Commercial LiFePO4 Research Articles

A Method of Efficiently Regenerating Waste LiFePO4 Cathode Material after Air Firing Treatment.

Waste LiFePO4 (LFP) batteries can be harmful to the environment and lead to waste of resources if not properly disposed of. In this study, an efficient and environmentally friendly method for solid-phase recycling waste LFP cathode material (W-LFP) is proposed. Most of the impurities in the W-LFP are removed by air firing. The regenerated LFP is then obtained by adding lithium carbonate and triethanolamine for repair during heat treatment. The addition of triethanolamine converts Fe3+ to Fe2+ and also allows the formation of an N-doped modified carbon layer on the surface of the LFP particles, which improves the electrochemical properties of the regenerated material. Physical characterization and electrochemical tests are used to investigate the attenuation and regeneration mechanism of LFP. The regenerated LFP possesses a high specific discharge capacity (152.87 mAh g-1 at 0.2 C), which is about 95.32% of the commercial LFP, and the capacity retention rate is 88.52% after 600 cycles at 1 C. It is worth noting that we do not use solvents such as acids and alkalis in the regeneration process, thus avoiding the generation of large quantities of acid and alkaline waste liquids, which is friendly to the environment. This solid-phase regeneration process offers a promising method for the future recycling of used LFP batteries because of its simplicity, environmental friendliness, and high efficiency.

Formicarium-Like Micron Porous Si Synergistically Adjusted by Surface Hard-Soft Nanoencapsulation as Long-Life Lithium-Ion Battery Anode.

Micron porous silicon (MPSi) is a promising lithium-ion battery (LIB) anode that can provide enough space to effectively alleviate the volume expansion and large number of transmission channels to rapidly transport the Li-ions. However, a long-term stable MPSi anode at high current density is still a great challenge. Herein, a double-regulated formicarium like-MPSi composite using the surface hard-soft titanium dioxide-few layered MXene nanotemplate (FMPSi@TiO2@FMXene) was designed and synthesized via an in situ assembly strategy as long-life LIB anode. Such hard-soft TiO2-FMXene nanoencapsulation can collaboratively tune the internal/external stress, inhibit the volume expansion, reduce the interfacial reactions, and improve the electrical conductivity of MPSi, resulting in the great enhancement of structural stability and electrochemical performance in cycling even at high current density. Especially, this FMPSi@TiO2@FMXene anode exhibits a high reversible capacity of 1254.9 and 970.4 mAh/g after 500 cycles at 0.5 and 1 A/g, respectively. Moreover, a full cell is assembled with the FMPSi@TiO2@FMXene anode and commercial LiFePO4 (LFP) cathode, exhibiting a high capacity retention rate of 91.6% in 100 cycles. This work provides an effective surface nanoengineering tactic to obtain the structurally stable MPSi anodes by hard-soft nanotemplate for large-scale and long-term LIB application.

Magnesium Fluoride Interlayers Enabled by Wet‐Chemical Process for High‐Performance Solid‐State Batteries

AbstractGarnet‐type solid‐state electrolytes (SSEs) exemplified by Li6.5La3Zr1.5Ta0.5O12 (LLZT) are chemically unstable when exposed to air, leading to the formation of impurities and poor wettability with Li metal. Herein, a protocol to address this Li/LLZT interface challenge is demonstrated by constructing a lithiophilic MgF2 nanofilm on the LLZT pellet. Specifically, a solution‐based process is developed for the surface engineering of LLZT, utilizing magnesium trifluoroacetate (MTF) as the molecular precursor while poly(acrylic acid) (PAA) as the coordinating agent in a sol‐gel process. It is demonstrated that a facile spin‐coating treatment followed by high‐temperature annealing reliably forms crack‐free MgF2 nanofilms with precise thickness control. Introduction an MgF2 interlayer transforms the LLZT pellet into a highly lithophilic, facilitating close contact with the lithium anode, thereby leading to a significantly reduced interfacial resistance from 1190 Ω cm2 to 6 Ω cm2. Such an interfacial engineering enables stable cycling of full batteries with high reversibility and rate capability using commercial LiFePO4 and LiNi0.83Co0.07Mn0.1O2 as cathodes. This study unfolds the possibility of a solution‐based method as a facile and scalable process for the construction of fluoride nanofilms, which is promising to address the critical interfacial challenges of solid‐state batteries (SSBs) to facilitate its practical applications.

Regulating of Lithium‐Ion Dynamic Trajectory by Ferromagnetic CoF2 to Achieve Ultra‐Stable Deep Lithium Deposition Over 10000 h

AbstractCurrently, the realization of controllable Li electrodeposits to further extend the cycling life of Li metal anode remains challenging. Herein, it is reported that carbon nanosheet array‐loaded ferromagnetic CoF2 nanoparticles on carbon cloth (CC@CoF2/C) as an internal micro‐magnetic field source to manipulate the dynamic trajectory of Li+ deposition via the magnetohydrodynamic effect. This approach ensures uniform lithium‐ion distribution and improves deep plating capacity, achieving a prolonged cycle life of the dendrite‐free Li anode. Finite element simulations, in situ characterizations, and electrochemical tests confirm that magnetic CoF2 not only guides Li+ migration through Lorentz force to prevent dendritic growth but also improves uniform Li deposition due to the in situ conversion of LiF‐rich solid electrolyte interphase during electroplating. Meanwhile, a CC@CoF2/C‐based half‐cell operates stably over 10 000 h at 1 mA cm−2 with a low 7.8 mV overpotential. When matched with a commercial LiFePO4 cathode, the full cell reveals a high capacity of 122.96 mAh g−1 at a 2 C rate after 1000 cycles, retaining 91.95% capacity. The proposed strategy can be effectively expanded and adapted to investigate the deposition behavior of a wide range of metal anodes, offering a versatile and robust analytical framework for addressing diverse metal‐based electrochemical systems.

Facile Electrodeposition Method for Constructing Li2S as Artificial Solid Electrolyte Interphase for High-Performance Li Metal Anode.

Designing current collectors and constructing efficient artificial solid electrolyte interphase (SEI) layers are promising strategies for achieving dendrite-free Li deposition and practical applications in Li metal batteries (LMBs). Electrodeposition is advantageous for large-scale production and allows the direct formation of current collectors without binders, making them immediately usable as electrodes. In this study, an adherent Cu2S thin-layer on Cu foil is synthesized through anodic electrodeposition from a Na2S solution in a one-step process, followed by the generation of Li2S layers as artificial SEI layers via a conversion reaction (3DLi2S-Cu foil). The Li2S layers move from the 3D Cu surface to the deposited Li surface, facilitating uniform and dense Li deposition. The 3DLi2S-Cu foil structure demonstrates stable cycling performance over 350 cycles in an asymmetric cell, with a capacity of 1 mAh cm-2 at 1 mA cm-2. Moreover, symmetric cells with 5 mAh cm-2 of deposited Li exhibit a stable cycle life for over 1200 h. When paired with commercial LiFePO4 (LFP), the full cells show substantially enhanced cyclability, regardless of the amount of deposited Li. This study provides new insights into the construction of artificial SEIs for facilitating commercial applications.

Natural Polyphenol‐Reinforced Ion‐Selective Separators for High‐Performance Lithium‐Sulfur Batteries with High Sulfur Loading and Lean Electrolyte

Ion‐selective separators are promising to inhibit soluble intermediates shuttle in practical lithium‐sulfur (Li‐S) batteries. However, designing and fabricating such high‐performance ion‐selective separators using cost‐effective, eco‐friendly, and versatile methods remains a formidable challenge. Here we present ion‐selective separators fabricated via the spontaneous deposition of green tea‐derived polyphenols onto a polypropylene separator, aimed at enhancing the stability of Li‐S batteries. The resulting natural polyphenol‐reinforced ion‐selective (NPRIS24) separators exhibit rapid Li ion transport and high soluble intermediates inhibition capability with an ultralow shuttle rate of 0.67% for Li2S4, 0.19% for Li2S6 and 0.10% for Li2S8. This superior ion‐selectivity arises from the high electronegativity and strong lithiophilic nature of the phenolic compounds. Consequently, we have achieved high‐performance Li‐S batteries that are steadily cyclable under the challenging conditions of an S loading of 5.7 mg cm−2, an electrolyte‐to‐S ratio of 5.1 μL mg−1, and a 50 μm Li foil anode. Furthermore, the NPRIS24 separator enhances the performance of other Li metal batteries utilizing commercial LiFePO4 (5.3 mg cm−2) and LiNi0.5Co0.2Mn0.3O2 (9.9 mg cm−2) cathodes. This work underscores the potential of utilizing natural polyphenols for the design of advanced ion‐selective separators in energy storage systems.

Natural Polyphenol-Reinforced Ion-Selective Separators for High-Performance Lithium-Sulfur Batteries with High Sulfur Loading and Lean Electrolyte.

Ion-selective separators are promising to inhibit soluble intermediates shuttle in practical lithium-sulfur (Li-S) batteries. However, designing and fabricating such high-performance ion-selective separators using cost-effective, eco-friendly, and versatile methods remains a formidable challenge. Here we present ion-selective separators fabricated via the spontaneous deposition of green tea-derived polyphenols onto a polypropylene separator, aimed at enhancing the stability of Li-S batteries. The resulting natural polyphenol-reinforced ion-selective (NPRIS24) separators exhibit rapid Li ion transport and high soluble intermediates inhibition capability with an ultralow shuttle rate of 0.67% for Li2S4, 0.19% for Li2S6 and 0.10% for Li2S8. This superior ion-selectivity arises from the high electronegativity and strong lithiophilic nature of the phenolic compounds. Consequently, we have achieved high-performance Li-S batteries that are steadily cyclable under the challenging conditions of an S loading of 5.7 mg cm-2, an electrolyte-to-S ratio of 5.1 μL mg-1, and a 50 μm Li foil anode. Furthermore, the NPRIS24 separator enhances the performance of other Li metal batteries utilizing commercial LiFePO4 (5.3 mg cm-2) and LiNi0.5Co0.2Mn0.3O2 (9.9 mg cm-2) cathodes. This work underscores the potential of utilizing natural polyphenols for the design of advanced ion-selective separators in energy storage systems.

Sustainable Grease Lubrication Induced by Graphene Oxide and LiFePO4

This study investigates the possibility of modifying lubricating greases by 2D graphene oxide (GO) and lithium iron phosphate (LiFePO4) to enhance their tribological performance. GO's layered structure plays a crucial role in reducing friction by facilitating easy sliding between rubbing surfaces, making it an effective solid lubricant. The impact of these additives on friction reduction, wear resistance, and the tribolayer formation ability is evaluated by ball‐on‐disc tribometry with an emphasis on durability and sustainability. Comparative results reveal that unmodified greases exhibit a high susceptibility to wear, including oxide formation and severe plastic deformation. In contrast, greases with GO show a notable reduction in friction, while the addition of LiFePO4 contributes to the formation of a continuous protective layer that substantially reduces abrasive wear. The combination of GO and LiFePO4 results in a homogeneous, durable tribofilm that effectively protects surfaces against severe wear providing long‐term friction stability. Although lab‐scale LiFePO4 is used, the findings suggest a great potential for extending the useful life of recycled LiFePO4 from lithium‐ion batteries, similar to commercial LiFePO4 thus confirming significant improvements in the grease performance but also highlighting the potential to advance toward more sustainable solutions in industrial applications and electric vehicles.

Catalytic Strategies Enabled Rapid Formation of Homogeneous and Mechanically Robust Inorganic‐Rich Cathode Electrolyte Interface for High‐Rate and High‐Stability Lithium‐Ion Batteries

AbstractLithium iron phosphate (LFP) cathode is renowned for high thermal stability and safety, making them a popular choice for lithium‐ion batteries. Nevertheless, on one hand, the fast charge/discharge capability is fundamentally constrained by low electrical conductivity and anisotropic nature of sluggish lithium ion (Li+) diffusion. On the other hand, the interface and internal structural degradation occurs when subjected to high‐rate condition. Herein, a multifunctional boron‐doping graphene/lithium carbonate (BG/LCO) nanointerfacial layer on surface of commercial LiFePO4 particles is designed, in which the BG layer catalyzes the rapid reaction of Li2CO3‐LiPF6 for homogeneous and mechanically robust inorganic LiF‐rich structure across the cathode‐electrolyte interphase (CEI), forms a conductive network to significantly enhance both electron and Li+ transport, and strengthens the FeO bonding to minimize both Fe loss and the formation of Fe‐Li antisite defects. Correspondingly, the modified LFP cathode achieves a high capability of 113.2 mAh g−1 at 10 C and extraordinary cyclic stability with 88.0% capacity retention over 1000 cycles as compared to the pristine LFP cathode with a capacity of only 94.0 mAh g−1 and 64.6% capacity retention. It also exhibits great enhancements of 20.1% and 3.7% at higher‐rate condition (room temperature/15 C) and the low temperature condition (−10 °C/1 C), respectively.

Diagnosis and Management of Thermal Runaway Factors in Commercial LiFePO4 LIBs

Diagnosis and Management of Thermal Runaway Factors in Commercial LiFePO4 LIBs

Amino Group-Aided Efficient Regeneration Targeting Structural Defects and Inactive FePO4 Phase for Degraded LiFePO4 Cathodes.

It is urgent to develop efficient recycling methods for spent LiFePO4 cathodes to cope with the upcoming peak of power battery retirement. Compared with the traditional metallurgical recovery methods that lack satisfactory economic and environmental benefits, the direct regeneration seems to be a promising option at present. However, a simple direct lithium replenishment cannot effectively repair and regenerate the cathodes due to the serious structural damage of the spent LiFePO4. Herein, the spent LiFePO4 cathodes are directly regenerated by a thiourea-assisted solid-phase sintering process. The density functional theory calculation indicates that thiourea has a targeted repair effect on the antisite defects and inactive FePO4 phase in the spent cathode due to the associative priority of amino group (─NH2) in thiourea with Fe ions: Fe3+─N > Fe2+─N. Meanwhile, the pyrolysis products of thiourea can also create an optimal reducing atmosphere and inhibit the agglomeration of particles in the high temperature restoration process. The regenerated LiFePO4 exhibits an excellent electrochemical performance, which is comparable to that of commercial LiFePO4. This targeted restoration has improved the efficiency of direct regeneration, which is expected to achieve large-scale recycling of spent LiFePO4.

Insights into the swelling force in commercial LiFePO4 prismatic cell

Lithium-ion batteries undergo reversible and irreversible swelling force during cycling. The mechanical behavior and swelling force of lithium-ion batteries are important in practical applications. In this study, the variation and the aging mechanism of swelling force, and the growth pattern under different cycling conditions have been studied with commercial cells. The findings reveal distinct dynamic stress peaks corresponding to the state of charge (SOC) increase, indicative of notable lattice expansions in both cathode and anode. This expansion intensifies over cycles, with the most significant escalation observed at 30 % SOC, gradually assuming a pivotal role in battery expansion dynamics. Post-mortem analysis, coupled with stress-strain evaluations, attributes this phenomenon primarily to moduli variations across SOC during the aging process. Moreover, the trajectory of swelling force amplification varies across aging paths, with high-temperature cycling demonstrating accelerated growth. This accelerated growth stems from the broadened expansion of battery components beyond solid electrolyte interphase (SEI) formation induced by high-temperature aging.

High‐Energy Sodium Ion Batteries Enabled by Switching Sodiophobic Graphite into Sodiophilic and High‐Capacity Anodes

Owing to the crustal abundance of sodium element, sodium ion batteries (SIBs) are considered a promising complementary to lithium‐ion battery for stationary energy storage applications. The cointercalation chemistry enables the use of cost‐effective graphite as anodes, whereas the low capacity (<130 mAh g‐1) and high redox potential (>0.6 V vs. Na/Na+) of graphite significantly limit the energy density of SIBs. Herein, we induce the high‐capacity Na metal into sodiophilic ternary graphite intercalation compounds (t‐GICs) via co‐intercalation and deposition reactions, thereby achieving Na/t‐GIC anodes with high capacities and low working voltage (0.18 V). The new anodes exhibit high coulombic efficiencies of above 99.7 % over 550 cycles and a high‐rate capacity of 588.4 mAh g‐1 at 6 C (10 min per charge). When it is paired with Na3V2(PO4)2F3 (NVPF) cathodes, the SIBs demonstrate a high energy density of 259 Wh kg‐1both electrodes surpassing that of commercial LiFePO4//graphite batteries. The outstanding anode performance is attributed to the tailored sodiophilicity of graphite through manipulating the ether solvents and the in‐situ generated space among t‐GIC flakes to stably accommodate Na metal. Our findings for stable Na plating/striping on sodiophilic graphite materials provide an effective approach for developing advanced SIBs.

High-Energy Sodium Ion Batteries Enabled by Switching Sodiophobic Graphite into Sodiophilic and High-Capacity Anodes.

Owing to the crustal abundance of sodium element, sodium ion batteries (SIBs) are considered a promising complementary to lithium-ion battery for stationary energy storage applications. The cointercalation chemistry enables the use of cost-effective graphite as anodes, whereas the low capacity (<130 mAh g-1) and high redox potential (>0.6 V vs. Na/Na+) of graphite significantly limit the energy density of SIBs. Herein, we induce the high-capacity Na metal into sodiophilic ternary graphite intercalation compounds (t-GICs) via co-intercalation and deposition reactions, thereby achieving Na/t-GIC anodes with high capacities and low working voltage (0.18 V). The new anodes exhibit high coulombic efficiencies of above 99.7 % over 550 cycles and a high-rate capacity of 588.4 mAh g-1 at 6 C (10 min per charge). When it is paired with Na3V2(PO4)2F3 (NVPF) cathodes, the SIBs demonstrate a high energy density of 259 Wh kg-1both electrodes surpassing that of commercial LiFePO4//graphite batteries. The outstanding anode performance is attributed to the tailored sodiophilicity of graphite through manipulating the ether solvents and the in-situ generated space among t-GIC flakes to stably accommodate Na metal. Our findings for stable Na plating/striping on sodiophilic graphite materials provide an effective approach for developing advanced SIBs.

Second-Life Assessment of Commercial LiFePO4 Batteries Retired from EVs

Second-Life Assessment of Commercial LiFePO4 Batteries Retired from EVs

In-situ repair of failed LiFePO4 cathode using residual Li- and C-containing impurities from active material separation process

Effectively recovering spent lithium-ion batteries can reduce resource waste and environmental pollution. LiFePO4 (LFP) batteries have been widely used in new energy vehicles. The main reason for the performance degradation of LFP cathodes is the loss of Li, oxidation of Fe, and the destruction of crystal structure and surface carbon layer. Here, an in-situ repair strategy of high-temperature calcination, using impurities remaining in cathode blackmass (e.g., LiPF6, LiPO3, Fe2O3, acetylene black, binder, and electrolyte) as raw materials, was proposed. During the calcination process, the residual LiPF6 is converted into Li, acting as a lithium source to fill the vacancies. The residual binder and electrolyte are pyrolyzed into amorphous carbon and carbon nanotubes, which deposit on the LFP particles to repair the missing carbon layer and enhance the conductivity of the electrode material. The pyrolytic carbon and residual acetylene black can provide a reducing atmosphere, converting Fe3+ to Fe2+. Additionally, the residual LiPO3 and Fe2O3 impurities undergo recrystallization forming new LFP. The failed LFP was restored to the same level as commercial LFP by calcining at 750 °C for 3 h. This in-situ repair strategy reduces the input of raw materials, providing a valuable reference for large-scale recycling of lithium batteries.

Electrochemical model boosting accurate prediction of calendar life for commercial LiFePO4|graphite cells by combining solid electrolyte interface side reactions

The lithium-ion battery (LIB) is considered an ideal next-generation energy storage device owing to its high safety, high energy density, and low cost. Calendar loss of LIBs is the most important element in the long-term degradation of batteries. However, the calendar life is difficult to measure precisely because of the uncertain and overlong storage years. Consequently, accurately predicting the calendar life of LIBs is a key but challenging issue. In this work, a calendar life prediction model is developed for commercial large-capacity LiFePO4|graphite LIBs based on the pseudo-two-dimensional (P2D) electrochemical model integrated with solid electrolyte interface (SEI) growth side reactions and an empirical degradation rate model for reliability research. The excellent agreement between the model and the experimental storage data over a wide range of temperatures (−40 °C ∼ 70 °C) and SOCs demonstrates the high-fidelity of the model. The established model is sufficiently generic to predict the storage aging of LIBs over a long period of years. On the basis of the verified model, the impact of graphite particle radius distribution on the calendar loss of Li-ion batteries throughout a broad temperature range is investigated. This modeling work contributes to an improved understanding of the calendar loss behavior of LIBs and provides valuable guidance for future battery design optimization.

Experimental Investigation on the Temperature Dependence of Open-Circuit Voltage Hysteresis in LiFePO4 Lithium-Ion Batteries

A commercial LiFePO4 Lithium-ion (LFP-LIB) cell was adopted to investigate hysteresis of open circuit voltage (OCV) in Lithium-ion batteries. Experiments were conducted within the typical operating temperature range of 0℃, 10℃, 20℃, 30℃, 40℃ and 45℃, covering state of charge (SOC) from 0% to 100%. The results showed that (i) OCV hysteresis is dependence on temperature and increases as the temperature decreases, and (ii) bimodality appears in certain SOCs. Comparing the impedances confirmed by electrochemical impedance spectroscopy (EIS), we found that charge-transfer resistance (Rct) increases significantly as the temperature decreases. This means that the LFP-LIB operating at lower temperatures suffers a higher polarization. This result indicates that identification of OCV hysteresis is essential for accurate SOC estimation. Figure 1

Re-Functionalization of Aged Lithium Iron Phosphate Cathode Materials

As lithium-ion batteries continue to be implemented in everyday technologies, it is imperative to repurpose these battery materials upon their degradation. Carbon-coated lithium iron phosphate (LFP/C) is considered one of the most stable cathode materials for application in lithium-ion batteries. Due to this stability, LFP/C possesses a remarkably long cycle life of greater than 3000 cycles.1 Extended cycling of these cathode materials may result in multiple modes of degradation, including degradation of the carbon coating, and loss of contact between the cathode and the current collector.2,3 In this work, a suitable process and reagents have been selected to isolate and purify the LFP/C from the cathodes of cycled batteries. Isolating and purifying aged LFP/C materials enables the diagnosis of the mode(s) of degradation of these materials and their coatings using a variety of techniques including X-ray diffraction, scanning electron microscopy, and transmission electron microscopy methods.Furthermore, additional work was pursued to give new life to these isolated, spent cathode materials. The addition of a coating with a relatively high lithium conductivity to the aged LFP/C particles was sought to provide a second life to these electrochemically aged materials. Half-cells were fabricated using the coated, aged LFP/C cathode materials to compare their performance to both pristine LFP/C nanoparticles and aged LFP/C nanoparticles without the addition of this custom coating. Electrochemical testing techniques such as galvanostatic cycling, cyclic voltammetry, and electrochemical impendence spectroscopy were used to probe the performance of each type of LFP/C nanoparticle as cathode materials in lithium-ion batteries. The coated, aged LFP/C particles were also characterized using transmission electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy techniques. The techniques developed herein can be used to isolate, purify, and re-functionalize other cathode materials from lithium-ion batteries. Lewerenz, M.; Munnix, J.; Schmalstieg, J.; Kabitz, S.; Knips, M.; Sauer, D. U. Systematic aging of commercial LiFePO4|Graphite cylindrical cells including a theory explaining rise of capacity during aging. Power Sources. 2017, 345, 254-263.Wang, L.; Qiu, J.; Wang, X.; Chen, L.; Cao, G.; Wang, J.; Zhang, H.; He, X. Insights for understanding multiscale degradation of LiFePO4 cathodes. eScience 2022, 2(2), 125-137.

Synergistic effect of LixSi/Li3N artificial interface and 3D framework for enabling Dendrite-free, long-life lithium metal anodes

Lithium metal is highly favored as an ideal anode material in future high-capacity lithium batteries due to its appealing properties. Nevertheless, the implementation of lithium metal batteries (LMBs) is severely plagued by challenges such as instable solid electrolyte interface (SEI), uncontrolled growth of dendrite, and severe volume expansion. Herein, to address the aforementioned issues, an artificial SEI layer is fabricated, which is comprised of LixSi alloy and Li3N. The in-situ generated LixSi/Li3N interface is formed on the carbon fiber (denoted as CF/LixSi/Li3N) through a spontaneous reaction between molten Li and Si3N4. Density functional theory (DFT) calculations reveal that LixSi alloy has low ion diffusion energy barrier, which facilitates the low nucleation overpotential of Li+ and enables homogeneous lithium deposition. Li3N can further promote the rapid Li+ transport due to the excellent Li+ conductivity. In addition, the reserved 3D space effectively mitigates the volume change along cycling procedure. Owing to the synergistic effect of the LixSi/Li3N protective layer and the 3D structure, the composite anode shows higher cycling stability with a lifetime of more than 3000 cycles at 1 mA cm−2. Furthermore, matched with commercial LiFePO4 (LFP) and LiNi5Co2Mn3O2 (NCM523) cathodes, the full cells also exhibit impressive electrochemical properties. This work introduces an ingenious approach for constructing stable lithium metal anodes and effective lithium metal batteries.