Lithium metal negative electrode composite artificial solid electrolyte interface for space lithium battery and in-situ construction method of lithium metal negative electrode composite artificial solid electrolyte interface
By constructing a lithium nitride/lithium carbonate composite artificial solid electrolyte interface film on the lithium metal surface, the problem of insufficient interface stability in lithium metal batteries was solved, achieving a synergistic effect of rapid lithium-ion transport and interface compatibility, thereby improving the cycle life and stability of the battery.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-12
- Publication Date
- 2026-04-10
AI Technical Summary
In existing quasi-solid-state lithium metal batteries, the lithium metal anode interface has a single function, making it difficult to simultaneously achieve rapid lithium-ion transport and long-term interface compatibility. During cycling, interface debonding and contact degradation are prone to occur, leading to local current concentration and uneven lithium deposition, increased interface impedance, and insufficient stability in aerospace environments.
By combining electrochemical reduction conversion and thermal curing, a composite artificial solid electrolyte interface film composed of lithium nitride/lithium carbonate is formed on the surface of lithium metal. Combined with electrochemical conversion and thermal treatment, a composite ASEI structure with ion conduction region and interface compatibility functional region is constructed.
It achieves a synergistic effect of rapid lithium-ion transport and long-term interface compatibility, suppresses interface debonding and contact degradation, reduces polarization, extends cycle life, and improves the stability and safety of lithium metal batteries in aerospace environments.
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Figure CN121839901A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of lithium metal battery interface regulation and quasi-solid-state battery, and particularly relates to a lithium metal negative electrode composite artificial solid electrolyte interface for space lithium and an in-situ construction method thereof. BACKGROUND
[0002] The lithium metal negative electrode is considered as a key electrode material for the next generation of high-energy-density energy storage systems due to its extremely high theoretical specific capacity (3860 mAh g - ¹) and the lowest electrochemical potential. It has great application prospects in the fields of space power supply such as deep space exploration, satellite platform, manned spaceflight and space station. Space missions have extremely high requirements for battery systems: not only do they need high specific energy and long cycle life, but they must also adapt to complex space environments such as high vacuum, strong radiation, large temperature difference and strong vibration, and have extremely high safety and reliability. Traditional liquid electrolytes have the risk of leakage, volatilization and combustion, and are difficult to meet the stringent standards of safety and stability of power systems for spacecraft. Therefore, quasi-solid-state electrolyte systems that have certain mechanical stability, low leakage risk and good interface contact have become an important development direction for high-specific-energy lithium metal batteries in space.
[0003] However, in the quasi-solid-state system, the interface stability problem of the lithium metal negative electrode is particularly prominent. The continuous volume change and interface dynamic reconstruction during lithium deposition / stripping process easily lead to the failure of electrode-electrolyte interface contact, causing local current concentration, lithium dendrite growth and repeated rupture and regeneration of the solid-state electrolyte interface film (SEI). In the space application scenario, this interface instability will be further intensified: the long-term microgravity environment may affect the uniform distribution and interface wetting of the electrolyte; thermal cycling load will cause interface expansion-shrinkage mismatch; the radiation environment may accelerate the interface side reaction and material degradation. These factors jointly restrict the practical application of quasi-solid-state lithium metal batteries in space missions.
[0004] To improve the interface stability, artificial solid-state electrolyte interface (ASEI) construction strategies have been widely studied, mainly including inorganic coating (such as Li3N, oxide, fluoride, etc.), polymer interface and organic-inorganic composite layer, etc. Among them, nitrogen-containing interface (such as Li3N) can be used to reduce the interface impedance due to high ionic conductivity and wide electrochemical window; flexible polymer interface helps to buffer volume change and improve mechanical adaptation. However, the existing ASEI strategies generally have the limitation of "single function, insufficient synergy": under high current, long cycle and space environment alternating stress, the interface is prone to polymer chain rearrangement, electrolyte redistribution and structure and chemical stability decay, and it is difficult to achieve the persistent stability of the interface in the dynamic process by simply improving the ionic conductivity or mechanical flexibility. Especially for gel polymer-based quasi-solid-state systems, the affinity and contact retention ability between the interface and the electrolyte are crucial, otherwise the contact loss is easy to occur under space temperature cycling or mechanical vibration, leading to battery performance degradation or even failure.
[0005] Therefore, facing the demand of high reliability and long life energy storage in space, the quasi-solid-state lithium metal negative electrode interface must simultaneously meet the dual functions of fast and uniform lithium ion transmission and long-term dynamic interface compatibility. At present, it is difficult for a single material or simple layered interface to realize the organic unity of the two under complex working conditions, and it is urgent to develop a new artificial solid-state electrolyte interface construction method that can integrate ion conduction and interface self-adaptive functions. SUMMARY
[0006] Based on this, the present application proposes a composite artificial solid-state electrolyte interface in-situ construction strategy for space application background, which constructs a composite ASEI structure with ion conduction zone and interface compatibility function zone by combining interface engineering of electrochemical conversion and thermal curing / synchronous polymerization, to enhance the interface stability, cycle life and environmental adaptability of quasi-solid-state lithium metal batteries under simulated space environment, and to provide key technical support for promoting the practical application of high specific energy and high safety lithium metal batteries in space power systems.
[0007] The present application aims to solve the shortcomings in the process of regulating lithium metal negative electrode interface in the existing quasi-solid-state lithium metal battery, such as single function of artificial solid-state electrolyte interface film, difficulty in simultaneously considering fast lithium ion transmission and long-term interface compatibility and contact retention, easy occurrence of interface debonding and contact recession during cycling and resulting in local current concentration and uneven lithium deposition, continuous growth of interface impedance and insufficient stability under high current density or long cycle conditions, etc., and to provide a composite artificial solid-state electrolyte interface film in-situ construction method with function partition synergy, strong interface stability, low polarization and suitable for dynamic interface of gel polymer electrolyte, and a lithium metal negative electrode and quasi-solid-state lithium metal battery obtained therefrom.
[0008] The lithium metal negative electrode composite artificial solid-state electrolyte interface film provided by the application is formed on the surface of lithium metal through a two-step in-situ method of "electrochemical reduction conversion-heat curing synergistic generation", the composite artificial solid-state electrolyte interface film is of lithium nitride / lithium carbonate composite composition, and can contain a small amount of inorganic components such as lithium oxide; the interface film as a whole is of a composite structure, and carbon, nitrogen and oxygen elements are uniformly distributed in a submicron scale, and can realize continuous coverage on the surface of lithium metal. The thickness of the composite artificial solid-state electrolyte interface film can be about 1.1 μm; when different amounts of precursors are used, the thickness of the interface film can change, for example, when the amount of the precursor is high, the thickness of the interface film can increase to about 5.2 μm, and the charge transfer kinetics is slowed down and polarization is increased.
[0009] Preferably, the lithium carbonate in the interface film is the main carbonate component of the interface film, and the lithium nitride is the main inorganic component containing nitrogen; the surface of the interface film can present a more significant characteristic of the lithium carbonate signal, thereby facilitating the establishment of more stable interface contact with the gel polymer electrolyte.
[0010] In order to achieve the above technical problems, the application adopts the following technical solutions: On the surface of the lithium metal negative electrode, a uniform lithium nitrate (LiNO3) coating layer is constructed in advance. The coating layer serves as a precursor for subsequent in-situ reaction, and the assembled battery is subjected to initial charging and discharging cycles. In this process, through specific electrochemical conditions, the reduction and decomposition of the lithium nitrate coating layer is induced, and an initial composite interface layer of lithium nitride (Li3N) and lithium oxide (Li2O) is generated in-situ. The battery after the initial cycle is subjected to programmed heat treatment, and during the heating process, the lithium oxide reacts with the carbon dioxide generated by the trace decomposition of the electrolyte. This step aims to further convert the Li2O generated in the second step into lithium carbonate (Li2CO3). Finally, an artificial / composite solid electrolyte interface (SEI) film is formed on the surface of the lithium metal, which is mainly composed of high ionic conductive Li3N and good mechanical performance Li2CO3: Li3N as the key component of the SEI film has extremely high lithium ion conductivity, which can significantly improve the migration speed of lithium ions in the interface layer, reduce the electrode polarization, and thus improve the rate performance of the battery. The Li2CO3 component has good elasticity and mechanical strength, and has strong affinity with the electrolyte, which can effectively adapt to the significant volume change of lithium metal during deposition / detachment, maintain the structural integrity of the SEI film, maintain the close interface contact with the electrode, prevent continuous side reactions and lithium dendrite growth caused by the rupture of the SEI, and thus improve the cycle life and safety of the battery.
[0011] This invention introduces a nitrate-containing precursor onto the lithium metal surface and, through the synergistic effect of electrochemical reduction conversion and thermal treatment during the curing process of the gel polymer electrolyte, constructs an artificial solid-state electrolyte interface film in situ, composed of lithium nitride and inorganic components such as lithium carbonate. This stabilizes the lithium metal anode interface and improves the cycle performance and safety reliability of quasi-solid-state lithium metal batteries. The improvement lies in proposing a novel in-situ interface construction method of "electrochemical conversion-thermal curing synergistic generation," enabling the artificial solid-state electrolyte interface film to establish a stable and compatible interface with the gel polymer electrolyte during formation. This avoids the problems of existing artificial interface films, such as limited functionality, easy debonding and instability, and impedance growth.
[0012] The purpose of this invention is to provide an in-situ construction method for a lithium metal anode composite artificial solid electrolyte interface for space lithium batteries, comprising the following steps: Step 1: Prepare a precursor solution of lithium nitrate; Step 2: Under an inert atmosphere, clean the lithium metal surface, then uniformly coat the lithium metal surface with the precursor solution, and then heat to remove the solvent to obtain the negative electrode. Step 3: Assemble the negative electrode and the gel polymer electrolyte system, perform electrochemical pretreatment on the precursor layer, and then perform heat treatment to complete the process. Further specifying, in step 1, the concentration of the precursor solution is 0.2 wt.%-1.0 wt.%.
[0013] The concentration of the lithium nitrate precursor has a significant impact on the chemical composition and charge transfer kinetics of the interfacial film: when the concentration is 0.2 wt.%, the interfacial modification is insufficient and the interfacial stability is poor; when the concentration is 1.0 wt.%, the interfacial film is prone to be too thick, leading to increased impedance and increased polarization; when the concentration is 0.5 wt.%, a better balance can be achieved between interfacial composition and kinetics, thereby obtaining more stable cycling performance.
[0014] To further specify, in step 1, the precursor solution is prepared using tetrahydrofuran as the solvent.
[0015] To further specify, all operations in step 2 are performed under an inert atmosphere, which is argon.
[0016] To further specify, in step 2, lithium metal is cleaned with dimethyl carbonate, and the lithium metal is in the form of foil.
[0017] Further specifying, in step 2, heating at 50 °C is used to remove the solvent.
[0018] Further specifying, in step 3, the gel polymer electrolyte is composed of a liquid electrolyte containing lithium hexafluorophosphate and a cross-linked polymer matrix, wherein the cross-linked polymer matrix is formed by cross-linking polyethylene glycol dimethacrylate and pentaerythritol tetraacrylate.
[0019] Further specifying, in step 3, the electrochemical pretreatment is performed at a current density of 0.2 mA cm⁻¹. 2 Perform 10 cycles under the given conditions.
[0020] Further specifying, in step 3, heat treatment is performed at 60 ℃.
[0021] The present invention also provides a lithium metal anode composite artificial solid electrolyte interface for space lithium batteries prepared by any of the above methods, with a thickness of 1.0 μm-5.2 μm.
[0022] A solid-state lithium metal battery, characterized in that it comprises a lithium metal anode prepared by any of the methods described above. The gel polymer electrolyte is composed of a liquid electrolyte containing lithium hexafluorophosphate and a cross-linked polymer matrix, wherein the cross-linked polymer matrix is formed by cross-linking polyethylene glycol dimethacrylate and pentaerythritol tetraacrylate; the lithium metal anode and cathode obtained in steps (A) to (C) and the gel polymer electrolyte are assembled to obtain a quasi-solid-state lithium metal battery. Compared with the prior art, the present invention has the following beneficial effects: Compared with existing lithium metal anode interface modification technologies, this invention can construct an artificial solid electrolyte interface film composed of lithium nitride and inorganic components such as lithium carbonate in situ on the lithium metal surface. This film combines lithium-ion transport capability with interface compatibility and contact retention capability, thereby effectively suppressing interface debonding and contact decay during cycling, reducing local current concentration and promoting uniform lithium deposition. It has a better overall technical effect in improving the interface stability of quasi-solid-state lithium metal batteries, reducing polarization and extending cycle life.
[0023] Meanwhile, this invention proposes an in-situ interface construction approach of "precursor coating - electrochemical conversion - thermal treatment synergistic generation", which enables the interface film to establish a stable and compatible interface with the gel polymer electrolyte during the formation stage. This approach is different from traditional single coating or single reaction interface modification schemes, and is more innovative in concept and has better applicability and reliability.
[0024] For a deeper understanding of the features and technical content of this invention, please refer to the accompanying detailed description and drawings. It should be noted that the drawings are provided for illustrative purposes only and are not intended to limit the scope of the invention. Attached Figure Description
[0025] Figure 1 The quasi-solid-state symmetric cell assembled in Example 1 operates at a current density of 0.2 mA cm⁻¹. 2 Voltage-time curves of lithium deposition / stripping cycle tests under the specified conditions; Figure 2The quasi-solid-state symmetric cell assembled in Example 2 operates at a current density of 0.2 mA cm⁻¹. 2 Voltage-time curves of lithium deposition / stripping cycle tests under the specified conditions; Figure 3 The quasi-solid-state symmetric cell assembled in Example 3 operates at a current density of 0.2 mA cm⁻¹. 2 Voltage-time curves of lithium deposition / stripping cycle tests under the specified conditions; Figure 4 Example 1 was performed at a current density of 0.2 mA cm⁻¹ 2 SEM images of the surface morphology and energy dispersive spectroscopy (EDS) of the surface elemental distribution after lithium deposition / stripping cycle testing under the specified conditions; Figure 5 Example 2 was performed at a current density of 0.2 mA cm⁻¹ 2 SEM images of the surface morphology and energy dispersive spectroscopy (EDS) of the surface elemental distribution after lithium deposition / stripping cycle testing under the specified conditions; Figure 6 Example 3 was performed at a current density of 0.2 mA cm⁻¹. 2 SEM images of the surface morphology and energy dispersive spectroscopy (EDS) of the surface elemental distribution after lithium deposition / stripping cycle testing under the specified conditions; Figure 7 This is a comparison curve of capacity versus number of cycles in a quasi-solid-state full cell assembled with a conventional lithium metal anode and a lithium iron phosphate cathode, respectively, under a cyclic charge-discharge test at a rate of 0.3 C.
[0026] Figure 8 The quasi-solid-state full cells assembled in Example 1 with ordinary lithium metal anodes and lithium iron phosphate cathodes were tested under different ultraviolet radiation conditions of 0 ESH, 200 ESH, and 400 ESH at 0.2 mA cm⁻¹. 2 Capacity-cycle count curves from cyclic charge-discharge tests. Detailed Implementation
[0027] The present invention will be described in detail below with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but should not be considered as limiting the present invention. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention. These all fall within the protection scope of the present invention.
[0028] Example 1: The in-situ construction method of the lithium metal anode composite artificial solid electrolyte interface for space lithium batteries in this example is achieved through the following steps: Lithium metal foil (200 μm thick) was taken under an argon atmosphere (argon volume purity of 99.9999%), and the surface of the lithium foil was cleaned with dimethyl carbonate to obtain a relatively smooth lithium metal substrate.
[0029] Using tetrahydrofuran as a solvent, lithium nitrate was prepared into a precursor solution with a mass percentage of 0.5%. The precursor solution was uniformly coated onto the surface of lithium metal foil by spin coating to form a continuous precursor layer, and then heated at 50°C for 5 minutes under an inert atmosphere to remove the solvent.
[0030] The obtained negative electrode was assembled with a gel polymer electrolyte system (specifically, a gel electrolyte containing LiPF6, with PETEA and PEGDMA as polymer monomers), and the precursor layer was subjected to electrochemical pretreatment at a current density of 0.2 mAcm⁻¹. 2 Perform 10 cycles under the given conditions.
[0031] The battery was then subjected to heat treatment at a temperature of 60 °C for 3 hours to obtain a lithium metal anode with a composite artificial solid electrolyte interface film on its surface.
[0032] The gel polymer electrolyte is composed of a liquid electrolyte containing lithium hexafluorophosphate (1 mol / L LiPF6 dissolved in a mixed solvent of EC, DEC, and DMC, with a volume ratio of 1:1:1 for the three solvent components) and a cross-linked polymer matrix. The cross-linked polymer matrix is formed by cross-linking polyethylene glycol dimethacrylate and pentaerythritol tetraacrylate (with a mass ratio of 10:90 to the liquid electrolyte) (polymerization conditions: addition of 0.01 wt.% AIBN and heating at 60 °C for 2 hours).
[0033] Example 2: The in-situ construction method of the lithium metal anode composite artificial solid electrolyte interface for space lithium batteries in this example is achieved through the following steps: Lithium metal foil (200 μm thick) was taken under an argon atmosphere (argon volume purity 99.9999%), and the surface of the lithium foil was cleaned with dimethyl carbonate to obtain a relatively smooth lithium metal substrate.
[0034] Using tetrahydrofuran as a solvent, lithium nitrate was prepared into a precursor solution with a mass percentage of 0.2%. The precursor solution was uniformly coated onto the surface of lithium metal foil by spin coating to form a continuous precursor layer. The solution was then heated at 50°C for 5 minutes under an inert atmosphere to remove the solvent, thereby obtaining the negative electrode.
[0035] The obtained negative electrode was assembled with a gel polymer electrolyte system, and the precursor layer was subjected to electrochemical pretreatment: at a current density of 0.2 mA cm⁻¹ 2 Perform 10 cycles under the given conditions.
[0036] The gel polymer electrolyte is composed of a liquid electrolyte containing lithium hexafluorophosphate (1 mol / L LiPF6 dissolved in a mixed solvent of EC, DEC, and DMC, with a volume ratio of 1:1:1 for the three solvent components) and a cross-linked polymer matrix. The cross-linked polymer matrix is formed by cross-linking polyethylene glycol dimethacrylate and pentaerythritol tetraacrylate (with a mass ratio of 10:90 to the liquid electrolyte) (polymerization conditions: addition of 0.01 wt.% AIBN and heating at 60 °C for 2 hours).
[0037] The battery was then subjected to heat treatment at a temperature of 60 °C for 3 hours to obtain a lithium metal anode with a composite artificial solid electrolyte interface film on its surface.
[0038] Example 3: The in-situ construction method of the lithium metal anode composite artificial solid electrolyte interface for space lithium batteries in this example is achieved through the following steps: Lithium metal foil (200 μm thick) was taken under argon gas (argon volume purity 99.9999%), and the surface of the lithium foil was cleaned with dimethyl carbonate to obtain a relatively smooth lithium metal substrate.
[0039] Using tetrahydrofuran as a solvent, lithium nitrate was prepared into a precursor solution with a mass percentage of 1.0%. The precursor solution was uniformly coated onto the surface of lithium metal foil by spin coating to form a continuous precursor layer. The solution was then heated at 50°C for 5 minutes under an inert atmosphere to remove the solvent, thereby obtaining the negative electrode.
[0040] The obtained negative electrode was assembled with a gel polymer electrolyte system, and the precursor layer was subjected to electrochemical pretreatment: at a current density of 0.2 mA cm⁻¹ 2 Perform 10 cycles under the given conditions.
[0041] The gel polymer electrolyte is composed of a liquid electrolyte containing lithium hexafluorophosphate (1 mol / L LiPF6 dissolved in a mixed solvent of EC, DEC, and DMC, with a volume ratio of 1:1:1 for the three solvent components) and a cross-linked polymer matrix. The cross-linked polymer matrix is formed by cross-linking polyethylene glycol dimethacrylate and pentaerythritol tetraacrylate (with a mass ratio of 10:90 to the liquid electrolyte) (polymerization conditions: addition of 0.01 wt.% AIBN and heating at 60 °C for 2 hours).
[0042] The battery was then subjected to heat treatment at a temperature of 60 °C for 3 hours to obtain a lithium metal anode with a composite artificial solid electrolyte interface film on its surface.
[0043] Performance testing The performance of the modified negative electrodes of Examples 1-3 was tested using the following methods: Symmetrical battery cycle stability test: Examples 1-3 were assembled into quasi-solid-state symmetric cells, respectively, at 0.2 mA cm⁻¹. 2 Lithium deposition / stripping cycle tests were performed under specific conditions to evaluate interface stability and polarization trends. The results are as follows: Figures 1-3 As shown.
[0044] Morphology test of modified negative electrode: To complete 0.2 mA cm 2 Examples 1-3 of lithium deposition / stripping cycle tests under the specified conditions were used to observe the morphology using scanning electron microscopy and the surface elemental distribution using energy dispersive spectroscopy. The results are as follows: Figures 4-6 As shown.
[0045] Full battery cycle test: Example 1 and ordinary lithium metal were respectively assembled with lithium iron phosphate cathodes to form quasi-solid-state full cells. The full cells were subjected to cycle charge-discharge tests at a rate of 0.3 C, and the results are as follows: Figure 7 As shown.
[0046] Ultraviolet irradiation stability test: Quasi-solid-state symmetric cells assembled in Example 1 with ordinary lithium metal anodes were subjected to ultraviolet irradiation at different intensities of 0 ESH, 200 ESH, and 400 ESH at a rate of 0.2 mA cm⁻¹. 2 Lithium deposition / stripping cycle tests were performed to evaluate the UV irradiation stability of the interface, and the results are as follows: Figure 8 As shown.
[0047] The quasi-solid-state symmetric cell assembled in Example 1 operates at a current density of 0.2 mA cm⁻¹. 2 The voltage-time curves for lithium deposition / stripping cycle testing under the conditions are shown in the figure. Figure 1 As shown, it is used to evaluate the interface stability and polarization change trend.
[0048] The quasi-solid-state symmetric cell assembled in Example 2 operates at a current density of 0.2 mA cm⁻¹. 2 The voltage-time curves for lithium deposition / stripping cycle testing under the conditions are shown in the figure. Figure 2 As shown, it is used to evaluate the interface stability and polarization change trend.
[0049] The quasi-solid-state symmetric cell assembled in Example 3 operates at a current density of 0.2 mA cm⁻¹. 2 The voltage-time curves for lithium deposition / stripping cycle testing under the conditions are shown in the figure. Figure 3 As shown, it is used to evaluate the interface stability and polarization change trend.
[0050] Example 1 was completed at a current density of 0.2 mA cm⁻¹ 2 SEM images and energy dispersive spectroscopy (EDS) spectra of the surface morphology after lithium deposition / stripping cycling under the specified conditions are shown below. Figure 4 As shown, it is used to characterize the surface morphology and elemental distribution of the negative electrode after cycling.
[0051] Example 2 was performed at a current density of 0.2 mA cm⁻¹ 2 SEM images and energy dispersive spectroscopy (EDS) spectra of the surface morphology after lithium deposition / stripping cycling under the specified conditions are shown below. Figure 5 As shown, it is used to characterize the surface morphology and elemental distribution of the negative electrode after cycling.
[0052] Example 3 was completed at a current density of 0.2 mA cm⁻¹ 2 SEM images and energy dispersive spectroscopy (EDS) spectra of the surface morphology after lithium deposition / stripping cycling under the specified conditions are shown below. Figure 6 As shown, it is used to characterize the surface morphology and elemental distribution of the negative electrode after cycling.
[0053] The capacity-cycle comparison curves of quasi-solid-state full cells assembled with ordinary lithium metal anodes and lithium iron phosphate cathodes in Example 1, under 0.3 C conditions, are shown below. Figure 7 As shown, this is used to evaluate the effect of the modified negative electrode of the present invention on the improvement of the cycle performance of the full battery.
[0054] In Example 1, quasi-solid-state symmetric cells assembled with ordinary lithium metal anodes were subjected to ultraviolet irradiation at different intensities of 0 ESH, 200 ESH, and 400 ESH at a rate of 0.2 mA cm⁻¹. 2 The voltage-time curves for lithium deposition / stripping cycle testing under current density conditions are shown in the figure. Figure 8 As shown, this is used to evaluate the effect of the modified negative electrode of the present invention on the improvement of the ultraviolet irradiation stability of the full cell.
[0055] The specific embodiments of the present invention have been described in detail above. It should be noted that the present invention is not limited to the specific embodiments described above. Various modifications or alterations can be made by those skilled in the art without departing from the scope of protection defined by the claims, and all such modifications or alterations fall within the scope of the present invention.
Claims
1. A method for in-situ construction of a lithium metal anode composite artificial solid electrolyte interface for space lithium batteries, characterized in that, Includes the following steps: Step 1: Prepare a precursor solution of lithium nitrate; Step 2: Under an inert atmosphere, clean the lithium metal surface, then uniformly coat the lithium metal surface with the precursor solution, and then heat to remove the solvent to obtain the negative electrode. Step 3: Assemble the negative electrode and the gel polymer electrolyte system, perform electrochemical pretreatment on the precursor layer, and then perform heat treatment to complete the process.
2. The method according to claim 1, characterized in that, A precursor solution was prepared using tetrahydrofuran as a solvent.
3. The method according to claim 1, characterized in that, The concentration of the precursor solution was 0.2 wt.%–1.0 wt.%.
4. The method according to claim 1, characterized in that, Lithium metal was cleaned with dimethyl carbonate in an inert atmosphere of argon, and the lithium metal was in the form of foil.
5. The method according to claim 1, characterized in that, Heating to 50°C removes the solvent.
6. The method according to claim 1, characterized in that, The gel polymer electrolyte is composed of a liquid electrolyte containing lithium hexafluorophosphate and a cross-linked polymer matrix, wherein the cross-linked polymer matrix is formed by cross-linking polyethylene glycol dimethacrylate and pentaerythritol tetraacrylate.
7. The method according to claim 1, characterized in that, Electrochemical pretreatment was performed at a current density of 0.2 mA cm⁻¹. 2 Perform 10 cycles under the given conditions.
8. The method according to claim 1, characterized in that, Heat treatment at 60 ℃.
9. A composite artificial solid electrolyte interface for a space lithium-ion battery, prepared by the method of any one of claims 1-8, having a thickness of 1.0 μm-5.2 μm.
10. A quasi-solid-state lithium metal battery, characterized in that, Including lithium metal anodes prepared by the method according to any one of claims 1-8.