A modified current collector for self-generation of negative lithium metal battery, lithium metal battery
By introducing a nanoscale amorphous Ge layer on the surface of copper foil, the problem of uneven lithium deposition in lithium metal batteries was solved, achieving efficient lithium deposition and improved battery performance, especially increased coulombic efficiency and energy density.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- UNIV OF ELECTRONICS SCI & TECH OF CHINA
- Filing Date
- 2026-03-26
- Publication Date
- 2026-06-09
AI Technical Summary
In self-generated negative electrode lithium metal batteries, uneven deposition of lithium on the surface of copper foil current collectors leads to problems such as high nucleation barriers, dendritic growth, low coulombic efficiency, and high safety risks.
A nanoscale-thickness amorphous Ge layer is introduced onto the surface of copper foil and prepared by magnetron sputtering. This layer is then transformed in situ into a uniform intermetallic compound layer, reducing the lithium nucleation overpotential and guiding lithium to undergo high-density two-dimensional layered growth.
Uniform and dense lithium deposition was achieved, improving the cycle stability and safety of the battery, with a coulombic efficiency of 99.3%, more than 140 cycles, and an energy density of 307.4Wh/kg.
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Figure CN122177847A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of lithium metal battery technology, specifically relating to a modified current collector for self-generating negative electrode lithium metal batteries and lithium metal batteries. Background Technology
[0002] Lithium metal has 3860 mAh g -1 With its theoretical specific capacity and extremely low electrochemical potential, lithium metal is an ideal anode material for constructing high-energy-density rechargeable batteries. For self-generated lithium metal batteries, the initial state does not pre-place a lithium metal anode; instead, it uses a current collector to receive lithium ions from the positive electrode. This significantly reduces the introduction of excess lithium and inactive components on the anode side, potentially further improving battery energy density and simplifying electrode fabrication. However, during the first charge, these batteries require in-situ nucleation and growth of lithium metal on the current collector surface. The interfacial nucleation behavior and deposition uniformity directly determine the first-cycle coulombic efficiency, cycle life, and safety performance. Commercially available copper foil current collector surfaces are highly inert for lithium deposition, exhibiting an inherently high nucleation barrier. This leads to lithium tending to undergo heterogeneous nucleation at a few defect sites with low activation energies, following a three-dimensional island (Volmer-Weber) growth pattern. As a result, sparse, coarse nuclei form in the early stages of deposition. Subsequently, to reduce the high-energy lithium-copper interface, the nuclei preferentially grow vertically, eventually evolving into a dendritic, porous, and unstable lithium deposition layer. This uneven deposition morphology accelerates the formation of "dead lithium," exacerbates electrolyte consumption, leads to low coulombic efficiency (CE) and rapid capacity decay, and poses serious safety hazards. These problems are the root causes of the large loss of active lithium in the first cycle, poor cycle stability, and high safety risks in self-generated anode systems.
[0003] To address these issues, a common approach is to pre-introduce an alloyable metal layer on the surface of the copper current collector, allowing it to form an intermetallic compound interface layer during the initial lithiation process. This reduces the lithium nucleation barrier and improves deposition uniformity. For example, Zn, Ag, Au, or other metal or alloy layers can be deposited on the copper foil surface, followed by the formation of an intermetallic compound interface layer during cycling, or an intermetallic compound interface layer can be directly constructed. However, these methods still have two key drawbacks: First, some crystalline metal layers or discontinuous particle layers alloy slowly during the initial lithiation, making it difficult to quickly transform into a continuous and uniform intermetallic compound interface. This results in lithium preferentially depositing in exposed areas or localized low-energy sites before the interface is fully established, thus perpetuating uneven nucleation and growth. Second, to ensure coating integrity, sufficient interfacial reaction site density, and interface continuity, some existing solutions often require significantly increasing the coating thickness, even to the submicron or micron level. However, while thicker coatings can improve deposition stability to some extent, they also introduce more inactive mass and increase the Li-to-Li ratio. +The transmission path and interface impedance, and the generation of greater volumetric stress during repeated alloying / dealloying processes, thereby weaken the high energy density advantage that self-generated negative electrode batteries should have.
[0004] Therefore, developing current collector modification technology that combines ultra-thin characteristics, excellent interface stability, high ionic / electronic conductivity, and compatibility with large-scale production processes is key to realizing the practical application of self-generated negative electrode lithium metal batteries. Summary of the Invention
[0005] To address the problems existing in the background technology, the present invention aims to provide a modified current collector for self-generated lithium metal negative electrode batteries and a lithium metal battery. This modified current collector introduces a nanometer-thick Ge amorphous thin film on the surface of a copper foil, which is then transformed in situ into a uniform and dense intermetallic compound layer during the initial lithium deposition process. The rapid alloying speed significantly reduces the lithium nucleation overpotential, guiding the lithium metal to undergo high-density, two-dimensional layered growth, ultimately obtaining a flat and dense lithium deposition layer, greatly improving the cycle stability and safety of the battery.
[0006] To achieve the above objectives, the technical solution of the present invention is as follows:
[0007] A modified current collector for self-generating negative electrode lithium metal batteries, comprising a copper foil substrate;
[0008] An amorphous Ge layer is disposed on one side surface of the copper foil substrate. The amorphous Ge layer is prepared by magnetron sputtering and has a thickness of 10 nm - 50 nm.
[0009] Furthermore, the thickness of the copper foil substrate is 6 μm-20 μm.
[0010] Furthermore, the specific process of the magnetron sputtering method is as follows:
[0011] Step 1. Pre-treat the copper foil substrate;
[0012] Step 2. Place the pretreated copper foil substrate into the magnetron sputtering cavity. The target material is a high-purity germanium target with a purity of 99.99% or higher. Evacuate to a base vacuum level better than 5.0 × 10⁻⁶. -4 Pa; then introduce inert working gas and adjust the chamber pressure to 0.3 Pa - 1 Pa;
[0013] Step 3. Turn on the magnetron sputtering power supply and sputter to deposit an amorphous Ge metal layer on the surface of the copper foil substrate; wherein the sputtering power is 80 W-200 W, the deposition time is 10 s-600 s, and the desired modified current collector is obtained after sputtering.
[0014] Furthermore, in step 1, the pretreatment includes sequentially cleaning the copper foil substrate with organic solvents, acid washing or alkaline washing, deionized water washing and drying to remove surface oil and oxides.
[0015] A lithium metal battery for self-generating negative electrode is assembled from a modified current collector, a positive electrode, a separator, and an electrolyte.
[0016] The positive electrode is a lithium-containing positive electrode;
[0017] The amorphous Ge layer on the copper foil substrate faces the positive electrode;
[0018] During the initial lithium deposition process, an intermetallic compound Li was formed in situ on the surface of the amorphous Ge layer. x Ge layer, the Li x The Ge layer guides lithium ions to deposit on the surface of the modified current collector, forming an intermetallic compound anode interface.
[0019] Furthermore, the Li x Ge for Li 15 Ge4, Li 22 Ge5, etc.
[0020] Furthermore, the lithium-containing cathode is any one of lithium cobalt oxide, lithium iron phosphate doped with tungsten disulfide (WS2), or lithium-rich manganese-based materials.
[0021] Furthermore, the electrolyte is at least one of lithium salt-containing carbonate electrolyte and ether electrolyte.
[0022] The mechanism of this invention is as follows:
[0023] Germanium, as a group IV narrow bandgap semiconductor material, possesses high intrinsic electronic conductivity and fast Li diffusion capability. Therefore, it is more likely to undergo a rapid alloying reaction with Li during the first charge process, forming Li... x The Ge interface layer has both good electron transport and lithium-ion transport capabilities, and its lithiation process is more uniform, and stress is more easily released through local structural rearrangement and plastic deformation. This is conducive to the rapid formation of a continuous and stable lithium-loving interface and guides the uniform deposition of Li on the current collector surface.
[0024] This invention employs an ultrathin amorphous Ge layer to modify the surface of a copper foil current collector. Its core lies in utilizing the rapid alloying reaction between Ge and Li to construct a continuous Li layer in situ during the initial charging phase. x Ge-lithophile interface layer. The formation sequence of this interface layer is: first, rapid alloying to form Li... x Ge, and then in Li xThe process of "continuous deposition of metallic lithium on the Ge surface" transforms the high-barrier, discrete nucleation process that originally occurred on the inert copper surface into a low-barrier, in-plane uniform nucleation process that occurs on the lithium-loving alloy surface.
[0025] On the one hand, Li x Ge can guide uniform lithium deposition. The Ge layer forms after the initial lithiation of Li. x Ge exhibits better interfacial compatibility and lithiophilicity with subsequently deposited metallic lithium, thus lithium is more readily deposited in Li. x Lithium nucleates uniformly across the Li / Cu interface, rather than growing locally at a few defect sites. The interface energy between the two is significantly lower than that between the Li / Cu and Cu interfaces. According to classical nucleation theory, a lower interface corresponds to a lower nucleation barrier and a smaller nucleation overpotential, thus lithium is more readily absorbed across the entire Li / Cu interface. x High-density, uniform nucleation occurs at the Ge interface, rather than concentrated local growth at a few defect sites. Simultaneously, continuously formed Li... x The Ge layer can serve as a uniform ion / electron transport interface, promoting Li + The electrode surface exhibits a more uniform distribution, reducing localized current density concentration; and lithium atoms are deposited on the Li... x The lower lateral migration barrier of Ge surfaces facilitates interface spreading and two-dimensional layered growth, thereby suppressing the formation of dendrites, loose accumulation, and pointed protrusions. This reduces the generation of "dead lithium" and continuous electrolyte decomposition at the source, improves coulombic efficiency, slows capacity decay, and lowers the safety risk of short circuits caused by dendrites.
[0026] On the other hand, the Li-Ge system exhibits a rapid alloying rate. This invention utilizes a nanoscale ultrathin amorphous Ge layer, which, due to its small thickness and short Li diffusion path, significantly shortens the time required for the interfacial reaction to complete. Furthermore, amorphous Ge lacks a long-range ordered lattice and significant differences in crystal orientation; its atomic arrangement is disordered and highly isotropic, typically possessing more high-energy active sites. This allows for simultaneous lithiation reactions across the entire thin layer, avoiding the lithiation front lag and unreacted regions caused by differences in reactivity across different crystal planes in crystalline materials. Simultaneously, the small film thickness and short Li diffusion path of the ultrathin amorphous Ge layer during lithiation reduce lithiation inhomogeneities along the thickness direction, thereby reducing local stress concentration caused by volume expansion gradients. Moreover, the amorphous structure is not constrained by fixed crystal orientations and grain boundaries, making it easier to release alloying stress through local atomic rearrangement and plastic deformation, thus benefiting Li… x The rapid and continuous formation of the Ge interface layer and the improved interface stability are key advantages. Ultrathin amorphous layers are more prone to releasing volumetric stress during alloying, and are less susceptible to localized cracking, pulverization, or delamination. Therefore, they can be transformed into continuous Li more quickly and completely. xGe interface layer. It is precisely because of this "rapid and continuous" interface formation process that the present invention can effectively cover the copper substrate surface in the early stage of the first charge, avoid disordered lithium deposition in the exposed copper area, and ultimately achieve a uniform and dense lithium deposition morphology.
[0027] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:
[0028] 1. The modified current collector prepared in this invention only has an additional nanometer-thick metal Ge layer on the surface of the conventional current collector. Compared with the conventional lithium anode, it can enable the battery to have a higher energy density, up to 307.4Wh / kg.
[0029] 2. The modified current collector prepared in this invention generates a Li metal anode by itself during the electrochemical reaction. The uniform and dense lithium deposition reduces the side reaction area between active lithium and electrolyte, effectively suppressing the generation of "dead lithium" and continuous electrolyte consumption. The average coulombic efficiency of the lithium copper half-cell can reach 99.3%, and the number of stable cycles with CE>99% can reach more than 140 cycles. In the LFP||Ge-Cu self-generated anode full cell, the coulombic efficiency of the first charge is increased from 78.3% to 91.5%, and the capacity retention rate after 100 cycles can reach 41.7%.
[0030] 3. The preparation process of this invention is simple, easy to scale up, and has good compatibility with existing battery electrode processing procedures, and has the potential for large-scale production. Attached Figure Description
[0031] Figure 1 Crystal structure testing of the modified current collector obtained in Example 1;
[0032] Among them, (a) is the grazing incidence X-ray diffraction pattern of the modified current collector obtained in Example 1 and the conventional copper foil substrate of Comparative Example 1; (b) is the laser confocal Raman spectrum of the modified current collector.
[0033] Figure 2 SEM images of the modified current collector obtained in Example 1 and the lithium metal deposition morphology on a conventional copper foil substrate in Comparative Example 1.
[0034] Figure 3 The images show the SEM morphology and EDS elemental distribution of the modified current collector obtained in Example 1 and the conventional copper foil substrate in Comparative Example 1.
[0035] Figure 4 The Li||Ge-Cu half-cell assembled using the current collector of Example 1 and the half-cell assembled using the current collector of Comparative Example 1 were compared at 1 mA·cm⁻¹. -2 1 mAh·cm -2 Coulomb efficiency cycle curve under the given conditions.
[0036] Figure 5 The graph shows the cycle performance of the LFP||Ge-Cu self-generated negative electrode pouch cell assembled using the current collector of Example 1 and the comparative cell assembled using the current collector of Comparative Example 1.
[0037] Figure 6 This is a comparison graph showing the energy density of the LFP||Ge-Cu self-generated negative electrode pouch cell assembled using the current collector of Example 1 and the comparative cell assembled using the current collector of Comparative Example 1. Detailed Implementation
[0038] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the embodiments and accompanying drawings.
[0039] Example 1
[0040] A method for preparing a modified current collector (Cu@Ge-20) for self-generated negative electrode lithium metal batteries includes the following steps:
[0041] Step 1. Select a 10 μm thick commercial electrolytic copper foil as the substrate, and then pretreat the copper foil substrate. The specific pretreatment process is as follows:
[0042] The copper foil was placed in acetone and ethanol in sequence and ultrasonically cleaned for 15 minutes each. Then, the cleaned copper foil was immersed in 5wt% dilute hydrochloric acid solution for 30 seconds. After taking it out, it was immediately rinsed with a large amount of deionized water until neutral. The surface was dried with high-purity nitrogen gas and finally transferred to an 80℃ vacuum oven to dry for 2 hours.
[0043] Step 2. Fix the pretreated copper foil substrate on the sample stage of the magnetron sputtering equipment. The sputtering target used is a high-purity germanium target (99.999%).
[0044] The sputtering chamber was evacuated to a background vacuum of 6.0 × 10⁻⁶. -4 Pa, then high-purity argon gas (99.999%) is introduced, and the flow rate is adjusted to stabilize the working gas pressure at 0.5 Pa;
[0045] Step 3. Turn on the magnetron sputtering power supply and sputter to deposit an amorphous Ge metal layer on the surface of the copper foil substrate; wherein, the DC power supply power is 120 W, the deposition time is 120 s, the thickness of the amorphous Ge metal layer is 20 nm, and the desired modified current collector is obtained after sputtering.
[0046] Example 2
[0047] A modified current collector (Cu@Ge-10) differs from Example 1 only in that the magnetron sputtering deposition time is controlled to 60 seconds, resulting in a germanium coating with a thickness of approximately 10 nm.
[0048] Example 3
[0049] A modified current collector (Cu@Ge-50) differs from Example 1 only in that the magnetron sputtering deposition time is controlled to 300 seconds, resulting in a germanium coating with a thickness of approximately 50 nm.
[0050] Example 4
[0051] A modified current collector differs from Example 1 only in that the DC power of the magnetron sputtering is 80 W, and the deposition time is adjusted proportionally to obtain a thickness of about 20 nm.
[0052] Comparative Example 1
[0053] The pretreated copper foil substrate is used directly as the current collector, without depositing any coating.
[0054] Comparative Example 2
[0055] A modified current collector (Cu@Al-100) is prepared in a similar manner to that in Example 1, except that an aluminum target is used and the process parameters are controlled to deposit an aluminum coating with a thickness of approximately 20 nm.
[0056] The modified current collector prepared in this embodiment was subjected to crystal structure testing, such as... Figure 1 As shown, (a) is the grazing incidence X-ray diffraction pattern of the modified current collector obtained in Example 1 and the conventional copper foil substrate of Comparative Example 1; (b) is the laser confocal Raman spectrum of the modified current collector. Figure 1 As can be seen in (a), no obvious diffraction peaks of crystalline Ge were observed in Example 1, but the diffraction peaks of copper were consistent with those of Comparative Example 1; combined with Figure 1 (b) The Raman spectrum of Example 1 at 270-280 cm⁻¹ -1 It exhibits a broad and gentle scattering peak, which is a typical characteristic of amorphous Ge. Therefore, the current collector prepared in Example 1 is amorphous.
[0057] Performance testing
[0058] 1. Half-cell electrochemical testing:
[0059] Using the current collectors obtained in the above examples and comparative examples as the working electrode and lithium metal sheets as the counter / reference electrode, CR2025 coin cell half-cells were assembled. The electrolyte was 1 M LiTFSI in DOL / DME (1:1 v / v) + 2% LiNO3. Test conditions: at 0.5 mA·cm⁻¹ -2 Deposition at current density of 0.1 mAh·cm -2 Lithium, record the nucleation overpotential; at 1 mA·cm -2 1 mAh·cm -2Deposition / stripping cycles were performed under the specified conditions, and the coulombic efficiency was tested. The results are shown in Table 1.
[0060] 2. Characterization of sedimentary morphology:
[0061] After depositing a certain capacity, the above half-cell was disassembled, the working electrode was removed, and after cleaning and drying with DOL solvent, the lithium deposition morphology was observed using a scanning electron microscope. SEM images of the modified current collector obtained in Example 1 and the conventional copper foil substrate deposition morphology in Comparative Example 1 are shown below. Figure 2 As shown. From Figure 2 As can be seen, lithium is deposited uniformly and densely on the current collector of Example 1, resembling moss; while on the copper foil of Comparative Example 1, obvious dendrites and a loose porous structure are observed. Figure 3 The images show the SEM surface morphology and EDS distribution before and after magnetron sputtering deposition of amorphous germanium. Figure 3 As can be seen from the data, the surface of Example 1 after depositing 20 nm of amorphous germanium is flatter than that of Comparative Example 1, and the elemental distribution is also more uniform as can be seen from the EDS spectrum.
[0062] 3. Self-generated negative electrode full cell test:
[0063] With a surface capacity of 3.5 mAh·cm -2 LiFePO4 (LFP) was used as the positive electrode, and the current collectors of Example 1 and Comparative Example 1 were used as the negative electrode current collectors (self-generated negative electrode configuration). The separator was a polyolefin microporous separator, and the electrolyte was 1 M LiTFSI inDOL / DME (1:1 v / v) + 2% LiNO3. The soft-pack full cells were assembled and cycle tested.
[0064] The lithium iron phosphate batteries prepared in the above examples and comparative examples were subjected to capacity retention tests: the voltage range was 3.0-3.8V, the current ratio was 1C, and the test results are shown in Table 2.
[0065] Table 1. Lithium nucleation overpotential and half-cell cycle performance with different current collectors
[0066] plan Coating material and thickness Nucleation overpotential (mV) Average Coulomb efficiency (laps 2-50) Cycle life (CE > 99% of cycles) Example 1 Ge, 20 nm 9 ± 2 99.3% >140 Example 2 Ge, 10 nm 15 ± 3 98.9% 120 Example 3 Ge, 50 nm 11 ± 2 99.1% >140 Example 4 Ge (80W), 20 nm 12 ± 3 99.0% 130 Comparative Example 1 None (Bare Cu) 82 ± 15 96.5% 49 Comparative Example 2 Al, 20 nm 75 ± 10 97.2% 65
[0067] Table 2 Cycle performance of self-generated negative electrode full cell (NCM811 current collector)
[0068] Negative current collector First charge coulomb efficiency 100-cycle capacity retention Example 1 (Cu@Ge-20) 91.5% 41.7% Comparative Example 1 (Bare Cu) 78.3% 2.0%
[0069] As shown in Table 1, all examples (1-4) with Ge coatings exhibited significantly lower nucleation overpotentials than pure copper foil (Comparative Example 1) and Al coating control (Comparative Example 2), with Example 1 showing the lowest at 9 ± 2 mV. The corresponding average coulombic efficiency remained between 98.9% and 99.3%, significantly higher than the 96.5% of bare copper, and the number of stable cycles with CE>99% increased from 49 cycles to over 120 cycles. These results indicate that the Ge layer can effectively reduce the nucleation barrier and improve interface stability during the initial deposition stage, which is related to the in-situ formation of Li. x This is consistent with the mechanism of the Ge-lithiophilic interface. Full-cell data further demonstrates that, with the Cu@Ge-20 current collector, the first-charge coulombic efficiency increased to 91.5%, and the capacity retention after 100 cycles increased to 41.7%, indicating that the current collector of this invention can solve the problems of large active lithium loss in the first cycle, unstable lithium deposition / stripping, and rapid cycle decay.
[0070] Figure 4 The Li||Ge-Cu half-cell assembled using the current collector of Example 1 and the half-cell assembled using the current collector of Comparative Example 1 were compared at 1 mA·cm⁻¹. -2 1 mAh·cm -2 The Coulomb efficiency cyclic curve under the given conditions. (See diagram.) Figure 4 As shown, the half-cell using the current collector of Example 1 can maintain a stable coulombic efficiency of over 99% after initial activation and for more than 140 cycles; while the control half-cell using bare copper current collector shows obvious fluctuations and a continuous decline after about 50 cycles, indicating that the Ge coating can significantly improve the reversibility of the lithium deposition / stripping process.
[0071] Figure 5 The graph shows the cycle performance of the LFP||Ge-Cu self-generated negative electrode pouch cell assembled using the current collector of Example 1 and the comparative cell assembled using the current collector of Comparative Example 1. Figure 5 As shown, the LFP self-generated negative electrode full cell using Cu@Ge-20 current collector exhibits significantly slower capacity decay during cycling, while the bare copper control cell rapidly decays to near failure within the first 100 cycles. Combined with Table 2, it can be seen that Example 1 retains 41.7% of its capacity after 100 cycles, significantly better than the 2.0% of Comparative Example 1, indicating that the modified current collector of this invention can significantly improve the cycling stability of the self-generated negative electrode full cell.
[0072] Figure 6 This is a comparison graph showing the energy density of the LFP||Ge-Cu self-generated negative electrode pouch cell assembled using the current collector of Example 1 and the comparative cell assembled using the current collector of Comparative Example 1. As can be seen from the graph, the pouch cell assembled using the current collector of this invention has a higher energy density, reaching 307.4 Wh / kg.
[0073] The above description is merely a specific embodiment of the present invention. Any feature disclosed in this specification may be replaced by other equivalent or similar features unless otherwise specified. All disclosed features, or steps in all methods or processes, may be combined in any way except for mutually exclusive features and / or steps.
Claims
1. A modified current collector for self-generating lithium metal negative electrode batteries, characterized in that, The modified current collector includes a copper foil substrate and an amorphous Ge layer disposed on one side surface of the copper foil substrate; the amorphous Ge layer is prepared by magnetron sputtering and has a thickness of 10 nm - 50 nm.
2. The modified current collector as described in claim 1, characterized in that, The thickness of the copper foil substrate is 6 μm-20 μm.
3. The modified current collector as described in claim 1, characterized in that, The specific process of magnetron sputtering is as follows: Step 1. Pre-treat the copper foil substrate; Step 2. Place the pretreated copper foil substrate into the magnetron sputtering cavity. The target material is a high-purity germanium target with a purity of 99.99% or higher. Evacuate to a base vacuum level better than 5.0 × 10⁻⁶. -4 Pa; then introduce inert working gas and adjust the chamber pressure to 0.3 Pa - 1 Pa; Step 3. Turn on the magnetron sputtering power supply and sputter to deposit an amorphous Ge metal layer on the surface of the copper foil substrate; wherein the sputtering power is 80 W-200 W, the deposition time is 10 s-600 s, and the desired modified current collector is obtained after sputtering.
4. The modified current collector as described in claim 3, characterized in that, In step 1, the pretreatment includes sequentially cleaning the copper foil substrate with organic solvents, acid washing or alkaline washing, deionized water washing, and drying.
5. A self-generating negative electrode lithium metal battery, characterized in that, It is assembled from the modified current collector, positive electrode, separator and electrolyte as described in any one of claims 1-4; The positive electrode is a lithium-containing positive electrode; The amorphous Ge layer on the copper foil substrate faces the positive electrode; During the initial lithium deposition process, an intermetallic compound Li was formed in situ on the surface of the amorphous Ge layer. x Ge layer, the Li x The Ge layer guides lithium ions to deposit on the surface of the modified current collector, forming an intermetallic compound anode interface.
6. The self-generating negative electrode lithium metal battery as described in claim 5, characterized in that, The Li x Ge is Li 15 Ge4, Li 22 Ge5.
7. The self-generating negative electrode lithium metal battery as described in claim 5, characterized in that, The lithium-containing cathode is any one of lithium cobalt oxide, lithium iron phosphate doped with tungsten disulfide, or lithium-rich manganese-based materials.
8. The self-generating negative electrode lithium metal battery as described in claim 5, characterized in that, The electrolyte is at least one of lithium salt-containing carbonate electrolyte and ether electrolyte.