Copper selenide / cellulose fabric composite current collector of high-performance lithium metal battery and preparation method of copper selenide / cellulose fabric composite current collector

Abstract

The invention belongs to the technical field of lithium metal batteries, and discloses a copper selenide / cellulose fabric composite current collector of a high-performance lithium metal battery and a preparation method of the copper selenide / cellulose fabric composite current collector. The method comprises the following steps: carrying out silanization treatment, polymerization reaction, catalyst adsorption and chemical copper plating reaction on a cellulose fabric to obtain a copper-plated fabric; and then reacting the copper-plated fabric with selenium powder through chemical vapor deposition to obtain the copper selenide-loaded cellulose fabric current collector. The current collector provided by the invention has a three-dimensional conductive skeleton structure, has high conductivity and excellent lithium affinity, and can effectively reduce lithium nucleation overpotential, guide uniform deposition of lithium ions and inhibit formation and growth of lithium dendrites, thereby improving coulombic efficiency and cycling stability of a lithium metal battery.

Description

Technical Field

[0001] This invention belongs to the technical field of lithium metal batteries, specifically relating to a copper selenide / cellulose fabric composite current collector for lithium metal batteries and its preparation method. Background Technology

[0002] In lithium metal batteries, lithium metal boasts an extremely high theoretical specific capacity (3860 mAh g⁻¹). -1 With its lowest electrochemical potential (-3.04 V vs. SHE), lithium metal anodes are considered one of the ideal anodes for realizing next-generation high-energy-density batteries. However, the practical application of lithium metal anodes still faces many challenges: uneven lithium nucleation easily induces dendrite growth, which not only shortens cycle life but also poses safety hazards; the unstable solid-state electrolyte interface (SEI) continuously consumes active lithium and electrolyte, reducing coulombic efficiency; in addition, the significant volume change of the electrode during charge and discharge also limits its application prospects in flexible devices.

[0003] To address the aforementioned issues, researchers have proposed various improvement strategies, including electrolyte engineering, SEI construction, and the design of three-dimensional conductive frameworks. Three-dimensional frameworks (such as porous metal foams and carbon fiber fabrics) effectively reduce local current density through their high specific surface area and provide space for lithium deposition, thereby suppressing dendrite formation and mitigating volume expansion to some extent. However, three-dimensional conductive frameworks such as copper foam and nickel foam, when used as lithium metal anodes, can lead to uneven lithium deposition due to factors such as varying pore sizes and uneven current distribution on the framework surface, easily resulting in lithium dendrite growth and the formation of dead lithium. Furthermore, the intrinsic lithiophore nature of copper or nickel materials creates a large nucleation barrier for lithium, also easily inducing lithium dendrite growth. Therefore, improving the pore size uniformity of the current collector and enhancing the lithiophilicity of the current collector surface are key factors in improving the performance of lithium metal anodes. Summary of the Invention

[0004] To address the problems of existing technologies, the present invention aims to provide a high-performance copper selenide / cellulose fabric composite current collector for lithium metal batteries and its preparation method. The current collector of the present invention is obtained by composited copper selenide and cellulose fabric. The cellulose fabric is uniformly coated with copper selenide. The hierarchical porous structure of the cellulose fabric optimizes the mass transfer process inside the electrode and provides sufficient lithium-containing space. Furthermore, the lithiophilic copper selenide can improve the interfacial lithiophilicity, reduce the nucleation overpotential, and effectively induce lithium-ion diffusion and uniform nucleation in the early stages of lithium deposition. This allows the lithium metal battery to effectively suppress lithium dendrite growth and achieve excellent electrochemical performance.

[0005] The objective of this invention is achieved through the following technical solution:

[0006] A method for preparing a high-performance copper selenide / cellulose fabric composite current collector for lithium metal batteries includes the following steps:

[0007] S1. The cellulose fabric is immersed in a silanization solution for silanization treatment to obtain a silanized fabric; the silanization solution is obtained by dissolving 3-(methacryloyloxy)propyltrimethoxysilane (MPTS) in a mixed solution of anhydrous ethanol, glacial acetic acid and water during the silanization treatment.

[0008] S2. The silanized fabric is immersed in the polymerization solution, and a polymerization reaction is carried out to obtain the polymerized fabric; the polymerization solution is composed of methacryloyloxyethyltrimethylammonium chloride (METAC), an initiator and water;

[0009] S3. The polymer-treated fabric is immersed in an aqueous solution of ammonium tetrachloropalladium for adsorption in the dark to obtain a fabric with adsorbed catalyst.

[0010] S4. The fabric with the adsorbed catalyst is immersed in a chemical plating solution to carry out a chemical copper plating reaction to obtain a copper-plated fabric; the chemical plating solution is obtained by mixing a copper-containing solution and a formaldehyde solution; the copper-containing solution is composed of sodium hydroxide, copper sulfate pentahydrate, potassium sodium tartrate and water.

[0011] S5. Copper-plated fabric and selenium powder are reacted by chemical vapor deposition to obtain a copper selenide-loaded cellulose fabric current collector, namely a copper selenide / cellulose fabric composite current collector.

[0012] The volume ratio of anhydrous ethanol, glacial acetic acid and water in the mixed solution in step S1 is 95:1:4.

[0013] The volume ratio of 3-(methacryloyloxy)propyltrimethoxysilane to the mixed solution is (2~5):(50~100).

[0014] Silanization treatment conditions: Silanization treatment at room temperature for 0.5~2 h.

[0015] After silanization, the sample is washed with water.

[0016] In step S2, the volume ratio of methacryloyloxyethyltrimethylammonium chloride (METAC) to water in the polymerization solution is (10~20):(30~50), and the volume-to-mass ratio of methacryloyloxyethyltrimethylammonium chloride to the initiator is (10~20) mL:(50~150) mg. The initiator is potassium sulfate.

[0017] The polymerization reaction conditions described in step S2 are: 80~90 ℃ for 1~2 h.

[0018] After the polymerization reaction, the mixture is washed with water.

[0019] In step S3, the mass-to-volume ratio of ammonium tetrachloropalladium to water in the aqueous solution of ammonium tetrachloropalladium is (0.1~0.5) g : (200~500) mL.

[0020] Adsorption conditions in the dark: stand in the dark for 15~90 min.

[0021] After adsorption is complete, the product is washed with water.

[0022] In step S4, the concentration of sodium hydroxide in the copper-containing solution is 10-15 g / L, the concentration of copper sulfate pentahydrate is 10-15 g / L, and the concentration of potassium sodium tartrate is 25-35 g / L.

[0023] The volume ratio of formaldehyde to aqueous solution in the formaldehyde solution is 8~12 mL:1L.

[0024] The volume ratio of the copper-containing solution to the formaldehyde solution is 1:1.

[0025] Conditions for electroless copper plating reaction: electroless copper plating at room temperature for 0.5~2 h, with the plating surface turned over every 5~15 min during the chemical process.

[0026] After the copper plating reaction, the product is washed with water and anhydrous ethanol in sequence, and then dried at 60~80 ℃.

[0027] The chemical vapor deposition described in step S5 refers to placing the copper-plated fabric in the downstream temperature zone, placing the selenium powder in the upstream temperature zone, and introducing a carrier gas. The temperature of the upstream temperature zone is 500~700 ℃ (preferably 550~650 ℃), and the temperature of the downstream temperature zone is 100~200 ℃. The deposition reaction is carried out for 2~6 h (preferably 3~5 h).

[0028] The mass ratio of selenium powder to copper-plated fabric is 2:1 to 5:1, preferably 3:1 to 4.5:1.

[0029] The heating rate in the upstream and downstream temperature zones is 2~10 ℃ / min.

[0030] The carrier gas is argon or an argon-hydrogen mixture, and the flow rate is 8–20 mL / min, preferably 9–15 mL / min.

[0031] After the reaction is complete, the mixture can be washed with water and anhydrous ethanol in sequence, and then dried at 60~80 °C to obtain copper selenide-supported cellulose fabric current collector (denoted as CuSe@CF).

[0032] Cellulose fabrics require pretreatment, specifically:

[0033] The cellulose fabric is immersed in an ethanol solution and ultrasonically cleaned for 10-30 minutes to remove surface impurities, and then dried in an oven at 60-80 ℃ until constant weight.

[0034] Flexible fabrics with cellulose as the main component or fiber fabrics with hydroxyl functional groups on the surface are selected. The hydroxyl groups on the surface can participate in the silanization reaction and have a continuous fiber structure and interconnected pore structure. They can withstand silanization treatment, polymer-assisted deposition treatment and metal selenization process, thereby forming a firmly bonded and uniformly distributed metal layer on its surface.

[0035] Cellulose fabric is at least one of hemp cellulose fabric or cotton cellulose fabric.

[0036] The cellulose fabric has a thickness of 50–120 μm, an average pore size of 5–25 μm, a porosity of 60–85%, and a specific surface area of ​​0.3–0.6 m². 2 / g, the weaving method is plain weave.

[0037] The copper selenide / cellulose fabric composite current collector was prepared by the above method.

[0038] The copper selenide / cellulose fabric composite current collector is used to prepare electrodes for lithium metal batteries, preferably the negative electrode of lithium metal batteries.

[0039] The electrodes are the working electrode, the positive electrode, and the negative electrode.

[0040] The lithium metal battery has the following configurations: a half-cell uses CuSe@CF as the working electrode and a lithium metal sheet as the counter electrode and reference electrode; a symmetrical cell uses electrodes formed by depositing lithium metal on CuSe@CF as the positive and negative electrodes; the electrolyte is a 1 mol / L LiTFSI DOL:DME mixed solution containing 2 wt% LiNO3 additive; and the separator is a polypropylene (PP) separator or an alumina (Al2O3) separator.

[0041] Compared with the prior art, the present invention has the following advantages:

[0042] (1) The current collector of the present invention has both high conductivity and lithium affinity, significantly reducing the lithium nucleation overpotential and outperforming traditional commercial copper foil current collectors.

[0043] (2) The hierarchical porous structure of cellulose fabric in the current collector of the present invention provides sufficient lithium storage space, optimizes the internal mass transfer of the electrode, and effectively suppresses volume expansion and dendrite growth.

[0044] (3) The method of the present invention is simple and the conditions are mild.

[0045] (4) The lithium metal half-cell assembled by the current collector of the present invention exhibits low nucleation overpotential, high coulombic efficiency and long cycle stability. Attached Figure Description

[0046] Figure 1This is a schematic flowchart of the method for preparing copper selenide / cellulose fabric composite current collector according to the present invention;

[0047] Figure 2 The XRD pattern of Cu@CF prepared in Comparative Example 2 is shown.

[0048] Figure 3 The XRD patterns of CuSe@CF prepared in Examples 1-3 are shown below.

[0049] Figure 4 SEM images of Cu@CF prepared in Comparative Example 2 and CuSe@CF prepared in Example 3;

[0050] Figure 5 EDS image of CuSe@CF obtained in Example 3;

[0051] Figure 6 The lithium copper half-cells assembled for Comparative Examples 1, 2, and Examples 1-3 were tested at 1 mA cm⁻¹. -2 Current density and 1mAh cm -2 Nucleation overpotential diagram under area capacity;

[0052] Figure 7 The lithium copper half-cells assembled for Comparative Examples 1, 2, and 3 were tested at 1 mA cm⁻¹. -2 Current density and 1mAh cm -2 Cyclic performance diagram under area capacity;

[0053] Figure 8 The symmetrical cell assembled in Example 3 was at 1 mA cm⁻¹ -2 Current density and 1 mAh cm -2 Cyclic performance diagram under area capacity. Detailed Implementation

[0054] The present invention will now be described in detail with reference to specific embodiments, but the scope of protection of the present invention is not limited to the following embodiments.

[0055] Example 1: Hemp cellulose fabric, selenium powder and copper-plated fabric in a mass ratio of 2:1

[0056] A method for preparing a copper selenide / cellulose fabric composite current collector includes the following steps:

[0057] (1) A hemp cellulose fabric is used as the substrate. The hemp cellulose fabric is mainly composed of natural hemp cellulose, has a continuous fiber network and an interconnected porous structure, has a thickness of 100 μm, large pore size (average pore size of 15 μm), a porosity of 75%, and a specific surface area of ​​0.46 m². 2 / g, the weaving method is plain weave, immersed in ethanol for ultrasonic cleaning for 30 min, and dried at 80 ℃;

[0058] (2) Silanization treatment: Dissolve 2 mL of MPTS in 50 mL of anhydrous ethanol / glacial acetic acid / deionized water (the volume ratio of aqueous ethanol, glacial acetic acid and deionized water is 95:1:4), soak the fabric for 1 h, and rinse 3 times with deionized water:

[0059] (3) Polymerization treatment: Mix 10 mL METAC with 40 mL deionized water, add 100 mg potassium sulfate, cover and react in an oven at 85 °C for 1 h, then rinse 3 times with deionized water;

[0060] (4) Adsorption catalyst: 0.284 g ammonium tetrachloropalladium was dissolved in 200 mL of deionized water, soaked in the dark for 30 min, and rinsed 3 times with deionized water;

[0061] (5) Chemical copper plating: Mix equal volumes of solution A (NaOH 12 g / L, CuSO4·5H2O 13 g / L, NaKC4H4O6·4H2O 29 g / L, solvent is water) and solution B (formaldehyde 9.5 mL / L, each 1L of solution B contains 9.5 mL of formaldehyde, solvent is water), plate copper for 1 h, rinse 3 times in deionized water and anhydrous ethanol respectively, and dry.

[0062] (6) Chemical vapor deposition: The mass ratio of selenium powder to copper-plated fabric is 2:1. Argon flow rate is 10 mL / min. The temperature is increased by 5 °C / min. The upstream temperature is 600 °C and the downstream temperature is 150 °C for 4 h to obtain copper selenide / cellulose fabric composite current collector CuSe@CF.

[0063] The copper selenide / cellulose fabric composite current collector is used to prepare lithium metal batteries.

[0064] Assemble a lithium metal half-cell: CuSe@CF is used as the working electrode, lithium sheet is used as the counter electrode and reference electrode, the electrolyte is 1M LiTFSI in DOL:DME (1:1) + 2% LiNO3, and the separator is PP membrane.

[0065] Battery test results: such as Figure 6 As shown, overpotential comparisons revealed that a larger overpotential indicates a tendency for the surface to exhibit a "whisker growth mode," making it prone to lithium dendrite formation. Testing revealed that the copper selenide / cellulose fabric composite current collector prepared in Example 1 exhibited a lower nucleation overpotential (19.1 mV), significantly lower than that of the copper / cellulose fabric current collector in Comparative Example 2 (38.5 mV) and the commercial conventional copper foil current collector in Comparative Example 1 (56.6 mV), indicating enhanced lithiophilicity and the ability to promote lithium nucleation.

[0066] Example 2: Hemp cellulose fabric, selenium powder and copper-plated fabric in a mass ratio of 3:1

[0067] (1)~(5) are the same as in Example 1.

[0068] (6) Chemical vapor deposition: the mass ratio of selenium powder to copper-plated fabric is 3:1, the argon flow rate is 10 mL / min, and the temperature is maintained at 600 ℃ upstream and 150 ℃ downstream for 4 h.

[0069] The lithium metal battery assembly is the same as in Example 1.

[0070] Battery test results: such as Figure 6 As shown, the copper selenide / cellulose fabric composite current collector prepared in Example 2 exhibited a lower nucleation overpotential (13.8 mV), which was better than that of Example 1 (19.1 mV) and much lower than that of the copper / cellulose fabric current collector in Comparative Example 2 (38.5 mV) and the commercial conventional current collector copper foil in Comparative Example 1 (56.6 mV), indicating that it has enhanced lithiophilicity and the ability to promote lithium nucleation.

[0071] Example 3: Hemp cellulose fabric, selenium powder and copper-plated fabric in a mass ratio of 4:1

[0072] (1)~(5) are the same as in Example 1.

[0073] (6) Chemical vapor deposition: the mass ratio of selenium powder to copper-plated fabric is 4:1, the argon flow rate is 10 mL / min, and the upstream temperature is 600 ℃ and the downstream temperature is 150 ℃ for 4 h.

[0074] The lithium metal battery assembly is the same as in Example 1. Specifically, a lithium metal symmetric battery is assembled by depositing CuSe@CF at a density of 5 mAh / cm³. -2 The positive and negative electrodes are lithium metal electrodes, the electrolyte is 1M LiTFSI in DOL:DME (1:1) + 2% LiNO3, and the separator is PP separator.

[0075] Battery test results: such as Figure 6 As shown, the copper selenide / cellulose fabric composite current collector prepared in Example 3 exhibited a lower nucleation overpotential (12.8 mV), which was superior to that of Example 1 (19.1 mV) and Example 2 (13.8 mV), and significantly lower than that of the copper / cellulose fabric current collector in Comparative Example 2 (38.5 mV) and the commercial conventional current collector copper foil in Comparative Example 1 (56.6 mV), indicating that it possesses enhanced lithiophilicity and the ability to promote lithium nucleation. Figure 7 As shown, the assembled half-cell at 1 mA cm⁻¹ -2 Current density and 1mAh cm -2Under the given area capacity, it can stably cycle for over 400 cycles with an average coulombic efficiency greater than 98.3%, significantly outperforming Comparative Example 1 (60 cycles, 91.1%) and Comparative Example 2 (130 cycles, 95.2%). Figure 8 As shown, the assembled symmetrical cell at 1 mA cm⁻¹ -2 Current density and 1 mAh cm -2 It can cycle stably for more than 330 hours under the area capacity.

[0076] Example 4: Hemp cellulose fabric, upstream temperature 500 °C, selenium powder to copper-plated fabric mass ratio 4:1

[0077] (1)~(5) are the same as in Example 1.

[0078] (6) Chemical vapor deposition: the mass ratio of selenium powder to copper-plated fabric is 4:1, the argon flow rate is 10 mL / min, and the temperature is maintained at 500 ℃ upstream and 150 ℃ downstream for 4 h.

[0079] Example 5: Hemp cellulose fabric, upstream temperature 700 °C, selenium powder to copper-plated fabric mass ratio 4:1

[0080] (1)~(5) are the same as in Example 1.

[0081] (6) Chemical vapor deposition: the mass ratio of selenium powder to copper-plated fabric is 4:1, the argon flow rate is 10 mL / min, and the upstream temperature is 700 ℃ and the downstream temperature is 150 ℃ for 4 h.

[0082] Comparative Example 1: Commercial conventional current collector copper foil

[0083] The lithium metal battery was assembled using a commercial copper foil current collector instead of the cellulose fabric-based current collector of the present invention, and the assembly and testing steps were the same as in Example 1.

[0084] Battery test results: such as Figure 6 As shown, the nucleation overpotential is 56.6 mV, indicating poor lithiophilicity; Figure 7 As shown, the assembled half-cell at 1 mA cm⁻¹ -2 Current density and 1 mAh cm -2 It can stably cycle for 60 cycles with an area capacity of [specific value] and an average coulombic efficiency greater than 91.1%, but its overall cycle stability is poor.

[0085] Comparative Example 2: Preparation of current collectors using only polymer-assisted deposition method

[0086] The current collector is only coated with copper by polymer-assisted deposition and is not subjected to selenization treatment, as in Example 1 (1) to (5).

[0087] Electrical performance test results: such as Figure 6As shown, the nucleation overpotential is 38.5 mV, lower than that of the commercial conventional current collector copper foil in Comparative Example 1 (56.6 mV). Figure 7 As shown, the assembled half-cell at 1 mA cm⁻¹ -2 Current density and 1 mAh cm -2 At its area capacity, it can stably cycle for more than 130 cycles with an average coulombic efficiency greater than 95.2%, which is better than Comparative Example 1 (60 cycles, 91.1%). This indicates that due to the presence of cellulose fabric, its hierarchical porous structure optimizes the mass transfer process inside the electrode and provides sufficient lithium storage space, thus improving the battery performance to a certain extent. However, the intrinsic lithium affinity of copper is still poor.

[0088] Figure 1 This is a schematic flowchart of the method for preparing the copper selenide / cellulose fabric composite current collector of the present invention.

[0089] Figure 2 The image shows the XRD pattern of Cu@CF prepared in Comparative Example 2.

[0090] Figure 3 The images show the XRD patterns of CuSe@CF prepared in Examples 1-3.

[0091] Figure 4 SEM images of Cu@CF prepared in Comparative Example 2 and CuSe@CF prepared in Example 3.

[0092] Figure 5 The image shows the EDS diagram of CuSe@CF obtained in Example 3.

[0093] Figure 6 The lithium copper half-cells assembled for Comparative Examples 1, 2, and Examples 1-3 were tested at 1 mA cm⁻¹. -2 Current density and 1mAh cm -2 Nucleation overpotential diagram under area capacity.

[0094] Figure 7 The lithium copper half-cells assembled for Comparative Examples 1, 2, and 3 were tested at 1 mA cm⁻¹. -2 Current density and 1mAh cm -2 Cyclic performance diagram under area capacity.

[0095] Figure 8 The symmetrical cell assembled in Example 3 was at 1 mA cm⁻¹ -2 Current density and 1 mAh cm -2 Cyclic performance diagram under area capacity.

Claims

1. A method for preparing a high-performance copper selenide / cellulose fabric composite current collector for lithium metal batteries, characterized in that: Includes the following steps: S1. The cellulose fabric is immersed in a silanization solution for silanization treatment to obtain a silanized fabric; the silanization solution is obtained by dissolving 3-(methacryloyloxy)propyltrimethoxysilane in a mixed solution of anhydrous ethanol, glacial acetic acid and water during the silanization treatment. S2. The silanized fabric is immersed in the polymerization solution, and a polymerization reaction is carried out to obtain the polymerized fabric; the polymerization solution is composed of methacryloyloxyethyltrimethylammonium chloride, an initiator and water; S3. The polymer-treated fabric is immersed in an aqueous solution of ammonium tetrachloropalladium for adsorption in the dark to obtain a fabric with adsorbed catalyst. S4. The fabric with the adsorbed catalyst is immersed in a chemical plating solution to carry out a chemical copper plating reaction to obtain a copper-plated fabric; the chemical plating solution is obtained by mixing a copper-containing solution and a formaldehyde solution; the copper-containing solution is composed of sodium hydroxide, copper sulfate pentahydrate, potassium sodium tartrate and water. S5. Copper-plated fabric and selenium powder are reacted by chemical vapor deposition to obtain copper selenide-loaded cellulose fabric current collector, i.e., copper selenide / cellulose fabric composite current collector. The volume ratio of anhydrous ethanol, glacial acetic acid and water in the mixed solution in step S1 is 95:1:4; In step S4, the concentration of sodium hydroxide in the copper-containing solution is 10-15 g / L, the concentration of copper sulfate pentahydrate is 10-15 g / L, and the concentration of potassium sodium tartrate is 25-35 g / L. The volume ratio of formaldehyde to formaldehyde solution in the formaldehyde solution is 8-12 mL:1 L; the volume ratio of copper-containing solution to formaldehyde solution is 1:

1. The chemical vapor deposition described in step S5 refers to placing the copper-plated fabric in the downstream temperature zone, the selenium powder in the upstream temperature zone, and introducing a carrier gas. The temperature of the upstream temperature zone is 500~700 ℃, and the temperature of the downstream temperature zone is 100~200 ℃. The deposition reaction is carried out for 2~6 h. The mass ratio of selenium powder to copper-plated fabric is 2:1~5:

1.

2. The method for preparing the copper selenide / cellulose fabric composite current collector for high-performance lithium metal batteries according to claim 1, characterized in that: In step S5, the temperature of the upstream temperature zone is 550~650 ℃; The mass ratio of selenium powder to copper-plated fabric is 3:1 to 4.5:

1.

3. The method for preparing the copper selenide / cellulose fabric composite current collector for high-performance lithium metal batteries according to claim 1, characterized in that: In step S1, the volume ratio of 3-(methacryloyloxy)propyltrimethoxysilane to the mixed solution is (2~5):(50~100). Silanization treatment conditions: Silanization treatment at room temperature for 0.5~2 h.

4. The method for preparing the copper selenide / cellulose fabric composite current collector for high-performance lithium metal batteries according to claim 1, characterized in that: In step S2, the volume ratio of methacryloyloxyethyltrimethylammonium chloride to water in the polymerization solution is (10~20):(30~50), and the volume-to-mass ratio of methacryloyloxyethyltrimethylammonium chloride to initiator is (10~20) mL:(50~150) mg; The initiator is potassium sulfate; The polymerization reaction conditions described in step S2 are: 80~90 ℃ for 1~2 h.

5. The method for preparing the copper selenide / cellulose fabric composite current collector for high-performance lithium metal batteries according to claim 1, characterized in that: In step S3, the mass-to-volume ratio of ammonium tetrachloropalladium to water in the aqueous solution is (0.1~0.5) g : (200~500) mL; Adsorption conditions in the dark: stand in the dark for 15~90 min; The conditions for the electroless copper plating reaction in step S4 are: electroless copper plating at room temperature for 0.5~2 h, with the plating surface turned over every 5~15 min during the chemical process; In step S5, the heating rate of the upstream and downstream temperature zones is 2~10 ℃ / min; The carrier gas is argon or an argon-hydrogen mixture, and the flow rate is 8–20 mL / min.

6. The method for preparing the copper selenide / cellulose fabric composite current collector for high-performance lithium metal batteries according to claim 1, characterized in that: In step S1, the cellulose fabric is at least one of hemp cellulose fabric and cotton cellulose fabric; The cellulose fabric has a thickness of 50–120 μm, an average pore size of 5–25 μm, a porosity of 60–85%, and a specific surface area of ​​0.3–0.6 m². 2 / g, the weave method is plain weave; After the silanization treatment in step S1, the sample is washed with water; After the polymerization reaction in step S2, the mixture is washed with water. After adsorption is complete in step S3, the product is washed with water. After the copper plating reaction in step S4, the product is washed with water and anhydrous ethanol in sequence, and then dried at 60~80 ℃.

7. A copper selenide / cellulose fabric composite current collector for a high-performance lithium metal battery obtained by the method of any one of claims 1 to 6.

8. The application of the copper selenide / cellulose fabric composite current collector in the high-performance lithium metal battery according to claim 7, characterized in that: The copper selenide / cellulose fabric composite current collector of the high-performance lithium metal battery is used to prepare the electrode of the lithium metal battery.

9. The application according to claim 8, characterized in that: The lithium metal battery is either a half-cell or a symmetrical cell, both comprising electrodes, an electrolyte, and a separator. In the half-cell, the copper selenide / cellulose fabric composite current collector as described in claim 7 is used as the working electrode, and a lithium metal sheet is used as the counter electrode and reference electrode. In the symmetrical cell, both the positive and negative electrodes are formed by depositing lithium metal on the copper selenide / cellulose fabric composite current collector as described in claim 7. The electrolyte is a 1 mol / L LiTFSI DOL:DME mixed solution containing 2 wt% LiNO3 additive. The separator is a polypropylene separator or an alumina separator.

10. The application of the copper selenide / cellulose fabric composite current collector in the high-performance lithium metal battery according to claim 8, characterized in that: The copper selenide / cellulose fabric composite current collector of the high-performance lithium metal battery is used to prepare the negative electrode of the lithium metal battery.

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