vinyl pyrrolidone) (PVP) nanofibers via a facial rolling process is reported. TiO₂/PVP nanofibers with good Li affinity provide low-tortuosity and directly inward Li⁺ transport paths to facilitate Li nucleation and deposition under high areal capacities and current densities. The micrometer-scale interspaces between TiO₂/PVP walls offer enough space to circumvent the huge volume variation and avoid structure collapsing during the repeated deep Li plating/stripping. The unique structure enables stable cycling under ultrahigh currents (12 mA cm⁻²), and ultra-deep plating/stripping up to 60 mAh cm⁻² with a long cycle life in commercial carbonate electrolytes. The gassing behavior in operating pouch cells is observed using ultrasonic transmission mapping. When paired with LiFePO₄ (5 mAh cm⁻²), sulfur (3 mAh cm⁻²), and high-voltage LiNi_0.8Co_0.1Mn_0.1O₂ cathodes, the composite Li anodes deliver remarkably improved rate performance and cycling stability, demonstrating that it could be a promising strategy for balancing high-energy density and high-power density in Li metal batteries.     

Solvent-Free Electrolyte for High-Temperature Rechargeable Lithium Metal Batteries

The formation of lithiophobic inorganic solid electrolyte interphase (SEI) on Li anode and cathode electrolyte interphase (CEI) on the cathode is beneficial for high-voltage Li metal batteries. However, in most liquid electrolytes, the decomposition of organic solvents inevitably forms organic components in the SEI and CEI. In addition, organic solvents often pose substantial safety risks due to their high volatility and flammability. Herein, an organic-solvent-free eutectic electrolyte based on low-melting alkali perfluorinated-sulfonimide salts is reported. The exclusive anion reduction on Li anode surface results in an inorganic, LiF-rich SEI with high capability to suppress Li dendrite, as evidenced by the high Li plating/stripping CE of 99.4% at 0.5  mA cm⁻² and 1.0 mAh cm⁻², and 200-cycle lifespan of full LiNi_0.8Co_0.15Al_0.05O₂ (2.0 mAh cm⁻²) || Li (20 µm) cells at 80 °C. The proposed eutectic electrolyte is promising for ultrasafe and high-energy Li metal batteries.     

Lithium-Ion Desolvation Induced by Nitrate Additives Reveals New Insights into High Performance Lithium Batteries

Electrolyte additives have been widely used to address critical issues in current metal (ion) battery technologies. While their functions as solid electrolyte interface forming agents are reasonably well-understood, their interactions in the liquid electrolyte environment remain rather elusive. This lack of knowledge represents a significant bottleneck that hinders the development of improved electrolyte systems. Here, the key role of additives in promoting cation (e.g., Li⁺) desolvation is unraveled. In particular, nitrate anions (NO₃⁻) are found to incorporate into the solvation shells, change the local environment of cations (e.g., Li⁺) as well as their coordination in the electrolytes. The combination of these effects leads to effective Li⁺ desolvation and enhanced battery performance. Remarkably, the inexpensive NaNO₃ can successfully substitute the widely used LiNO₃ offering superior long-term stability of Li⁺ (de-)intercalation at the graphite anode and suppressed polysulfide shuttle effect at the sulfur cathode, while enhancing the performance of lithium–sulfur full batteries (initial capacity of 1153 mAh g⁻¹ at 0.25C) with Coulombic efficiency of ≈100% over 300 cycles. This work provides important new insights into the unexplored effects of additives and paves the way to developing improved electrolytes for electrochemical energy storage applications.     

High‐Power Lithium Metal Batteries Enabled by High‐Concentration Acetonitrile‐Based Electrolytes with Vinylene Carbonate Additive

To enable next‐generation high‐power, high‐energy‐density lithium (Li) metal batteries (LMBs), an electrolyte possessing both high Li Coulombic efficiency (CE) at a high rate and good anodic stability on cathodes is critical. Acetonitrile (AN) is a well‐known organic solvent for high anodic stability and high ionic conductivity, yet its application in LMBs is limited due to its poor compatibility with Li metal anodes even at high salt concentration conditions. Here, a highly concentrated AN‐based electrolyte is developed with a vinylene carbonate (VC) additive to suppress Li⁺ depletion at high current densities. Addition of VC to the AN‐based electrolyte leads to the formation of a polycarbonate‐based solid electrolyte interphase, which minimizes Li corrosion and leads to a very high Li CE of up to 99.2% at a current density of 0.2 mA cm^‐2. Using such an electrolyte, fast charging of Li||NMC333 cells is realized at a high current density of 3.6 mA cm^‐2, and stable cycling of Li||NMC622 cells with a high cathode loading of 4 mAh cm^‐2 is also demonstrated.     

Enabling High-Performance NASICON-Based Solid-State Lithium Metal Batteries Towards Practical Conditions

Solid-state lithium metal batteries (SSLMBs) are promising next-generation high-energy rechargeable batteries. However, the practical energy densities of the reported SSLMBs have been significantly overstated due to the use of thick solid-state electrolytes, thick lithium (Li) anodes, and thin cathodes. Here, a high-performance NASICON-based SSLMB using a thin (60 µm) Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) electrolyte, ultrathin (36 µm) Li metal, and high-loading (8 mg cm⁻²) LiFePO₄ (LFP) cathode is reported. The thin and dense LAGP electrolyte prepared by hot-pressing exhibits a high Li ionic conductivity of 1 × 10⁻³ S cm⁻¹ at 80 °C. The assembled SSLMB can thus deliver an increased areal capacity of ≈1 mAh cm⁻² at C/5 with a high capacity retention of ≈96% after 50 cycles under 80 °C. Furthermore, it is revealed by synchrotron X-ray absorption spectroscopy and in situ high-energy X-ray diffraction that the side reactions between LAGP electrolyte and LFP cathode are significantly suppressed, while rational surface protection is required for Ni-rich layered cathodes. This study provides valuable insights and guidelines for the development of high-energy SSLMBs towards practical conditions.     

Critical Review of Fluorinated Electrolytes for High-Performance Lithium Metal Batteries

Lithium metal batteries (LMBs), due to their ultra-high energy density, are attracting tremendous attentions. However, their commercial application is severely impeded by poor safety and unsatisfactory cycling stability, which are induced by lithium dendrites, side reactions, and inferior anodic stability. Electrolytes, as the indispensable and necessary components in lithium metal batteries, play a crucial role in regulating the electrochemical performance of LMBs. Recently, the fluorinated electrolytes are widely investigated in high-performance LMBs. Thus, the design strategies of fluorinated electrolytes are thoroughly summarized, including fluorinated salts, fluorinated solvents, and fluorinated additives in LMBs, and insights of the fluorinated components in suppressing lithium dendrites, improving anodic stability and cycling stability. Finally, an outlook with several design strategies and challenges will be proposed for novel fluorinated electrolytes.     

Fast Li+ Transport via Silica Network-Driven Nanochannels in Ionomer-in-Framework for Lithium Metal Batteries

For the development of all-solid-state lithium metal batteries (LMBs), a high-porous silica aerogel (SA)-reinforced single-Li⁺ conducting nanocomposite polymer electrolyte (NPE) is prepared via two-step selective functionalization. The mesoporous SA is introduced as a mechanical framework for NPE as well as a channel for fast lithium cation migration. Two types of monomers containing weak-binding imide anions and Li⁺ cations are synthesized and used to prepare NPEs, where these monomers are grafted in SA to produce SA-based NPEs (SANPEs) as ionomer-in-framework. This hybrid SANPE exhibits high ionic conductivities (≈10⁻³ S cm⁻¹), high modulus (≈10⁵ Pa), high lithium transference number (0.84), and wide electrochemical window (>4.8 V). The resultant SANPE in the lithium symmetric cell possesses long-term cyclic stability without short-circuiting over 800 h under 0.2 mA cm⁻². Furthermore, the LiFePO₄|SANPE|Li solid-state batteries present a high discharge capacity of 167 mAh g⁻¹ at 0.1 C, good rate capability up to 1 C, wide operating temperatures (from −10 to 40 °C), and a stable cycling performance with 97% capacity retention and 100% coulombic efficiency after 75 cycles at 1 C and 25 °C. The SANPE demonstrates a new design principle for solid-state electrolytes, allowing for a perfect complex between inorganic silica and organic polymer, for high-energy-density LMBs.     

Intercalated Electrolyte with High Transference Number for Dendrite‐Free Solid‐State Lithium Batteries

Solid‐state lithium (Li) batteries using solid electrolytes and Li anodes are highly desirable because of their high energy densities and intrinsic safety. However, low ambient‐temperature conductivity and poor interface compatibility of solid electrolytes as well as Li dendrite formation cause large polarization and poor cycling stability. Herein, a high transference number intercalated composite solid electrolyte (CSE) is prepared by the combination of a solution‐casting and hot‐pressing method using layered lithium montmorillonite, poly(ethylene carbonate), lithium bis(fluorosulfonyl)imide, high‐voltage fluoroethylene carbonate additive, and poly(tetrafluoroethylene) binder. The electrolyte presents high ionic conductivity (3.5 × 10^?4 S cm^?1), a wide electrochemical window (4.6 V vs Li⁺/Li), and high ionic transference number (0.83) at 25 °C. In addition, a 3D Li anode is also fabricated via a facile thermal infusion strategy. The synergistic effect of high transference number intercalated electrolyte and 3D Li anode is more favorable to suppress Li dendrites in a working battery. The solid‐state batteries based on LiFePO₄ (Al₂O₃ @ LiNi_0.5Co_0.2Mn_0.3O₂), CSE, and 3D Li deliver admirable cycling stability with discharge capacity 145.9 mAh g^?1 (150.7 mAh g^?1) and capacity retention 91.9% after 200 cycles at 0.5 C (92.0% after 100 cycles at 0.2 C) at 25 °C. This work affords a splendid strategy for high‐performance solid‐state battery.     

Long Cycle Life Lithium Metal Batteries Enabled with Upright Lithium Anode

The lithium metal anode is the holy grail of the battery field due to its lowest reduction potential and high specific capacity; however, its application is hindered by severe safety hazards and inferior cyclic stability due to dendrites and unstable solid electrolyte interphase (SEI). Aiming at these problems, a coiled Li anode with a unique upright structure is proposed. The upright structure endows coiled Li anode with abundant inner reaction interface/space/mass for lithium deposit/storage/transport, which can induce the inner growth of Li dendrites and SEI. The Li⁺ transport/deposit behavior and mechanism of coiled Li anode are clarified via in situ observation and numerical simulation. Benefiting from the small volume expansion and sufficient Li⁺ transport, the coiled Li anodes combined with Li₄Ti₅O₁₂ cathodes achieve a long life of over 2000 cycles at 5C with a reversible capacity of 129 mAh g^?1 and 100% Coulombic efficiency.