High-loading Cathode Research Articles

High‐Capacity and Stable Sodium‐Sulfur Battery Enabled by Novel Molybdenum Carbide Electrocatalyst and Carbon Nanoporosity

Room-temperature sodium - sulfur (RT Na-S) batteries are highly promising due to the favorable techno-economics and the greater availability of both sodium and sulfur. RT Na-S cells are held back by several primary challenges including dissolution of polysulfides species in liquid electrolytes, sluggish sulfur redox kinetics, as well as the large cathode volume expansion (170%) on cell discharge. Here, we develop a novel molybdenum carbide (MoC/Mo2C) electrocatalyst to promote Na-S reaction kinetics and extend batteries’ cycling lifetime. MoC/Mo2C nanoparticles is in-situ grown in conjunction with activation of nitrogen-doped hollow porous carbon nanotubes. Sulfur impregnation (50wt.% S) results in unique triphasic architecture termed MoC/Mo2C@PCNT-S. MoC/Mo2C electrocatalyst and carbon nanoporosity synergistically promote the sulfur utilization in carbonate electrolyte. In-situ time-resolved Raman, XPS and optical analysis demonstrate a quasi-solid-state phase transformation within MoC/Mo2C@PCNT-S, where minimal polysulfides are dissolved in electrolyte. As results, MoC/Mo2C@PCNT-S cathodes performed promising rate performance of 987 mAh g-1 at 1 A g-1, 818 mAh g-1 at 3 A g-1, and 621 mAh g-1 at 5 A g-1. The cells delivered a retained capacity of 650 mAh g-1 after 1000 cycles at 1.5 A g-1, which corresponds to only 0.028% capacity decay per cycle. Such promising cycling stability is also obtained for high mass loading cathodes (64wt.% S, 12.7 mg cm-2). Complementary Density Functional Theory (DFT) simulation provide fundamental insight regarding the electrocatalytic role of MoC/Mo2C nanoparticles. Favorable charge transfer between the sulfur and Mo sites on the surface of carbides contributes to a strong binding of Na2Sx (1 ≤ x ≤ 4) on MoC/Mo2C surfaces. Consequently, the formation energy of Na2Sx (1 ≤ x ≤ 4) on MoC/Mo2C is significantly lowered compared to the analogous redox in liquid, as well as the case of baseline ordered carbon.

Delocalized Lithium Ion Flux by Solid-State Electrolyte Composites Coupled with 3D Porous Nanostructures for Highly Stable Lithium Metal Batteries.

This work investigates the root cause of failure with the ultimate anode, Li metal, when employing conventional/composite separators and/or porous anodes. Then a feasible route of utilizing Li metal is presented. Our operando and microscopy studies have unveiled that Li+ flux passing through the conventional separator is not uniform, resulting in preferential Li plating/stripping. Porous anodes alone are subject to clogging with moderate- or high-loading cathodes. Here we discovered it is necessary to seek synergy from our separator and anode pair to deliver delocalized Li+ to the anode and then uniformly plate Li metal over the large surface areas of the porous anode. Our polymer composite separator containing a solid-state electrolyte (SE) can provide numerous Li+ passages through the percolated SE and pore networks. Our finite element analysis and comparative tests disclosed the synergy between the homogeneous Li+ flux and current density reduction on the anode. Our composite separators have induced compact and uniform Li plating with robust inorganic-rich solid electrolyte interphase layers. The porous anode decreased the nucleation overpotential and interfacial contact impedance during Li plating. Full cell tests with LiFePO4 and Li[Ni0.8Mn0.1Co0.1]O2 (NMC811) exhibited remarkable cycling behaviors: ∼80% capacity retention at the 750th and 235th cycle, respectively. A high-loading NMC811 (4 mAh cm-2) full cell displayed maximum cell-level energy densities of 334 Wh kg-1 and 783 Wh L-1. This work proposes a solution for raising energy density by adopting Li metal, which could be a viable option considering only incremental advancement in conventional cathodes lately.

New potential substitute of PVDF binder: poly(propylene carbonate) for solvent-free manufacturing high-loading cathodes of LiFePO4|Li batteries

New potential substitute of PVDF binder: poly(propylene carbonate) for solvent-free manufacturing high-loading cathodes of LiFePO4|Li batteries

Weakly coordinated Li ion in single-ion-conductor-based composite enabling low electrolyte content Li-metal batteries

The pulverization of lithium metal electrodes during cycling recently has been suppressed through various techniques, but the issue of irreversible consumption of the electrolyte remains a critical challenge, hindering the progress of energy-dense lithium metal batteries. Here, we design a single-ion-conductor-based composite layer on the lithium metal electrode, which significantly reduces the liquid electrolyte loss via adjusting the solvation environment of moving Li+ in the layer. A Li||Ni0.5Mn0.3Co0.2O2 pouch cell with a thin lithium metal (N/P of 2.15), high loading cathode (21.5 mg cm−2), and carbonate electrolyte achieves 400 cycles at the electrolyte to capacity ratio of 2.15 g Ah−1 (2.44 g Ah−1 including mass of composite layer) or 100 cycles at 1.28 g Ah−1 (1.57 g Ah−1 including mass of composite layer) under a stack pressure of 280 kPa (0.2 C charge with a constant voltage charge at 4.3 V to 0.05 C and 1.0 C discharge within a voltage window of 4.3 V to 3.0 V). The rational design of the single-ion-conductor-based composite layer demonstrated in this work provides a way forward for constructing energy-dense rechargeable lithium metal batteries with minimal electrolyte content.

Rational Design of a High-Loading Polysulfide Cathode and a Thin-Lithium Anode for Developing Lean-Electrolyte Lithium-Sulfur Full Cells.

Lithium-sulfur cells are attractive energy-storage systems because of their high energy density and the electrochemical utilization rates of the high-capacity lithium-metal anode and the low-cost sulfur cathode. The commercialization of high-performance lithium-sulfur cells with high discharge capacity and cyclic stability requires the optimization of practical cell-design parameters. Herein, a carbon structural material composed of a carbon nanotube skeleton entrapping conductive graphene is synthesized as an electrode substrate. The carbon structural material is optimized to develop a high-loading polysulfide cathode with a high sulfur loading capacity (6-12mg cm-2 ), rate performance (C/10-C/2), and cyclic stability for 200 cycles. A thin lithium anode based on the carbon structural material is developed and exhibits long lithium stripping/plating stability for ≈2500h with a lithium-ion transference number of 0.68. A lean-electrolyte lithium-sulfur full cell with a low electrolyte-to-sulfur ratio of 6µL mg-1 is constructed with the designed high-loading polysulfide cathode and the thin lithium anode. The integration of all the critical cell-design parameters endows the lithium-sulfur full cell with a low negative-to-positive capacity ratio of 2.4, while exhibiting stable cyclability with an initial discharge capacity of 550 mAh g-1 and 60% capacity retention after 200 cycles.

All-fluorinated electrolyte for non-flammable batteries with ultra-high specific capacity at 4.7 V

Li metal batteries (LMBs) with LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes could release a specific energy of >500 Wh kg−1 by increasing the charge voltage. However, high-nickel cathodes working at high voltages accelerate degradations in bulk and at interfaces, thus significantly degrading the cycling lifespan and decreasing the specific capacity. Here, we rationally design an all-fluorinated electrolyte with addictive tri(2,2,2-trifluoroethyl) borate (TFEB), based on 3, 3, 3-fluoroethylmethylcarbonate (FEMC) and fluoroethylene carbonate (FEC), which enables stable cycling of high nickel cathode (LiNi0.8Co0.1Mn0.1O2, NMC811) under a cut-off voltage of 4.7 V in Li metal batteries. The electrolyte not only shows the fire-extinguishing properties, but also inhibits the transition metal dissolution, the gas production, side reactions on the cathode side. Therefore, the NMC811||Li cell demonstrates excellent performance by using limited Li and high-loading cathode, delivering a specific capacity >220 mA h g−1, an average Coulombic efficiency >99.6% and capacity retention >99.7% over 100 cycles.

A facile in-situ polymerization of cross-linked Poly(ethyl acrylate)-Based gel polymer electrolytes for rechargeable aluminum batteries

Rechargeable aluminum batteries are of interest owing to the nonflammability of Al metal anode and the ionic liquid electrolytes together with the low cost and high capacity of Al metal anode. However, the ionic liquid electrolytes are also moisture sensitive and highly corrosive, bringing about irreversible activity loss, undesired gas production and destructive leakage corrosion, which thus hinder the practical application of rechargeable aluminum batteries. Herein, a gel polymer electrolyte is designed via in-situ cross-linking polymerization of ethyl acrylate (EA) monomer and pentaerythritol acrylate (PETEA) crosslinker in high molar ratio of AlCl3/1-ethyl-3-methylimidazolium chloride (EMIC) ionic liquid. This gel polymer electrolyte exhibits an ionic conductivity of 1.46 × 10−3 S cm−1, a wide electrochemical window up to 3.0 V (vs. Al), alleviated moisture sensitivity and appreciable interfacial stability at room temperature. The assembled solid-state Al//graphite batteries with the gel polymer electrolyte deliver stable capacities of ∼90 mAh g−1 for 1000 cycles at the current density of 100 mA g−1 at both ambient temperature and −10 °C. Even with high-loading graphite cathode of 11 mg cm−2, capacities of ∼60 mAh g−1 can still be obtained for 300 cycles. This work provides a promising strategy for developing reliable and flexible rechargeable aluminum batteries.

Self-Assembled Macrocyclic Copper Complex Enables Homogeneous Catalysis for High-Loading Lithium-Sulfur Batteries.

The practical viability of high energy density lithium-sulfur (Li-S) batteries stipulates the use of a high-loading cathode and lean electrolyte. However, under such harsh conditions, the liquid-solid sulfur redox reaction is much-retarded due to the poor sulfur and polysulfides utilization, leading to low capacity and fast fading. Herein, a self-assembled macrocyclic Cu(II) complex (CuL) is designed as an effective catalyst to homogenize and maximize the liquid-involved reaction. The four-N atoms coordinated Cu(II) ion features a planar dsp 2 hybridization, showing a strong bonding affinity towards lithium polysulfides (LiPSs) along the dz 2 orbital via steric effect. Such a structure not only lowers the energy barrier of the liquid-solid conversion (Li2 S4 to Li2 S2 ) but also guides a 3D deposition of Li2 S2 /Li2 S. As such, with a 1 wt% electrolyte additive of CuL, a high initial capacity of 925 mAh g-1 and areal capacity of 9.62 mAh cm-2 with a low decay of 0.3%/cycle can be achieved under a high sulfur loading of 10.4mg cm-2 and low electrolyte/sulfur ratio of 6μL mgs -1 . This work is expected to inspire the design of homogenous catalysts and accelerate the uptake of high-energy-density Li-S batteries. This article is protected by copyright. All rights reserved.

Sandwich-Structured Quasi-Solid Polymer Electrolyte Enables High-Capacity, Long-Cycling, and Dendrite-Free Lithium Metal Battery at Room Temperature.

The insufficient ionic conductivity, limited lithium-ion transference number (tLi +), and high interfacial impedance severely hinder the practical application of quasi-solid polymer electrolytes (QSPEs). Here, a sandwich-structured polyacrylonitrile (PAN) based QSPE is constructedin which MXene-SiO2 nanosheets act as a functional filler to facilitate the rapid transfer of lithium-ion in the QSPE, and a polymer and plastic crystalline electrolyte (PPCE) interface modification layer is coated on the surface of the PAN-based QSPE of 3wt.% MXene-SiO2 (SS-PPCE/PAN-3%) to reduce interfacial impedance. Consequently, the synthesized SS-PPCE/PAN-3% QSPE delivers a promising ionic conductivity of ≈1.7mScm-1 at 30°C, a satisfactory tLi + of 0.51, and a low interfacial impedance. As expected, the assembled Li symmetric battery with SS-PPCE/PAN-3% QSPE can stably cycle more than 1550h at 0.2 mA cm-2 . The Li||LiFePO4 quasi-solid-state lithium metal battery (QSSLMB) of this QSPE exhibits a high capacity retention of 81.5% after 300 cycles at 1.0C and at RT. Even under the high-loading cathode (LiFePO4 ≈10.0mgcm-2 ) and RT, the QSSLMB achieves a superior area capacity and good cycling performance. Besides, the assembled high voltage Li||NMC811(loading≈7.1 mgcm-2 ) QSSLMB has potential applications in high-energy fields.

Long-term cycling quasi-solid-state lithium batteries enabled by 3D nanofibrous TiO2−x@Li anodes and in-situ polymerized gel-electrolytes

Lithium (Li) metal battery is a promising next generation energy storage system due to its high energy density, but what hinders its commercialization is the safety hazard of Li-anode, especially under high current densities. Here, we report a dual strategy of using electronic conductive black TiO2−x nanofiber films to construct composite Li-metal anodes with stable 3D networks and applying an in-situ polymerized ionic conductive gel-electrolyte to construct efficient quasi-solid-state Li-batteries (QSSLBs). The 3D nanofibrous Li-anode shows a stable and small nucleation barrier and can run stably (>1600 h) at a high current density of 10 mA/cm2. When matching with high-loading cathodes of LiFePO4, the QSSLBs exhibit excellent long-term cycling stability (>500 cycles) and high-rate capability (>1 C). In addition, the in-situ polymerization strategy can be incorporated with the commercial lamination manufacturing to produce 63-Ah pouch cells of LiFePO4||graphite, which deliver a high initial Coloumbic efficiency, a large energy density at 0.3 C, excellent rate capability from 0.25 to 2 C, and long-term cycling performance at 0.3 and 1 C, showing potential commercial prospects.

Ferrocene-Based Artificial Interfacial Layer for High-Performance Lithium Metal Anodes: Continuous Regulation of Li+ Diffusion Behavior.

The diversified design of hybrid artificial layers is a promising method for suppressing the Li dendrite growth and maintaining high Colombic efficiency of lithium (Li) metal anode. Previously, various kinds of organic/inorganic hybrid artificial layers were constructed on the Li metal anode and possessed a positive effect on electrochemical performance. However, the tunable synthesis of artificial layers to continuously regulate the Li diffusion behavior remains a challenge. In this work, the Li diffusion behavior could be tuned by modulating the proportion of components (LiClO4, PMMA and ferrocene (Fc)) in the hybrid artificial layer (LF layer). After optimizing the proportion of each component, the resultant artificial SEI layer exhibits a high Li+ transference number (tLi+ = 0.66) and a high Young's modulus (4.8 GPa). Based on the excellent properties of the as-constructed Fc-based artificial SEI layer, a high-performance lithium anode with no volume effect and dendrite growth is achieved. The Li||Li symmetric cells with a Fc-based artificial SEI layer yielded a stable cycle performance for 1500 h with a high current density of 10 mA cm-2. The pouch cell with LF@Li anode coupled with high-loading LiFePO4 cathode (12.8 mg cm-2) exhibits excellent cyclic stability for 250 cycles with a capacity retention of 75% at 0.5C rate.

Artificial Graphite Paper as a Corrosion‐Resistant Current Collector for Long‐Life Lithium Metal Batteries

AbstractThe employment of ultra‐thin lithium metal anode with high loading cathode is the key to realizing high‐energy‐density rechargeable lithium batteries. Ultra‐thin lithium foils are routinely loaded on a copper substrate in batteries, however, the close contact of these two metals causes galvanic corrosion in the presence of electrolyte, which results in irreversible consumption of lithium and decomposition of electrolyte. Herein, a lightweight and highly conductive flexible graphite paper (GP) is applied to replace Cu foil as the current collector for lithium metal anode. It is demonstrated that the application of GP prevents galvanic corrosion and maintains intimate and steady contact between Li foil and GP current collector during cycling, thereby improving the electrochemical performance of the battery. A 1.08 Ah pouch cell assembled with Li@GP anode and LiNi0.8Co0.1Mn0.1O2 cathode exhibits a long lifetime of 240 cycles with a capacity retention of 91.6% under limited Li, high cathode loading and lean electrolyte conditions.

A Two-in-one host for High-loading cathode and Dendrite-free anode realized by activating metallic nitrides heterostructures toward Li-S full batteries

Lithium-sulfur (Li-S) batteries with high energy densities have attracted much attention as next-generation energy storage systems. However, the uncontrollable lithium dendrite growth at the anode and severe lithium polysulfides (LiPSs) shuttling at the cathode drastically hinder the commercial viability of Li-S batteries. Herein, the dual-functional nanosheet arrays supported by carbon cloth implanted with Ni3N/FeNi3N nanoparticles that simultaneously boosts the performance of the sulfur cathode and the lithium anode is developed. Computational results indicate that the Ni3N/FeNi3N endowed the cathode host with strong chemical anchoring and exceptional electrocatalytic activity for LiPSs. Through effective adjustment of the iron content, the optimized Ni3N/FeNi3N-0.2 heterostructure interface offers highly efficient bidirectional conversion kinetics of sulfur electrochemistry. Meanwhile, the Ni3N/FeNi3N-0.2 with superior lithiophilic nature guides uniform lithium deposition for inhibiting dendrite growth. Combined with these merits, the full battery (denotes as S@Ni3N/FeNi3N-0.2||Li@Ni3N/FeNi3N-0.2) with a sulfur loading (3.4 mg cm−2) exhibits a high specific capacity of 1270 mAh g−1 after 100cycles, super rate capability up to 5.0C and long cycle life of over 500cycles. This work provides a promising avenue for developing high-energy–density Li-S full batteries toward practical applications.

Single-Ion Conducting Multi-block Copolymer Electrolyte for Lithium-Metal Batteries with High Mass Loading NCM811 Cathodes

Lithium-metal batteries comprising a single-ion conducting polymer electrolyte and a nickel-rich LiNi1-x-yCoxMnyO2 (NCM) positive electrode (cathode) potentially offer very high energy density and great safety. However, such cell chemistry is very demanding concerning the required interfacial stability of the polymer electrolyte, and the realization of high mass loading cathodes remains a great challenge. Herein, the development of a new single-ion conducting multi-block copolymer electrolyte including trifluoromethyl groups in the ionophilic block is reported. After ethylene carbonate (EC) is incorporated into the self-standing and easily processable polymer membranes, high ionic conductivity along with very high limiting current density and suitable anodic stability are obtained. These enable stable cycling of Li∥NCM811 cells─also at high C rates (up to 5C) and active material mass loadings of the NCM811 cathode of >10 mg cm–2, which are both key steps toward the potential commercialization of this class of electrolytes.

Gradient design for constructing artificial SEI layer towards high-performace Lithium metal batteries

The construction of artificial interfacial layer on Li anode is one of the most effective methods to block Li dendrite growth and volume expansion. The charge transport and ion diffusion behavior can be regulated due to the variation of component gradients and diffusion kinetics at different depths. However, there are few researches on the regulation of components’ distribution in artificial interfacial layer (SEI layer), which is of great significance for enhancing the electrochemical performance of Li anode. Herein, a gradient-design SEI layer is constructed on the Li anode to regulate charge transport and Li ion diffusion behavior in the interface, which could optimize the lithium deposition process. Based on this gradient structure, the gradient distribution of inorganic and organic components in the as-constructed SEI can effectively regulate the Li+ configuration and hinder the volume change during Li plating/stripping progress. With this hybrid interfacial layer, an improved cycling performance of Li-Li symmetric cell is achieved over 1750 h with a low overpotential under an ultrahigh current density of 10 mA cm−2, and ultrahigh capacity of 10 mAh cm−2. Based on the gradient-design artificial SEI film, the pouch cells matched with high-loading LiFePO4 cathode (21 mg cm−2) demonstrates extremely long cycling life with almost no capacity fade, which is superior compared with previous reports.

Covalent netting restrains dissolution enabling stable high-loading and high-rate iron difluoride cathodes.

Metal fluoride conversion cathodes are promising for the production of cheap, sustainable, and high-energy lithium-ion batteries. Yet, such systems are plagued by active material dissolution that causes capacity fade and hinders commercialization. Here, a covalent netting strategy is proposed to overcome this hurdle. In a proof-of-concept design, polydopamine derived carbon-mediated covalent binding inhibited the dissolution, while the pyrolyzed bacterial cellulose netting structure furnished fast electronic and ionic transport pathways. We demonstrate high-capacity, high-rate and long-lasting stability attained at practical loading levels. Our investigations suggest that the covalent netting-enabled formation of a robust and efficient blocking layer, highly competent in suppressing the leaching, is key for a stable performance. The successful stabilization of metal difluorides in the absence of electrolyte engineering opens an avenue for their practical deployment in future higher-level but lower-cost batteries, and provides a solution to similar challenges encountered by other dissolving energy electrode materials.

A low-self-discharge high-loading polysulfide cathode design for lithium–sulfur cells

A low-self-discharge lithium–sulfur cell with a carbonized electrospun nanofiber substrate attains a long shelf life and stable electrochemistry with a capacity-fade rate of 0.26% per day and a long cycle life of 200 cycles after resting for 90 days.

Polymer Electrolyte/Sulfur Double-Shelled Anisotropic Reduced Graphene Oxide Lamellar Scaffold Enables Stable and High-Loading Cathode for Quasi-Solid-State Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs) can replace lithium-ion batteries by delivering a higher specific capacity. However, the areal capacity of current LSBs is low because the intrinsic limitations of sulfur make achieving a high sulfur loading difficult. Herein, the authors report vertically aligned reduced graphene oxide (rGO) with sulfur and poly(ethylene oxide)-based polymer electrolyte double-shell layers (VRG@S@PPE) as a high-loading sulfur cathode. The addition of vapor-grown carbon fiber (VGCF) into rGOis the key to success, as it allows for gas evacuation from internal nano/micropores without structural collapse, enabling perfect double-shell layer contact. Owing to the anisotropic rGO lamellar structure that enables straightforward ion/electron transport and provides numerous active sites, sulfur-infiltrated rGO reinforced via VGCF (VRG@S)exhibits a high capacity of 998 mAh g-1 after 100 cycles at 0.1 C under high sulfur loading (6mg cm-2 ). Interestingly, an additional polymer electrolyte layer further increases the cycle retention (1005 and 718 mAh g-1 after 100 cycles at 0.1 and 1 C, respectively), because intimate contact between the solid polymer electrolyte and sulfur could suppress the loss of sulfur due to lithium polysulfide (LPS) shuttling or volume change during lithiation/delithiation. Therefore, it is possible to realize safe and stable quasi-solid-state LSBs with high sulfur loading.

Enabling uniform Li deposition behavior by introducing a NO3−-based ionic liquid additive into carbonate electrolyte for high-voltage Li metal batteries

The nonuniform lithium deposition behavior and low deposition/dissolution reversibility are the most significant obstacles for practical high-energy-density lithium metal batteries (LMBs). Herein, a novel 1-ethyl-3-methylimidazolium nitrate ionic liquid ([EMIm][NO3] IL) is proposed to incorporate into the conventional carbonate electrolyte with a small amount of 1,2-dimethoxyethane (DME) as the cosolvent. A high solubility of 0.5 M [EMIm][NO3] in the carbonate electrolyte is achieved for high-voltage LMBs by replacing traditional lithium nitrate with [EMIm][NO3] IL, where the DME cosolvent with high donicity enables the solvation of NO3− in the electrolyte system. Benefitting from the electrochemical reduction of NO3− anions, the designed electrolyte promotes the formation of highly conductive and stable solid electrolyte interface abundant with N-containing species and achieves stable Li stripping/plating behavior. As a result, the IL-modified electrolyte enables excellent electrochemical performances with improved Coulombic efficiency (>98.5%) in Li|Cu cell and stable cyclability (900 h) in Li|Li symmetric cell, respectively. More importantly, a Li|LiNi0.8Co0.1Mn0.1O2 pouch-type battery composed of high mass loading cathode (20 mg cm−2) and thin Li foil (50 μm) maintains an impressive cycling lifespan of 100 cycles. The exploration of NO3− containing IL as a novel electrolyte additive offers a promising opportunity for achieving high-performance Li metal batteries.

Cooperative stabilization by highly efficient nanoseeds and reinforced interphase toward practical Li metal batteries

The practical implementation of Li metal has been severely obstructed by the uncontrolled dendritic Li growth and poor cycling efficiency. Herein, highly lithiophilic, ultrathin (∼60 nm) and conformal bismuth-oxygen-carbon layer-modified carbon fibers (CF@BOC) first prepared from the bismuth-based MOF membrane self-assembly were rationally adopted to stabilize Li metal. Highly efficient ultrasmall (∼1.8 nm) bismuth seeds and in-situ generated Li2O-enriched interphase can cooperatively enable the homogeneous Li nucleation/growth and extraordinarily high Li utilization efficiency. Consequently, the modified Li metal exhibits ultrahigh rate capability (10 mA cm−2) and ultralong lifespan stability (6900 cycles). Impressively, the Li|LiFePO4 full cell delivers an exceptional long-term cycling over 200 cycles under the rather harsh condition of low negative-to-positive-capacity (N/P) ratio (∼0.44) and electrolyte-to-capacity (E/C) ratio (5 g Ah−1). And the Li|LiCoO2 full cell also reveals a prolonged cycling performance even at the ultralow N/P ratio (∼0.26) with a remarkable energy density of 361.3 Wh kg−1. Furthermore, the pouch cell with a high loading cathode (3.6 mAh cm−2) still demonstrates prolonged cycling lifespan under the practical condition of extremely limited Li metal and lean electrolyte. This work enlightens a significant stride toward highly stable Li metal anode for practicability.