A water-based negative electrodeless battery based on pre-metallization treatment

Abstract

This invention discloses an aqueous electrodeless battery based on pre-metallization treatment, belonging to the field of aqueous battery technology. The invention relates to a novel pre-metallization method, the key being the loading of a sulfur / selenium host material onto a metal current collector. Through an initial charging cycle, the material undergoes a charging process, forming highly conductive metal sulfides / selenides in the bulk phase. This method utilizes the efficient charge carriers and redox activity of metal ions to construct an aqueous metal-sulfur battery, achieving effective and safe pre-metallization of the positive electrode through electrochemical methods. Compared to existing pre-metallization methods, this method is simpler and safer, has less stringent requirements for the operating environment, reduces the need for compensation or protection of the necessary metal negative electrode, and significantly saves production costs. Furthermore, this invention also solves the problems of poor cycle performance and low capacity in existing aqueous batteries.

Description

Technical Field

[0001] This invention belongs to the field of aqueous battery technology and relates to an aqueous non-anode battery based on pre-metallization treatment. Background Technology

[0002] The increasing demand for renewable energy and energy security urgently necessitates the development of high-performance, low-cost, and sustainable energy storage technologies. While lithium-ion batteries have long been the primary choice for energy devices in electronic products, their potential in transportation and large-scale stationary energy storage systems has been largely hampered by the high risks of fire and explosion associated with the use of flammable organic electrolytes. Aqueous batteries, as the name suggests, use water as the electrolyte solvent, fundamentally solving the safety issues caused by flammable organic electrolytes, avoiding the stringent manufacturing conditions and expensive electrolyte costs of organic systems, and fundamentally improving the power characteristics of the battery system (the ionic conductivity of aqueous electrolytes is two orders of magnitude higher than that of organic electrolytes). Furthermore, aqueous solvents are more environmentally friendly. Based on these advantages, research on aqueous batteries has once again aroused widespread interest among researchers to meet the future requirements for efficient and safe energy storage. However, the development of aqueous battery systems is limited by the poor conductivity, low capacity, and limited cycle stability of existing electrode materials.

[0003] Pre-metallization technology is an indispensable method in electrochemical energy storage systems. It can effectively compensate for irreversible capacity loss, increase operating voltage, and increase the concentration of metal ions in the electrolyte, making it key to advancing commercial energy storage devices. However, despite its benefits in improving electrochemical performance, pre-metallization technology has received relatively little attention, severely hindering the commercialization of electrochemical energy storage systems and requiring further in-depth research. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide an aqueous electrodeless battery based on pre-metallization treatment.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] 1. An aqueous electrodeless battery based on pre-metallization treatment, the aqueous electrodeless battery comprising a positive electrode, a separator, and an aqueous electrolyte;

[0007] The positive electrode is a positive electrode current collector with adsorption active sites or a specific surface area greater than or equal to 10 m². 2 / g of positive electrode current collector;

[0008] The aqueous, electrodeless battery is pre-metallized by constant current charging after assembly.

[0009] Preferably, the positive electrode current collector with adsorption active sites is a positive electrode current collector with a coating layer on its surface, and the coating layer is a material that can interact with the active substance.

[0010] The active substance is any one of sulfur, selenium, or selenium disulfide.

[0011] More preferably, the material is any one of reduced graphene oxide, porous titanium carbide, disordered mesoporous carbon, carbon nanotubes, or nitrogen-doped carbon nanotubes.

[0012] More preferably, the composite effect is carried out by melt diffusion method, which specifically involves heating to a pyrolysis temperature of 150-260°C at a rate of 2-10°C / min under an inert atmosphere and then holding the temperature for 12-15 hours.

[0013] The inert gas in the inert atmosphere specifically includes any one of N2, Ar, or a mixture of Ar and H2;

[0014] The volume ratio of Ar to H2 in the mixed gas is 95:5 to 60:40.

[0015] Preferably, the positive current collector includes any one of copper, iron, cobalt, nickel, magnesium, aluminum, zinc, manganese, cadmium, vanadium, or titanium foil.

[0016] Preferably, the solvent in the aqueous electrolyte is water and the solute is a water-soluble metal salt;

[0017] The metal salts include any one or more of copper salts, iron salts, cobalt salts, nickel salts, magnesium salts, aluminum salts, zinc salts, manganese salts, cadmium salts, vanadium salts, or titanium salts.

[0018] More preferably, the metal salt is any one or more of sulfate, nitrate, acetate, carbonate, acetic acid, or chloride.

[0019] More preferably, the concentration of metal ions in the aqueous electrolyte is 0.1–5 mol / L. -1 .

[0020] Preferably, the pre-metallization specifically involves: charging the battery with a constant current on a LAND battery testing system, replenishing the metal ion concentration as needed, and controlling the degree of pre-metallization by controlling the operation time or potential.

[0021] Preferably, the diaphragm is made of glass fiber GF / D.

[0022] The beneficial effects of this invention are as follows:

[0023] This invention discloses an aqueous electrodeless battery based on pre-metallization treatment. The battery includes a positive electrode, a separator, and an aqueous electrolyte. The main modification is to the positive electrode, which undergoes pre-metallization after assembly: using a positive electrode current collector with adsorption active sites or a specific surface area greater than or equal to 10 m². 2 Using a positive electrode current collector of / g as the positive electrode, this invention utilizes the high efficiency of metal ions as charge carriers and their certain redox activity to construct an aqueous metal-sulfur battery. It achieves effective and safe pre-metallization of the positive electrode through an electrochemical method. This method is simpler and safer than existing pre-metallization methods, has less stringent requirements for the operating environment, reduces the need for compensation or protection of the necessary metal negative electrode, and significantly saves production costs. Furthermore, this invention can also solve the problems of poor cycle performance and low capacity in existing aqueous batteries.

[0024] Other advantages, objectives, and features of the invention will be set forth in part in the description which follows, and in part will be apparent to those skilled in the art from the following examination, or may be learned from practice of the invention. The objectives and other advantages of the invention can be realized and obtained through the following description. Attached Figure Description

[0025] To make the objectives, technical solutions, and advantages of the present invention clearer, the preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings, wherein:

[0026] Figure 1 The images show a comparison of XRD patterns of the surface-modified MXene-based material (Sd-Ti3C2), the sulfur-loaded composite material (S@Sd-Ti3C2), pure Ti3C2, and pure sulfur prepared in Example 1.

[0027] Figure 2 SEM images of the surface-modified MXene-based material (Sd-Ti3C2) (a) and the sulfur-loaded composite material (S@Sd-Ti3C2) (b) prepared in Example 1;

[0028] Figure 3 The nitrogen adsorption-desorption curves are shown for the surface-modified MXene-based material (Sd-Ti3C2) prepared in Example 1.

[0029] Figure 4 The image shows the pore size distribution curve of the surface-modified MXene-based material (Sd-Ti3C2) prepared in Example 1.

[0030] Figure 5 The thermogravimetric analysis results are for the sulfur-loaded composite product (S@Sd-Ti3C2) prepared in Example 1.

[0031] Figure 6 The aqueous, electrodeless copper-sulfur battery prepared in Example 2, based on the pre-copper treatment of the composite product (S@Sd-Ti3C2), was tested at 1.9 Ag. -1 Capacity test curve at a current density of (1.2C);

[0032] Figure 7 The comparison of EIS impedance Nyquist spectra of the aqueous copper-sulfur battery without negative electrode (Pre-plating) based on the composite product (S@Sd-Ti3C2) and the aqueous copper-sulfur battery without pre-plating (No-Pre-plating) before cycling is shown.

[0033] Figure 8 The cycling performance (a) and rate performance (b) of the aqueous copper-sulfur battery without a negative electrode prepared in Example 2 based on the pre-copper treatment of the composite product (S@Sd-Ti3C2) are shown.

[0034] Figure 9 The rate performance of the aqueous electrodeless copper-sulfur battery based on the pre-copperization treatment of the composite product (S@C) prepared in Example 3;

[0035] Figure 10 The rate performance (a) and cycle performance (b) of the aqueous electrodeless copper selenium battery based on the pre-copper treatment of the composite product (S@Sd-Ti3C2) prepared in Example 4 are shown. Detailed Implementation

[0036] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that the illustrations provided in the following embodiments are only schematic representations of the basic concept of the present invention. Unless otherwise specified, the following embodiments and features can be combined with each other.

[0037] Example 1

[0038] A surface-modified MXene-based (Sd-Ti3C2) material, the specific method of which includes the following steps:

[0039] (1) First, the A phase in the MAX phase was etched using LiF and HCl to obtain Ti3C2T XNanosheet preparation, specific operation: 1g Ti3AlC2 was slowly added to a mixed solution of 20mL 9mol / L HCl and 1g LiF. After reacting at 35℃ for 24h, the product was repeatedly washed with deionized water by centrifugation until the pH reached approximately 6. The resulting precipitate was then dispersed in 150mL of deionized water and sonicated for 3h under inert gas protection to obtain a suspension. The suspension was then centrifuged at 3500rpm for 45min to obtain a few-layer Ti3C2T nanosheet. x -MXene colloidal solution and store in the refrigerator for later use.

[0040] (2) Dissolve 700 mg of sulfur powder in 10 mL of ethylenediamine (EDA) solution to form a deep red S-EDA solution, and gradually add the above deep red solution dropwise to 200 mL of Ti3C2T solution with a concentration of 0.5 mg / mL in step (1) while stirring at room temperature. x In an MXene colloidal solution, after stirring for 30 minutes, 140 mL of a 10% HCl solution was gradually added dropwise.

[0041] (3) Stir the solution obtained in step (2) for 30 min to obtain S / Ti3C2 precursor solution. First, wash with secondary water by vacuum filtration 2 to 3 times, then wash with anhydrous ethanol by vacuum filtration 2 to 3 times, and then vacuum dry at 60℃ for 12 h to obtain S / Ti3C2 precursor.

[0042] (4) The precursor obtained in step (3) is pyrolyzed at 400°C for 2 hours under a nitrogen atmosphere. After it cools down naturally, the surface-modified MXene-based material (Sd-Ti3C2) is obtained.

[0043] (5) The MXene-based material (Sd-Ti3C2) prepared above was ground and mixed with sulfur powder at a mass ratio of 4:6. Under an argon atmosphere, the temperature was raised to 155°C at a heating rate of 2°C / min and held for 12 hours. After cooling to room temperature, the sulfur-loaded composite product (S@Sd-Ti3C2) was obtained.

[0044] Figure 1 The images show a comparison of XRD patterns of the surface-modified MXene-based material (Sd-Ti3C2), the sulfur-loaded composite material (S@Sd-Ti3C2), pure Ti3C2, and pure sulfur prepared in Example 1. Figure 1 It can be seen that the characteristic peaks of pure Ti3C2 are fully displayed in the composite, proving that the surface-modified MXene-based material (Sd-Ti3C2) was successfully synthesized in Example 1; and the peaks of the sulfur-loaded composite material (S@Sd-Ti3C2) match well with the standard card of sulfur (PDF#08-0247), proving that sulfur was successfully injected into the composite.

[0045] Figure 2 SEM images of the surface-modified MXene-based material (Sd-Ti3C2) (a) and the sulfur-loaded composite material (S@Sd-Ti3C2) (b) prepared in Example 1. Figure 2 As can be seen from section a, after surface modification, MXene transforms from a two-dimensional nanosheet into a three-dimensional porous structure, capable of accommodating a larger amount of active substances or intermediate products. From Figure 2 The SEM image of the sulfur-loaded composite material (S@Sd-Ti3C2) in the middle b shows that the sulfur-impregnated material can maintain its original light and sheet-like morphology, and there are almost no large pieces of sulfur on the surface, which indicates that most of the sulfur has diffused into the host material.

[0046] Figure 3 This is a nitrogen adsorption-desorption curve of the surface-modified MXene-based material (Sd-Ti3C2) prepared in Example 1. Figure 4 This is a pore size distribution curve of the surface-modified MXene-based material (Sd-Ti3C2) prepared in Example 1. Figure 3 and Figure 4 As can be seen, the surface-modified MXene-based material (Sd-Ti3C2) has a relatively large specific surface area (140.573 m²). 2 g -1 ) and pore volume (0.33cm) 3 g -1 This allows for the subsequent injection of sulfur.

[0047] Figure 5 The thermogravimetric analysis results are for the sulfur-loaded composite product (S@Sd-Ti3C2) prepared in Example 1. Figure 5 The TGA curve shows a clear weight loss phase, which is due to the sublimation of sulfur. The test results indicate that the sulfur content in the sulfur-loaded composite product (S@Sd-Ti3C2) is about 52%.

[0048] Example 2

[0049] An aqueous, electrodeless copper-sulfur battery based on pre-copper treatment of composite product (S@Sd-Ti3C2) is described, and the assembly method of the battery specifically includes the following steps:

[0050] (1) The sulfur-loaded composite product (S@Sd-Ti3C2), polyvinylidene fluoride (PVDF), and conductive carbon black prepared in Example 1 were mixed and ground in a mass ratio of 8:1:1. N-methylpyrrolidone (NMP) (whose mass is 1% of the mass of the sulfur-loaded composite product (S@Sd-Ti3C2)) was added and wet-ground until the slurry could pass through a 200-mesh stainless steel sieve.

[0051] (2) Use a wet film coating machine to coat the slurry after grinding and sieving in step (1) onto the copper foil, control the thickness to be 200 μm, and then transfer it to a vacuum oven at 80°C to dry for 12 h to obtain a copper foil current collector coated with S@Sd-Ti3C2.

[0052] (3) Cut the copper foil current collector coated with S@Sd-Ti3C2 prepared in step (2) into small circular pieces with a diameter of 12 mm as the positive electrode. Assemble the button cell in the order of negative electrode shell, spring, gasket, separator, current collector and positive electrode shell (the button cell model used is CR2032, and the separator is glass fiber separator), and add 120 μL of electrolyte (the electrolyte is 0.5 mol / L CuSO4 aqueous solution);

[0053] (4) After assembly, the button cell battery is left to stand at room temperature for 8 hours, and then charged to 0.45V using the LAND battery testing system to achieve pre-coppering of the material.

[0054] Figure 6 The aqueous, electrodeless copper-sulfur battery based on pre-copper treatment prepared in Example 2 was tested at 1.9 Ag. -1 Capacity test curves at a current density of (1.2C). From Figure 6 It can be seen that the specific capacity at this point reaches 1547 mAh g. -1 It also exhibits a high initial coulombic efficiency of 93.4%. Furthermore, the voltage-specific capacity curve shows that the polarization range of this battery is only ≈0.1V, which is far lower than the polarization voltage of other aqueous metal-sulfur batteries.

[0055] Figure 7 The image shows a comparison of the EIS impedance Nyquist spectra of the pre-copper-treated aqueous copper-sulfur battery without a negative electrode prepared in Example 2 and the untreated aqueous copper-sulfur battery before cycling. The comparison results show that the pre-copper-treated aqueous copper-sulfur battery without a negative electrode has a lower internal resistance and a faster ion diffusion rate than the untreated aqueous copper-sulfur battery, indicating that this method effectively treats Cu… 2+ The lower activation energy of diffusion is beneficial to improving the reaction kinetics of the electrode and plays an important role in enhancing the ion diffusion capability of the material.

[0056] Figure 8The cycling performance (a) and rate performance (b) of the aqueous, electrodeless copper-sulfur battery based on pre-copper treatment prepared in Example 2 are shown. Figure 8 It can be seen that the aqueous, electrodeless copper-sulfur battery based on pre-copper treatment prepared in Example 2, at 2.2C (3.1Ag), -1 The current density achieved excellent electrochemical stability, retaining 92.1% capacity retention after 600 cycles, demonstrating that pre-copper treatment can effectively compensate for irreversible capacity loss in the bulk phase. Furthermore, the rate performance of the pre-copper-treated aqueous electrodeless copper-sulfur battery prepared in Example 2 is also outstanding; in rate tests from 0.1 to 5C, the capacity difference between the minimum and maximum current densities is only 19% (0.4C (1838.4 mAh g)). -1 ) / 4.8C (1489mAh g) -1 Its excellent rate performance is also attributed to Cu. 2+ The pre-doping significantly improves the Cu... 2+ The diffusion capability in the bulk phase fully demonstrates the positive role of the pre-copperization strategy in improving the electrochemical performance of materials.

[0057] Example 3

[0058] An aqueous, electrodeless copper-sulfur battery based on pre-copper treatment of composite products (S@C) is described, and the assembly method of the battery specifically includes the following steps:

[0059] (1) Mesoporous carbon CMK3 and sulfur powder are ground and mixed evenly at a mass ratio of 4:6. Under an argon atmosphere, the temperature is raised to 155℃ at a rate of 2℃ / min and held for 12h. After cooling to room temperature, the sulfur-loaded composite product (S@C) can be obtained.

[0060] (2) The sulfur-loaded composite product (S@C), polyvinylidene fluoride (PVDF) and conductive carbon black prepared above are mixed and ground in a mass ratio of 8:1:1. N-methylpyrrolidone (NMP) (whose mass is 1% of the mass of the sulfur-loaded composite product (S@C)) is added and wet-ground until the slurry can pass through a 200-mesh stainless steel screen.

[0061] (3) Use a wet film coating machine to coat the slurry after grinding and sieving in step (1) onto the copper foil, control the thickness to be 200 μm, and then transfer it to a vacuum oven at 80°C to dry for 12 h to obtain a copper foil current collector coated with S@C.

[0062] (4) Cut the copper foil current collector coated with S@C prepared in step (3) into small circular pieces with a diameter of 12 mm as the positive electrode. Assemble the button cell in the order of negative electrode shell, spring, gasket, separator, current collector and positive electrode shell (the button cell model used is CR2032, and the separator is glass fiber separator), and add 120 μL of electrolyte (the electrolyte is 0.5 mol / L CuSO4 aqueous solution).

[0063] (5) After assembly, the button cell battery is left to stand at room temperature for 8 hours, and then charged to 0.45V using the LAND battery testing system to achieve pre-coppering of the material.

[0064] Figure 9 The rate performance of the aqueous, electrodeless copper-sulfur battery based on pre-copperization treatment of the composite product (S@C) prepared in Example 3 is shown. Figure 9 It can be seen that the aqueous electrodeless copper-sulfur battery prepared in Example 3 based on the pre-copper treatment of the composite product (S@C) has good rate performance, ranging from 0.8 to 5 Ag. -1 In the rate test, the capacity difference between the minimum and maximum current densities was only 19.7% (of which 0.8Ag) -1 The discharge capacity is 1805.4 mAhg. -1 5Ag -1 The discharge capacity is 1448.1 mAhg. -1 ), and when the current density changes from 5Ag -1 Back to 0.8Ag -1 At that time, the discharge capacity recovered to 1922mAhg -1 (Capacity retention rate of 106.4%) indicates that this aqueous copper-sulfur battery without a negative electrode also has outstanding reversibility.

[0065] Example 4

[0066] An aqueous, electrodeless copper selenide battery based on pre-copper treatment of composite product (S@Sd-Ti3C2) is described, and the assembly method of the battery specifically includes the following steps:

[0067] (1) The surface-modified MXene-based material (Sd-Ti3C2) prepared in step (4) of Example 1 was ground and mixed with selenium powder at a mass ratio of 4:6. Under an argon atmosphere, the temperature was raised to 260°C at a heating rate of 2°C / min and kept at the temperature for 12 hours. After cooling to room temperature, the selenium-loaded composite product (Se@Sd-Ti3C2) was obtained.

[0068] (2) The above composite product (Se@Sd-Ti3C2), polyvinylidene fluoride (PVDF) and conductive carbon black are mixed and ground in a mass ratio of 8:1:1. N-methylpyrrolidone (NMP) (whose mass is 1% of the mass of the sulfur-loaded composite product (Se@Sd-Ti3C2)) is added and wet-ground until the slurry can pass through a 200-mesh stainless steel screen.

[0069] (3) The above-ground and sieved slurry was coated onto copper foil using a wet film coating machine, with a thickness of 200 μm. Then it was transferred to a vacuum oven at 80°C and dried for 12 h to obtain a copper foil current collector coated with Se@Sd-Ti3C2.

[0070] (4) Cut the copper foil current collector coated with Se@Sd-Ti3C2 prepared in step (3) into small circular pieces with a diameter of 12 mm as positive electrodes. Assemble the button cell in the order of negative electrode shell, spring, gasket, separator, current collector and positive electrode shell (the button cell model used is CR2032, and the separator is glass fiber separator), and add 120 μL of electrolyte (the electrolyte is 0.5 mol / L CuSO4 aqueous solution).

[0071] (5) After assembly, the button cell battery is left to stand at room temperature for 8 hours, and then charged to 0.45V using the LAND battery testing system to achieve pre-coppering of the material.

[0072] Figure 10 The rate performance (a) and cycle performance (b) of the aqueous, electrodeless copper selenide battery based on the pre-copper treatment of the composite product (S@Sd-Ti3C2) prepared in Example 4 are shown. Figure 10 As can be seen from Figure a, the aqueous electrodeless copper selenide battery prepared in Example 4 based on the pre-copper treatment of the composite product (S@Sd-Ti3C2) exhibits good rate performance at 0.85 Ag. -1 1.75Ag -1 2.55Ag -1 3.45Ag -1 4.25Ag -1 and 5Ag -1 At the given current density, their respective discharge capacities are 902.2 mAh g. -1 827.5mAhg -1 733mAhg -1 731.6mAhg -1 736.4mAhg -1 and 728.4mAhg -1 When the current density returns to 0.8 Ag -1 At that time, the discharge capacity can still reach 906mAhg -1(Capacity retention rate is 100.4%). Additionally, from... Figure 10 As can be seen from b, this aquatic copper selenide battery without a negative electrode operates at 4.8 Ag. -1 After 350 cycles at a current density, it still maintained 609.1 mAh g. -1 The discharge capacity showed no significant capacity loss, and the coulombic efficiency was close to 100%, indicating that the aqueous electrodeless copper selenide battery prepared in Example 4 based on the pre-copper treatment of the composite product (S@Sd-Ti3C2) has good cycle stability, which fully demonstrates that the pre-copperization strategy has a positive effect on improving the electrochemical performance of the material.

[0073] Based on the performance and principle of the batteries prepared by the methods in Examples 1-4 above, it is shown that the present invention, based on a pre-metallized aqueous electrodeless battery, utilizes the high-efficiency charge carriers of metal ions and certain redox activity to construct an aqueous metal-sulfur battery. Through electrochemical methods, it achieves effective and safe pre-metallization of the positive electrode, solving the problems of poor cycle performance and low capacity in existing aqueous batteries. Therefore, by modifying the relevant conditions in Examples 1-4, based on the same principle, an improved performance-based pre-metallized aqueous electrodeless battery can also be obtained, mainly manifested in:

[0074] First, in a pre-metallized aqueous electrodeless battery, the positive electrode is a positive electrode current collector with adsorption active sites or a specific surface area greater than or equal to 10 m². 2 g -1 The positive electrode current collector, having adsorption active sites, is a material coated on its surface that can recombine with the active material (the recombination reaction is a melt diffusion method, specifically: under an inert atmosphere, the temperature is raised to 150-260℃ at a rate of 2-10℃ / min, followed by pyrolysis and holding at that temperature for 12-15h, wherein the inert gas in the inert atmosphere specifically includes: N2, Ar, or a mixture of Ar and H2 (volume ratio of 95:5-60:40)). The active material is any one of sulfur, selenium, or selenium disulfide; and the positive electrode current collector includes any one of copper, iron, cobalt, nickel, magnesium, aluminum, zinc, manganese, cadmium, vanadium, or titanium foil.

[0075] Secondly, the solvent in the aqueous electrolyte is water, and the concentration of the solute, which is a water-soluble metal ion, is 0.1–5 mol / L. -1 Metal salts (metal salts include any one or more of copper salts, iron salts, cobalt salts, nickel salts, magnesium salts, aluminum salts, zinc salts, manganese salts, cadmium salts, vanadium salts, or titanium salts, such as any one or more of sulfates, nitrates, acetates, carbonates, acetic acid salts, or chlorides).

[0076] In summary, this invention employs a one-step constant-current charging electrochemical strategy to pre-metallize the material. This method is simpler and safer than existing pre-metallization methods, has less stringent requirements for the operating environment, reduces the need for compensation or protection with a necessary metal anode, significantly saves production costs, and is beneficial for industrial production applications. Simultaneously, this method can overcome the shortcomings of existing electrode materials, such as poor conductivity, low battery capacity, and limited cycle stability, providing insights into pre-metallization strategies for other electrochemical energy storage systems. Using this method, an aqueous, anode-free copper-sulfur battery based on pre-copper treatment was prepared. The material undergoes a charging process in the first cycle, causing it to form highly conductive CuS in the bulk phase. This method utilizes Cu... 2+ A copper-sulfur battery was constructed using high-efficiency charge carriers and certain redox activity, achieving a highly efficient and reversible self-conversion reaction process via electrochemical methods. Simultaneously, this method bypasses some major sulfur-related issues in copper storage, including the extremely low conductivity of sulfur and poor cycle stability caused by soluble polysulfides. Electrochemical results show that the stability of the material is further improved after pre-copperization treatment, achieving an initial efficiency of over 90% and a specific capacity of 1576.9 mAh g⁻¹. -1 With a capacity retention rate of over 90% after 600 cycles, its electrochemical performance is superior to other aqueous metal batteries. Therefore, this method is beneficial for realizing high-current charge-discharge and long-term cycling applications in aqueous electrodeless batteries.

[0077] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A pre-metallized aqueous electrodeless battery, characterized in that, Includes the positive electrode, the diaphragm, and the aqueous electrolyte; The positive electrode is a positive electrode current collector that meets the following conditions: (a) a surface coating layer with adsorption active sites, wherein the surface coating layer material is selected from graphene oxide, porous titanium carbide, disordered mesoporous carbon, carbon nanotubes or nitrogen-doped carbon nanotubes; (b) specific surface area ≥10m² / g. The surface coating layer is combined with the active material by melt diffusion method, and the active material is sulfur, selenium or selenium disulfide; The melt diffusion method includes: heating to 150-260℃ at a rate of 2-10℃ / min and holding at that temperature for 12-15 hours under an inert atmosphere; the inert atmosphere is Ar. The positive electrode current collector material is selected from copper; The solvent of the aqueous electrolyte is water, and the solute is a soluble metal salt, wherein the metal salt is a copper salt. Assemble the battery in the following order: negative electrode shell, spring, gasket, separator, current collector, and positive electrode shell. The battery is pre-metallized by charging with a constant current after assembly.

2. The aqueous, negative-electrode-less battery according to claim 1, characterized in that, The metal salt is at least one of sulfate, nitrate, acetate, carbonate, acetic acid, or chloride.

3. The aqueous, negative-electrode-less battery according to claim 1, characterized in that, The concentration of metal ions in the electrolyte is 0.1~5 mol·L⁻¹. -1 .

4. The aqueous, negative-electrode-less battery according to claim 1, characterized in that, The pre-metallization is achieved by charging with a constant current and adjusting the degree of pre-metallization by controlling the time or potential.

5. The aqueous, negative-electrode-less battery according to claim 1, characterized in that, The diaphragm is made of glass fiber GF / D.

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