Application Of Li Metal Batteries Research Articles

Surface fluorination of nickel nanowires enabling LiF-rich nanoscale solid electrolyte interface for stable lithium anodes

Lithium (Li) metal has become a research hotspot for anodes materials due to its ultra-high theoretical capacity and the lowest redox potential. However, the practical application of Li metal batteries is hampered by the formation of uncontrollable Li dendrites and the irreversible structural changes during long-term charge/discharge processes. Developing stable Li metal anode with uniform Li deposition is highly desirable. Herein, surface fluorination of nickel nanowires enabling LiF-rich nanoscale solid electrolyte interface was demonstrated for stable Li anodes. Free-standing three-dimensional (3D) nickel nanowires (NiNWs) current collector decorated with lithiophilic NiF2 nanosheets (NiNWs@NiF2) was constructed via a simple and scalable fluorination strategy. Theoretical and experimental analysis confirmed that the lithiophilic surface of NiF2 nanosheets could reduce the Li nucleation barrier, facilitating uniform Li ion deposition. The 3D conductive NiNWs network enabled fast electron transfer and mitigated volume changes during cycling. Additionally, a LiF-rich nanoscale solid electrolyte interface (SEI) layer formed between Li and the electrolyte significantly improved the interfacial stability. As a result, the as-assembled Li-NiNWs@NiF2 symmetrical cell provided a superior electrochemical performance, maintaining stability for 2500 h at 1.0 mA cm−2 and 900 h at 5.0 mA cm−2. Furthermore, the assembled Li-NiNWs@NiF2|| LiFePO4 (LFP) full cell demonstrated exceptional capacity retention of 93.9 % after 2000 cycles at a rate of 5C. Overall, the unique structure of NiNWs@NiF2 not only offers a straightforward method for designing a 3D lithiophilic host, but also provides the concept of interfacial engineering through the in-situ construction of an artificial LiF-rich nanoscale SEI layer.

Recent advances in robust and ultra‐thin Li metal anode

AbstractLi metal batteries have been widely expected to break the energy‐density limits of current Li‐ion batteries, showing impressive prospects for the next‐generation electrochemical energy storage system. Although much progress has been achieved in stabilizing the Li metal anode, the current Li electrode still lacks efficiency and safety. Moreover, a practical Li metal battery requires a thickness‐controllable Li electrode to maximally balance the energy density and stability. However, due to the stickiness and fragile nature of Li metal, manufacturing Li ingot into thin electrodes from conventional approaches has historically remained challenging, limiting the sufficient utilization of energy density in Li metal batteries. Aiming at the practical application of Li metal anode, the current issues and their initiation mechanism are comprehensively summarized from the stability and processability perspectives. Recent advances in robust and ultra‐thin Li metal anode are outlined from methodology innovation to provide an overall insight. Finally, challenges and prospective developments regarding this burgeoning field are critically discussed to afford future outlooks. With the development of advanced processing and modification technology, we are optimistic that a truly great leap will be achieved in the foreseeable future toward the industrial application of Li metal batteries.

In Situ-Initiated Poly-1,3-dioxolane Gel Electrolyte for High-Voltage Lithium Metal Batteries.

To realize high-energy-density Li metal batteries at low temperatures, a new electrolyte is needed to solve the high-voltage compatibility and fast lithium-ion de-solvation process. A gel polymer electrolyte with a small-molecular-weight polymer is widely investigated by combining the merits of a solid polymer electrolyte (SPE) and liquid electrolyte (LE). Herein, we present a new gel polymer electrolyte (P-DOL) by the lithium difluoro(oxalate)borate (LiDFOB)-initiated polymerization process using 1,3-dioxolane (DOL) as a monomer solvent. The P-DOL presents excellent ionic conductivity (1.12 × 10-4 S cm-1) at -20 °C, with an oxidation potential of 4.8 V. The Li‖LiCoO2 cell stably cycled at 4.3 V under room temperature, with a discharge capacity of 130 mAh g-1 at 0.5 C and a capacity retention rate of 86.4% after 50 cycles. Moreover, a high-Ni-content LiNi0.8Co0.1Mn0.1O2 (NCM811) cell can steadily run for 120 cycles at -20 °C, with a capacity retention of 88.4%. The underlying mechanism of high-voltage compatibility originates from the dense and robust B- and F-rich cathode interface layer (CEI) formed at the cathode interface. Our report will shed light on the real application of Li metal batteries under all-climate conditions in the future.

Engineering of lithiophilic hosts for stable lithium metal anodes

Lithium (Li0) metal has been deemed the desired anode for the future of cutting-edge rechargeable Li batteries benefiting from its lowest reduction potential and ultrahigh theoretical specific capacity. Nevertheless, the large-scale applications of Li metal batteries are restricted by scattered Li dendrite formation and uncontrollable volume expansion. To address these issues, a currently prevalent measure is to use structured lithiophilic hosts for Li metal. The enhanced lithiophilicity of hosts is significant for regulating the Li nucleation barrier. By virtue of these lithiophilic measures, the Li nucleation sites will be well controlled and the Li plating layer will be more stable. Through this article, we classified various lithiophilic hosts and described their applications for Li metal batteries, including heteroatom-doping carbon, lithiophilic-material loading hosts and gradient skeletons. We discussed the inherent advantages and lithophilic mechanisms of these hosts on optimizing the lithophilic properties and analyzed various factors that induced the formation of dendrite Li. Moreover, the review outlines the current challenges and perspectives for Li metal anodes, and some understanding of the lithiophilic chemistry is given.

Two-in-one strategy: Discretely functionalized electrolyte additive for stable lithium metal batteries coupled with Ni-rich cathode

Li metal batteries (LMBs) coupled with Ni-rich cathode are regarded as a holy grail to achieve high energy density for the application in electric vehicles. However, the practical applications of LMBs coupled with Ni-rich cathode are limited by the severe Li dendrite growth and structural deterioration of the Ni-rich cathode. Among the various strategies to address these undesirable issues, introducing a dual-functional electrolyte additive is considered as an attractive approach because it can construct beneficial interface on both electrodes with a single agent. Herein, the two-in-one electrolyte additive, calcium tetrafluoroborate (Ca(BF4)2), is proposed for the rational design of interfacial layers on both Li metal anode and Ni-rich cathode. The preferential reduction of Ca2+ formed the Ca-based SEI layer which prevents electrolyte decomposition. In particular, Li-Ca alloy with superior lithiophilicity suppresses the growth of Li dendrite by reducing the nucleation polarization. Concurrently, the preferential oxidation of BF4− in Ca(BF4)2 results in the formation of B-based surface film on the Ni-rich cathode, which protects the Ni-rich cathode from structural deterioration, including micro-crack and dissolution of transition metal ion. As a result of unique characteristics of Ca(BF4)2 as an electrolyte additive, outstanding electrochemical performance can be accomplished in LMBs configured with Ni-rich cathode in carbonate electrolyte.

Sp-Carbon-Conjugated Organic Polymer as Multifunctional Interfacial Layers for Ultra-Long Dendrite-Free Lithium Metal Batteries.

Fatal issues in lithium metal anodes (LMA), such as detrimental lithium dendrites growth and fragile solid-electrolyte interphase (SEI) during the Li plating/stripping process, often hinder the practical application of Li metal batteries (LMBs). Herein, cobalt-coordinated sp-carbon-conjugated organic polymer (Co-spc-COP) is constructed as the protective layer for regulating the interface stability of LMA. The unique synergistic beneficial effect of organic functional groups (C≡C linkage, C=N units and aromatic rings) and Co sites not only regulate the Li+ coordination environment and rearrange Li+ concentration to facilitate its transport by optimizing the electronic density, enhancing the compatibility with electrolyte interface and supplying "external magnetic driving strategy", but also strengthens the interfacial stiffness with high Young's modulus to better withstand the mechanical stress. These beneficial effects and relative underlying working mode and mechanism of uniform Li plating and rapid Li+ migration on the Co-spc-COP are also revealed by various in situ/ex situ experimental technologies and theory calculation. The Co-spc-COP-based cell delivers an extraordinary lifespan of 6600 h and ultrahigh capacity retention of 78.3 % (111.9 mAh g-1) after 1000 cycles at 1 C. This demonstrated synergistic strategy in Co-coordinated organic polymer may gain new insights to regulate the uniform and non-dendritic deposition/dissolution behaviors for highly stable LMBs.

Sp‐Carbon‐Conjugated Organic Polymer as Multifunctional Interfacial Layers for Ultra‐Long Dendrite‐Free Lithium Metal Batteries

AbstractFatal issues in lithium metal anodes (LMA), such as detrimental lithium dendrites growth and fragile solid‐electrolyte interphase (SEI) during the Li plating/stripping process, often hinder the practical application of Li metal batteries (LMBs). Herein, cobalt‐coordinated sp‐carbon‐conjugated organic polymer (Co‐spc‐COP) is constructed as the protective layer for regulating the interface stability of LMA. The unique synergistic beneficial effect of organic functional groups (C≡C linkage, C=N units and aromatic rings) and Co sites not only regulate the Li+ coordination environment and rearrange Li+ concentration to facilitate its transport by optimizing the electronic density, enhancing the compatibility with electrolyte interface and supplying “external magnetic driving strategy”, but also strengthens the interfacial stiffness with high Young's modulus to better withstand the mechanical stress. These beneficial effects and relative underlying working mode and mechanism of uniform Li plating and rapid Li+ migration on the Co‐spc‐COP are also revealed by various in situ/ex situ experimental technologies and theory calculation. The Co‐spc‐COP‐based cell delivers an extraordinary lifespan of 6600 h and ultrahigh capacity retention of 78.3 % (111.9 mAh g−1) after 1000 cycles at 1 C. This demonstrated synergistic strategy in Co‐coordinated organic polymer may gain new insights to regulate the uniform and non‐dendritic deposition/dissolution behaviors for highly stable LMBs.

Regulating Lithium Nucleation at the Electrolyte/Electrode Interface in Lithium Metal Batteries

AbstractLithium (Li) metal has emerged as a viable alternative anode material to address the current energy density shortfalls in Li batteries. However, its integration into widespread implementation remains somewhat constrained due to the substandard reversibility issues and safety concerns arising from erratic Li deposition. To effectively tackle these obstacles, considerable endeavors have been exerted to modulate the morphology of Li deposition. Nevertheless, it is exceedingly challenging for Li nuclei that tend to dendritic growth thermodynamically to transform into dense Li morphologies during their growth process. Therefore, it is crucial to understand what influences the formation process of Li nuclei and how to improve the state of Li nuclei. Herein, Li nucleation mechanisms involving mass transport across the solid electrolyte interface from electrolyte to electrode and electrode interfacial reactions are elucidated. Inspired by the understanding of Li nucleation, the corresponding design principles, including enhancing and homogenizing mass transport, stabilizing solid electrolyte interface film, and regulating surface interaction/selection, are summarized for optimizing Li nucleation and further inducing dendrite‐free Li deposition. In light of the competition among these design principles, a perspective on the existing challenges and opportunities for further promoting the application of Li metal batteries is proposed.

Compressible and Elastic Reduced Graphene Oxide Sponge for Stable and Dendrite-Free Lithium Metal Anodes.

Dendritic Li deposition, an unstable solid-electrolyte interphase (SEI), and a nearly infinite relative volume change during cycling are three major obstacles to the practical application of Li metal batteries. Herein, we introduce a compressible and elastic reduced graphene oxide sponge (rGO-S) to simultaneously eliminate Li dendrite growth, stabilize the SEI, and accommodate the volume change. The volume change is contained by compressing and expanding the rGO-S anode, which effectively releases the Li plating-induced stress during cycling. The smooth and dense Li metal is deposited on rGO-S without dendrites, which preserves the SEI, reduces consumption of the electrolyte, and prevents the formation of Li debris. The half-cells employing rGO-S show a steady and high Coulombic efficiency. The Li@rGO-S symmetric cells demonstrate excellent cycling stability over 1200 cycles with a low overpotential. When paired with LiFePO4 (LFP), the Li@rGO-S||LFP full cells exhibit a high specific capacity (150.3 mAh g-1 at 1C), superior rate performance, and good capacity retention.

“Three in one” 3D mixed skeleton design enables dendrite-free Li metal batteries

A 3D mixed ion/electron-conducting skeleton based on the lithiophilic h-MoS2-NC host with an inorganic-rich SEI layer is fabricated for balancing lithiophilicity, ionic, and electronic conductivity, and for improving the stability of LMAs.

Glycerol-tailored asymmetric polyethersulfone membranes with uniform ion transport for stable lithium metal batteries

Advancing the performance and stability of lithium metal batteries is crucial for future energy storage devices. One of the major challenges for practical applications of Li metal batteries is to mitigate the formation of Li dendrites during cycling. In this work, we prepared a series of asymmetrically structured polyethersulfone (PES) membranes, consisting of a nanoporous skin layer and a bulk with macrovoids, by incorporating different amounts of glycerol during membrane preparation. Under optimal conditions, the asymmetric PES membrane made with 1.2 wt% of glycerol (PES-G1.2) possesses a thin skin layer with a uniform nanopore distribution, which is ideal for regulating the ion flux near the Li anode surface, thus suppressing Li dendrite formation. Our results demonstrate that the PES-G1.2 possesses exceptional ionic conductivity of 1.76 mS cm−1, Li+ transference number of 0.52, and high compatibility with Li electrode. Additionally, the Li/PES-G1.2/LiFePO4 cells also present a remarkable rate capability with specific capacity of 150 mAh g−1 at 0.2 C and 81 mAh g−1 at 10 C, respectively, and 90 % of capacity can be retained after 100 charge-discharge cycles under 0.2 C. These findings shed light on the unique properties of asymmetric porous membrane as well as its promising potential for applications in lithium metal batteries.

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.

Designing Polymer Electrolytes via Ring‐Opening Polymerization for Advanced Lithium Batteries

AbstractReplacing liquid electrolytes with solid‐state polymer electrolytes (SPEs) can solve the safety hazards of Li metal batteries (LMBs) while increasing their energy density. However, there has been limited success so far in preparing advanced SPEs with controllable molecular structure and chemical composition, posing great obstacles to further promoting its application in LMBs. Recently, ring‐opening polymerization (ROP), including cationic ROP, anionic ROP, and ring‐opening metathesis polymerization, has become a dazzling new star in achieving SPEs due to its mild polymerization conditions and controllable chemical composition (molecular structure, functional group), etc. Besides, there is no small molecule released during the polymerization process, which means reduced interfacial side reaction. Hence, in this review, the merits of ROP in preparing SPEs and its mechanism as well as interfering factors, etc are evaluated from the perspective of synthetic chemistry. Furthermore, the review focuses on outlining the existing cases related to ROP as much as possible and summarize them from different ring structures (from triple ring to multivariate ring) and polymerization methods, hoping to provide a comprehensive understanding and serve as strategic guidance for designing high‐performance SPEs. Challenges and opportunities regarding this burgeoning field are also discussed at the end.

ZnO@C Coated Cellulose-Based Separators Control Lithium Deposition Direction to Stable Lithium Metal Batteries.

Li metal anodes have attracted attention due to their high specific capacity and low electrochemical potential. Nevertheless, the uncontrolled growth of Li dendrites hinders the practical application of Li metal batteries. Although the various approaches have made performance improvements, safety hazards still exist since Li dendrites are still growing along the anode to the separator during the continuous plating/stripping process. Herein, a straightforward method is proposed to achieve stable Li metal batteries with directional growth control by using a functional ZnO@C/cellulose membrane as a separator. The abundant pore structure and functional groups of biomass cellulose enhance the Li-ion transport and interface compatibility. The ZnO transforms in situ to form a Li-Zn alloy layer which is uniformly coated to the separator to direct uniform ion concentration polarization and charge distribution polarization, control the growth direction of Li, significantly improve the cycling stability, and promote the reversibility of the Li plating/exfoliation process. As a result, the symmetric cell exhibits an extreme lifetime of more than 4500h and low polarization at 3mAcm-2 . The cycling performance of the Li||LiFePO4 full cell reaches a capacity retention of 98% after 270 cycles at a mass loading of 10mgcm-2 .

Toward a quantitative interfacial description of solvation for Li metal battery operation under extreme conditions

The future application of Li metal batteries (LMBs) at scale demands electrolytes that endow improved performance under fast-charging and low-temperature operating conditions. Recent works indicate that desolvation kinetics of Li+ plays a crucial role in enabling such behavior. However, the modulation of this process has typically been achieved through inducing qualitative degrees of ion pairing into the system. In this work, we find that a more quantitative control of the ion pairing is crucial to minimizing the desolvation penalty at the electrified interface and thus the reversibility of the Li metal anode under kinetic strain. This effect is demonstrated in localized electrolytes based on strongly and weakly bound ether solvents that allow for the deconvolution of solvation chemistry and structure. Unexpectedly, we find that maximum degrees of ion pairing are suboptimal for ultralow temperature and high-rate operation and that reversibility is substantially improved via slight local dilution away from the saturation point. Further, we find that at the optimum degree of ion pairing for each system, weakly bound solvents still produce superior behavior. The impact of these structure and chemistry effects on charge transfer are then explicitly resolved via experimental and computational analyses. Lastly, we demonstrate that the locally optimized diethyl ether-based localized-high-concentration electrolytes supports kinetic strained operating conditions, including cycling down to -60 °C and 20-min fast charging in LMB full cells. This work demonstrates that explicit, quantitative optimization of the Li+ solvation state is necessary for developing LMB electrolytes capable of low-temperature and high-rate operation.

Data-Driven Insight into the Reductive Stability of Ion-Solvent Complexes in Lithium Battery Electrolytes.

Lithium (Li) metal batteries (LMBs) are regarded as one of the most promising energy storage systems due to their ultrahigh theoretical energy density. However, the high reactivity of the Li anodes leads to the decomposition of the electrolytes, presenting a huge impediment to the practical application of LMBs. The routine trial-and-error methods are inefficient in designing highly stable solvent molecules for the Li metal anode. Herein, a data-driven approach is proposed to probe the origin of the reductive stability of solvents and accelerate the molecular design for advanced electrolytes. A large database of potential solvent molecules is first constructed using a graph theory-based algorithm and then comprehensively investigated by both first-principles calculations and machine learning (ML) methods. The reductive stability of 99% of the electrolytes decreases under the dominance of ion-solvent complexes, according to the analysis of the lowest unoccupied molecular orbital (LUMO). The LUMO energy level is related to the binding energy, bond length, and orbital ratio factors. An interpretable ML method based on Shapley additive explanations identifies the dipole moment and molecular radius as the most critical descriptors affecting the reductive stability of coordinated solvents. This work not only affords fruitful data-driven insight into the ion-solvent chemistry but also unveils the critical molecular descriptors in regulating the solvent's reductive stability, which accelerates the rational design of advanced electrolyte molecules for next-generation Li batteries.

Efficient anion solvation modulation in carbonate electrolytes enables high-voltage lithium metal batteries

Developing electrolytes qualified for high-voltage (>4 V vs Li/Li+) conditions is of great significance for high-energy density Li-metal batteries (LMBs). Carbonate-based electrolytes possess high oxidation stability, whereas the uneven Li deposition, low Coulombic efficiency (CE) and poor anodic stability of such electrolytes severely impede the practical application in high-voltage LMBs. Herein, a 1.8 M lithium bis(trifluoromethanesulphonyl)imide (LiTFSI)-carbonate electrolyte with high compatibility with both Li anode and high-voltage cathode is designed. LiNO3 is introduced into the electrolyte as an additive with the assistance of CuF2 cosolvent, which efficiently enables robust and conductive interfaces at both anode and cathode sides. As a consequence, an average CE of 98.0% is achieved for Li||Cu half-cell at 1 mA cm−2. Li||LiNi0.8Co0.1Mn0.1O2 full cell fabricated with cathode areal capacity of 2.4 mAh cm−2 and 5× excess Li achieves a high capacity retention of 80.7% after 200 cycles with cut-off voltage of 4.3 V. This work provides a facile and effective approach to improve the application of carbonate-based electrolytes in high-voltage LMBs.

Recent Progress on the Low‐Temperature Lithium Metal Batteries and Electrolytes

AbstractThe emergence and development of lithium (Li) metal batteries shed light on satisfying the human desire for high‐energy density beyond 400 Wh kg−1. Great efforts are devoted to improving the safety and cyclability of such new‐type batteries, and certain progress is successfully achieved. However, given the diversity of application scenarios, the practical applications of Li metal batteries still remain challenges, especially in extremely low temperatures. The drop in temperature largely reduces the capacity and lifespan of batteries due to sluggish Li‐ion (Li+) transportation and uncontrollable Li plating behaviors. Recently, attention is gradually paid to Li metal batteries for low‐temperature operation, where the explorations on high‐performance low‐temperature electrolytes emerge as a hot topic. In this review, the progress of low‐temperature Li metal batteries is systematically summarized. The challenges and influences of low temperatures on Li metal batteries are concluded. Subsequently, the solutions to low‐temperature Li metal batteries based on electrolyte engineering are reviewed and discussed. Additionally, the techniques for low‐temperature characterizations are classified and discussed. Most importantly, the future development prospects of low‐temperature Li metal batteries are proposed from sustainable perspectives.

Nanophase separated, grafted alternate copolymer styrene-maleic anhydride as an efficient room temperature solid state lithium ion conductor

All solid-state lithium metal batteries (ASSLMBs) based on polymer solid electrolyte and lithium metal anode have attracted much attention due to their high energy density and intrinsic safety. However, the low ionic conductivity at room temperature and poor mechanical properties of the solid polymer electrolyte result in increased polarization and poor cycling stability of the Li metal batteries. In order to improve the ionic conductivity at room temperature while maintaining mechanical strength, we combine the conductivity of short chain polyethylene oxide (PEO) and strength of styrene-maleic anhydride copolymer (SMA) to obtain a grafted block copolymer with nanophase separation structure, which has room temperature ionic conductivity up to 1.14 × 10−4 S/cm and tensile strength up to 1.4 MPa. Li||Li symmetric cell can work stably for more than 1500 h under the condition of 0.1 mA/cm2. Li||LiFePO4 full cells can deliver a high capacity of 151.4 mAh/g at 25 °C and 0.2 C/0.2 C charge/discharge conditions, showing 85.6% capacity retention after 400 cycles. Importantly, the all solid state Li||LiFePO4 pouch cell shows excellent safety performance under different abuse conditions. These results demonstrate that the nanophase separated, grafted alternate copolymer electrolyte has huge potential for application in Li metal batteries.

Regulating the Electron Structure of Covalent Organic Frameworks by Strong Electron‐Withdrawing Nitro to Construct Specific Li+ Oriented Channel

AbstractThe growth of disordered lithium dendrite and the notorious reaction between Li and electrolyte hamper the practical application of Li metal batteries (LMBs). Herein, an artificial solid electrolyte interphase (ASEI) constructed by a nitro‐functionalized covalent organic framework (NO2‐COF) is designed to regulate Li+ deposition and stable Li anodes. Strong electron‐withdrawing nitro groups can gather the surrounding electrons of connected monomer by the donor‐acceptor (D‐A) effect, thus regulating the electron structure of the covalent organic framework (COF) and constructing a specific cation‐oriented channel. The uniform Li+ deposition and inhibition of Li dendrites are achieved under such a high‐selective Li+ transportation channel and regulated surface electric charge. In addition, the nitro can also be reduced to NO2− and further react with Li to produce high ionic‐conductivity Li3N and LiNxOy during the charging/discharging, which contributes to the migration of Li+. As a result, NO2‐COF‐modified symmetrical batteries realize an ultra‐long cycling life of more than 6000 h under a current density of 5 mA cm−2 compared to bare Li and TpBD‐COF/Li (without nitro). The full cells coupled with LiFePO4 stably cycle 1000 times with a capacity retention of 91%. Hence, effectively optimizing electron structure by the donor‐acceptor (D‐A) effect provides a better platform to elevate the performance of LMB.