A cobalt-doped antimony oxychloride composite negative electrode material, a preparation method thereof, and application in aqueous chloride ion batteries

Abstract

The present invention discloses a cobalt-doped antimony oxychloride composite negative electrode material, a preparation method thereof, and an application in aqueous chloride ion batteries. The present invention prepares a cobalt-doped antimony oxychloride composite negative electrode material with a doping amount of 1 to 5 mol% by a hydrothermal method by dispersing cobalt salt and antimony salt in a graphene aqueous solution with a pH of 0 to 6 according to a certain ratio and concentration. After drying, the material is annealed at 200 to 350°C to obtain antimony oxychloride layered crystals with good crystallinity. The present invention dissolves Co in water. 2+ Replace Sb in crystal 3+ The present invention improves the physical and chemical properties of the material by taking advantage of its inherent properties, while also having the advantages of simple preparation steps, low cost, easy control of process conditions, and suitability for mass production.

Description

Technical Field

[0001] The present invention belongs to the technical field of material engineering, and relates to a cobalt-doped antimony oxychloride composite negative electrode material, a preparation method thereof, and application thereof in aqueous chloride ion batteries. Background Art

[0002] Aqueous chloride-ion batteries are a new type of electrochemical power source device that has developed rapidly in recent years and has broad development prospects. On the one hand, aqueous electrolytes not only ensure the safety of energy storage batteries but are also environmentally friendly and green and pollution-free; on the other hand, seawater, minerals, salt lakes, etc. are rich in chlorine resources, which are low-cost and abundant in resources. However, unlike the electrode materials widely used in lithium batteries, sodium batteries, etc., chloride ions are usually difficult to embed into the lattice of transition metal oxides; at the same time, the instability of chloride ion redox materials and their solubility in electrolytes also lead to a short cycle life of the battery, thereby limiting its development and application in the field of energy storage. Therefore, the development of electrode materials with long life, high stability and high capacity is one of the technical bottlenecks that chloride-ion batteries urgently need to solve.

[0003] Compared with other materials, transition metal oxychlorides such as bismuth oxychloride and antimony oxychloride have great development and application potential. They have the following advantages:

[0004] 1. The crystal has a special layered structure, which allows chloride ions to freely escape and embed between layers to a certain extent;

[0005] 2. When selecting a suitable cathode material (such as a silver electrode), the extraction and insertion of chloride ions can be within a lower potential window, ensuring that the aqueous electrolyte is not decomposed;

[0006] 3. Transition metal oxychlorides have the advantages of abundant resources and low raw material costs, and are suitable for application fields such as large-scale energy storage that are more sensitive to energy storage costs.

[0007] However, transition metal oxychlorides suffer from low electronic conductivity, low charge and discharge efficiency, insufficient utilization of active materials, and poor rate performance, which limit their practical application. Furthermore, another major difficulty in constructing aqueous chloride-ion batteries is that transition metal oxychloride electrodes are prone to hydrolysis during operation, leading to the decomposition of transition metal oxychloride crystals and the failure of the electrode material.

[0008] To improve the electronic conductivity of transition metal chloride oxides, methods such as adding nanocarbon conductive agents (ACS Appl. Mater. Interfaces 11 (2019) 9144-9148) and constructing nanocarbon composite materials (J. Power Sources 433 (2019) 126685) have been proposed to improve the electrochemical reaction kinetics of the electrode. At the same time, to further slow down the hydrolysis reaction of transition metal chloride oxide electrodes in aqueous environments and improve the cycle life and cycle stability of the electrodes, the academic community has also proposed methods such as adjusting the pH value of the aqueous electrolyte (Energy Storage Mater. 7 (2017) 189-194) and using high-concentration "salt-in-water" electrolytes (iScience 24 (2021) 101976). Although the above method has improved the electrochemical performance of transition metal chloride oxide negative electrode materials to a certain extent, it has failed to fundamentally improve the problem of unstable structure and easy hydrolysis of antimony chloride oxide. Therefore, aqueous chloride ion batteries using the above electrode materials still face a series of defects such as short cycle life, low Coulombic efficiency, and poor cycle stability. Summary of the Invention

[0009] The first object of the present invention is to address the deficiencies in the prior art and provide a method for preparing a cobalt-doped antimony oxychloride composite negative electrode material.

[0010] The method for preparing a cobalt-doped antimony oxychloride composite negative electrode material according to the present invention comprises the following steps:

[0011] Step (1): dispersing graphene oxide in deionized water, adjusting the pH to 0-6, and stirring in air to form a uniform graphene aqueous solution.

[0012] Preferably, the graphene concentration of the graphene aqueous solution in step (1) is 0.2 to 0.6 mg / mL.

[0013] Preferably, hydrochloric acid is used to adjust the pH value of the graphene aqueous solution in step (1).

[0014] Preferably, the stirring time in step (1) is 0.5 to 2 hours.

[0015] Step (2), dissolving a certain proportion of cobalt salt and antimony salt in a certain amount of graphene aqueous solution, heating and stirring in air until the solution becomes an opaque suspension; the molar ratio of the cobalt and antimony elements is 1:100 to 1:20;

[0016] Preferably, the cobalt salt used in step (2) is one or more of cobalt acetate, Co(NO3)2, CoCl2, and CoSO4; the antimony salt is one or more of SbCl3, Sb(NO3)3, antimony ethanol, antimony sulfate, and antimony acetate;

[0017] Preferably, the molar ratio of antimony to water in the solution in step (2) is 1:500 to 1:1200.

[0018] Preferably, the stirring heating temperature in step (2) is 50-80° C., and the stirring time is 1-4 h.

[0019] Step (3): placing the solution obtained in step (2) in a hydrothermal reactor and performing a hydrothermal reaction under certain temperature and time conditions to generate cobalt-doped antimony oxychloride with a doping amount of 1 to 5 mol%.

[0020] Preferably, the hydrothermal reaction temperature selected in step (3) is 120-160° C., and the reaction time is 12-24 h.

[0021] As a preference, the cobalt-doped antimony oxychloride generated in step (3) may be SbOCl, Sb4O5Cl2, Sb8O 11 One or a mixture of Cl2.

[0022] Step (4): washing the cobalt-doped antimony oxychloride generated by the reaction in step (3) with a washing solvent, and then placing it in a vacuum oven for drying.

[0023] Preferably, the washing solvent in step (4) is one or more of deionized water, ethanol, methanol, chloroform, and acetonitrile.

[0024] Preferably, the drying temperature selected in step (4) is 60-100° C. and the drying time is 12-24 h.

[0025] Step (5): placing the sample obtained in step (4) in a muffle furnace and annealing it under certain temperature conditions and atmosphere.

[0026] Preferably, the calcination atmosphere selected in step (5) is an air environment or a pure oxygen environment.

[0027] Preferably, the annealing temperature of the sample in step (5) is 200-350° C., and the annealing time is 1-3 h.

[0028] Step (6): Grind and crush the sample annealed in step (5) to obtain cobalt-doped antimony oxychloride powder.

[0029] The second object of the present invention is to provide a cobalt-doped antimony oxychloride composite negative electrode material.

[0030] The third object of the present invention is to provide an application of a cobalt-doped antimony oxychloride composite negative electrode material in an aqueous chloride ion battery.

[0031] The beneficial effects of the present invention are:

[0032] The method of the present invention first disperses cobalt salt and antimony salt in a graphene aqueous solution with a pH of 0 to 6 according to a certain ratio and concentration, and then prepares a cobalt-doped antimony oxychloride composite material with a doping amount of 1 to 5 mol% by a hydrothermal method. After drying, the composite material is annealed at 200 to 350°C to obtain antimony oxychloride layered crystals with good crystallinity. 2+ Replace Sb in crystal 3+ The chlorine and oxygen vacancy formation energy is reduced after the position is positioned, which improves the chloride ion release performance and the stability of the crystal structure, significantly enhancing the cycle life and electrochemical performance of the material. Compared with existing methods for improving the electrochemical performance of transition metal chloride oxide electrodes, this method can improve its physical and chemical properties based on the inherent properties of the material. It also has the advantages of simple preparation steps, low cost, easy-to-control process conditions, and suitability for mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 1 and 2 are XRD patterns of the cobalt-doped antimony oxychloride composite material (Example 1) and the undoped antimony oxychloride composite material (Comparative Example 1) obtained in the present invention.

[0034] Figure 2 Graphs showing Raman spectra of the cobalt-doped antimony oxychloride composite material (Example 1) and the undoped antimony oxychloride composite material (Comparative Example 1) obtained in the present invention.

[0035] Figure 3 These are SEM images of (a) the cobalt-doped antimony oxychloride composite material (Example 1) and (b) the undoped antimony oxychloride composite material (Comparative Example 1) obtained in the present invention.

[0036] Figure 4 Schematic diagram of the assembly of the chloride ion test cell.

[0037] Figure 5 Specific capacity-cycle number graph of the cobalt-doped antimony oxychloride composite material (Example 1) and the undoped antimony oxychloride composite material (Comparative Example 1) obtained in the present invention. DETAILED DESCRIPTION

[0038] As mentioned above, in view of the shortcomings of the existing technology, the inventors of this case have proposed the technical solution of the present invention after long-term research and extensive practice, which is mainly based on at least:2+ Replace Sb in crystal 3+ After the position is changed, the formation energy of chlorine and oxygen vacancies is reduced, the chloride ion release performance and the stability of the crystal structure are improved, and the cycle life and electrochemical performance of the material are significantly improved.

[0039] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0040] In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0041] In a first aspect, the present invention provides a method for preparing a cobalt-doped antimony oxychloride composite material, the preparation process comprising the following steps:

[0042] Step (1): dispersing graphene oxide in deionized water, adjusting the pH to 0-6, and stirring in air to form a uniform graphene aqueous solution.

[0043] Preferably, the graphene concentration of the graphene aqueous solution in step (1) is 0.2 to 0.6 mg / mL.

[0044] Preferably, hydrochloric acid is used to adjust the pH value of the graphene aqueous solution in step (1).

[0045] Preferably, the stirring time in step (1) is 0.5 to 2 hours.

[0046] Step (2), dissolving a certain proportion of cobalt salt and antimony salt in a certain amount of graphene aqueous solution, heating and stirring in air until the solution becomes an opaque suspension; the molar ratio of the cobalt and antimony elements is 1:100 to 1:20;

[0047] Preferably, the cobalt salt used in step (2) is one or more of cobalt acetate, Co(NO3)2, CoCl2, and CoSO4; the antimony salt is one or more of SbCl3, Sb(NO3)3, antimony ethanol, antimony sulfate, and antimony acetate;

[0048] Preferably, the molar ratio of antimony to water in the solution in step (2) is 1:500 to 1:1200.

[0049] Preferably, the stirring heating temperature in step (2) is 50-80° C., and the stirring time is 1-4 h.

[0050] Step (3): placing the solution obtained in step (2) in a hydrothermal reactor and performing a hydrothermal reaction under certain temperature and time conditions to generate cobalt-doped antimony oxychloride with a doping amount of 1 to 5 mol%.

[0051] Preferably, the hydrothermal reaction temperature selected in step (3) is 120-160° C., and the reaction time is 12-24 h.

[0052] As a preference, the cobalt-doped antimony oxychloride generated in step (3) may be SbOCl, Sb4O5Cl2, Sb8O 11 One or a mixture of Cl2.

[0053] Step (4): washing the cobalt-doped antimony oxychloride generated by the reaction in step (3) with a washing solvent, and then placing it in a vacuum oven for drying.

[0054] Preferably, the washing solvent in step (4) is one or more of deionized water, ethanol, methanol, chloroform, and acetonitrile.

[0055] Preferably, the drying temperature selected in step (4) is 60-100° C. and the drying time is 12-24 h.

[0056] Step (5): placing the sample obtained in step (4) in a muffle furnace and annealing it under certain temperature conditions and atmosphere.

[0057] Preferably, the calcination atmosphere selected in step (5) is an air environment or a pure oxygen environment.

[0058] Preferably, the annealing temperature of the sample in step (5) is 200-350° C., and the annealing time is 1-3 h.

[0059] Step (6): Grind and crush the sample annealed in step (5) to obtain cobalt-doped antimony oxychloride powder.

[0060] In a second aspect, the present invention provides a cobalt-doped antimony oxychloride composite negative electrode material.

[0061] In a third aspect, the present invention provides an application of a cobalt-doped antimony oxychloride composite negative electrode material in an aqueous chloride ion battery.

[0062] The present invention will be further analyzed below in conjunction with specific implementation methods.

[0063] Example 1. Preparation of Cobalt-doped Antimony Oxychloride Composite Anode Material and Performance of Aqueous Chloride Ion Battery

[0064] 1.1 Preparation of Cobalt-doped Antimony Oxychloride Composite Anode Materials

[0065] Graphene oxide was dispersed in deionized water to prepare a 0.2 mg / mL graphene aqueous solution. Concentrated hydrochloric acid was added dropwise to adjust the pH to 2 and stirred in air for 0.5 h to form a uniform graphene aqueous solution. 0.1 mmol of cobalt acetate and 2.5 mmol of antimony trichloride were dissolved in 50 ml of the graphene aqueous solution. The solution was heated to 60°C in air and stirred for 4 h until the solution became an opaque suspension. The resulting solution was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 120°C for 12 h to synthesize a cobalt-doped antimony oxychloride composite anode material. The resulting cobalt-doped antimony oxychloride composite material was removed from the reaction, washed with deionized water and anhydrous ethanol, and dried in a vacuum oven at 60°C for 12 h. The dried sample was annealed in a muffle furnace at 300°C in air for 2 h. The annealed sample was ground to obtain the cobalt-doped antimony oxychloride composite material.

[0066] Figure 1 The XRD pattern of the cobalt-doped antimony oxychloride composite material obtained in Example 1 is shown. The main diffraction peaks of the XRD patterns before and after Co doping correspond to those of the standard card, demonstrating that the doping modification process has not changed its crystal structure type. By comparison with the standard PDF card, the phase of the synthesized antimony oxychloride is Sb4O5Cl2. From the magnified (001) crystal plane XRD diffraction peak, it can be seen that the (001) diffraction peak shifts significantly to a lower angle after the addition of the Co element, demonstrating that the lattice constant of the material has changed after doping. Figure 2 This is the Raman spectrum of the cobalt-doped antimony oxychloride composite negative electrode material obtained in Example 1. From the figure, we can see that there are significant graphene characteristic peaks in the sample, which are located at 1309 cm -1 (D peak) and 1586cm -1 (G peak). The intensity ratio of D peak and G peak before and after Co doping (I D / I G ) are very close, which are 3.71 and 3.73 respectively, proving that the introduction of Co element does not significantly change the properties of the graphene composite matrix. Figure 3 This is a SEM image of the cobalt-doped antimony oxychloride composite negative electrode material obtained in Example 1. As can be seen from the image, the microscopic morphology of the sample before and after Co doping does not change significantly, showing a similar irregular granular agglomerate structure.

[0067] 1.2 Performance testing of aqueous chloride ion batteries with cobalt-doped antimony oxychloride cathode materials

[0068] The cobalt-doped antimony oxychloride composite negative electrode material in Example 1 was mixed with the binder PVDF and the conductive agent Super P in a ratio of 70:10:20 wt.%, fully mixed in a mortar and then dispersed in N-methylpyrrolidone. After stirring evenly, the mixture was coated on the surface of graphite paper. The mixture was dried in an oven at 120°C for 12 hours, the coated slurry was dried, and cut into 15×10 mm square pieces as the negative electrode sheets of chloride ion batteries. The above-mentioned negative electrode sheet, silver electrode (Ag-coated graphite paper), and diaphragm (glass fiber filter membrane) were mixed in accordance with the method. Figure 4 The battery was assembled by sandwiching it between glass slides as shown. The battery was then immersed in a 1M NaCl aqueous solution and subjected to constant current charge and discharge testing using a Neware battery testing system. The capacity of the chloride ion battery was tested by constant current charge and discharge performance at a temperature of 25°C, a current density of 500 mA / g, and a charge and discharge voltage range of 0-1.4V for 50 cycles.

[0069] Figure 5 This is a graph showing the discharge capacity versus cycle number of the cobalt-doped antimony oxychloride composite negative electrode material obtained under the test conditions of a charge and discharge current density of 500mA / g and a charge and discharge potential range of 0-1.4V. As shown in the figure, the charge and discharge performance of the prepared chloride ion battery is as follows: the initial discharge capacity of the cobalt-doped antimony oxychloride composite negative electrode material reaches 142mAh / g. After 8 cycles, its capacity decay tends to stabilize at approximately 59.5mAh / g. After 50 cycles, it still has 57.5mAh / g, with a capacity retention rate of up to 96.7%. The initial discharge capacity of the undoped modified electrode is 140.2mAh / g. - In the subsequent process, the capacity continued to decay, and after 50 cycles, its capacity was only 9.8 mAh / g.

[0070] Example 2. Preparation of Cobalt-doped Antimony Oxychloride Composite Anode Material and Performance of Aqueous Chloride Ion Battery

[0071] Graphene oxide was dispersed in deionized water to prepare a 0.2 mg / mL graphene aqueous solution. Concentrated hydrochloric acid was added dropwise to adjust the pH to 2 and stirred in air for 0.5 h to form a uniform graphene aqueous solution. 50 mL of the graphene aqueous solution was dissolved with 0.125 mmol of cobalt acetate and 2.5 mmol of antimony trichloride. The solution was heated to 60°C in air and stirred for 4 h until the solution became an opaque suspension. The resulting solution was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 120°C for 12 h to synthesize a cobalt-doped antimony oxychloride composite anode material. The resulting cobalt-doped antimony oxychloride composite anode material was removed from the reaction, washed with deionized water and anhydrous ethanol, and dried in a vacuum oven at 60°C for 12 h. The dried sample was annealed in a muffle furnace at 300°C in air for 2 h. The annealed sample was ground to obtain the cobalt-doped antimony oxychloride composite anode material.

[0072] Example 3. Preparation of Cobalt-doped Antimony Oxychloride Composite Anode Material and Performance of Aqueous Chloride Ion Battery

[0073] Graphene oxide was dispersed in deionized water to prepare a 0.2 mg / mL graphene aqueous solution. Concentrated hydrochloric acid was added dropwise to adjust the pH to 2 and stirred in air for 0.5 h to form a uniform graphene aqueous solution. 50 mL of the graphene aqueous solution was dissolved with 0.05 mmol of cobalt acetate and 2.5 mmol of antimony trichloride. The solution was heated to 60°C in air and stirred for 4 h until the solution became an opaque suspension. The resulting solution was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 120°C for 12 h to synthesize a cobalt-doped antimony oxychloride composite anode material. The resulting cobalt-doped antimony oxychloride composite anode material was removed from the reaction, washed with deionized water and anhydrous ethanol, and dried in a vacuum oven at 60°C for 12 h. The dried sample was annealed in a muffle furnace at 300°C in air for 2 h. The annealed sample was ground to obtain the cobalt-doped antimony oxychloride composite anode material.

[0074] Example 4. Preparation of Cobalt-doped Antimony Oxychloride Composite Anode Material and Performance of Aqueous Chloride Ion Battery

[0075] Graphene oxide was dispersed in deionized water to prepare a 0.2 mg / mL graphene aqueous solution. Concentrated hydrochloric acid was added dropwise to adjust the pH to 2 and stirred in air for 0.5 h to form a uniform graphene aqueous solution. 50 ml of the graphene aqueous solution was dissolved with 0.025 mmol of cobalt acetate and 2.5 mmol of antimony trichloride. The solution was heated to 60°C in air and stirred for 4 h until the solution became an opaque suspension. The resulting solution was placed in a hydrothermal reactor and subjected to a hydrothermal reaction at 120°C for 12 h to synthesize a cobalt-doped antimony oxychloride composite anode material. The resulting cobalt-doped antimony oxychloride composite anode material was removed from the reaction, washed with deionized water and anhydrous ethanol, and dried in a vacuum oven at 60°C for 12 h. The dried sample was annealed in a muffle furnace at 300°C in air for 2 h. The annealed sample was ground to obtain the cobalt-doped antimony oxychloride composite anode material.

[0076] Comparative Example 1

[0077] The steps of Example 1 were followed, but the doping amount of Co was changed to produce a cobalt-doped antimony oxychloride composite negative electrode material. The cyclic charge-discharge performance test steps and parameters were the same as those of Example 1, and the test results are shown in Table 1.

[0078] Table 1 Chlorine electrocycling performance of Co-doped modified antimony oxychloride negative electrode material prepared in Comparative Example 1

[0079]

[0080] As can be seen from Table 1, the capacity retention rate of the antimony oxychloride composite negative electrode material after cobalt doping modification is significantly improved compared with the original sample. Therefore, this treatment method can be used as an effective modification method.

[0081] Comparative Example 2

[0082] The modified antimony oxychloride prepared in Examples 1, 2, 3, and 4 was compared with the lithium battery cycling performance reported in the literature (Acs Appl Mater Inter 11 (2019) 9144–9148). The electrochemical performance tests were conducted using the same electrolyte (1M NaCl aqueous solution) and test conditions (0-1.5V) as those used in the literature. Charge and discharge rates were 600 mA / g. The modified antimony oxychloride composite anode materials were cycled 50 times, and the initial and final discharge capacities were examined. The test results are shown in Table 2.

[0083] Table 2 Chlorine electrocycling performance of modified antimony oxychloride synthesized in Examples and Comparative Examples

[0084]

[0085]

[0086] As can be seen from Table 2, the discharge capacity retention of the antimony oxychloride composite anode material after cobalt doping modification is significantly improved compared to the method described in ACS Appl Mater Inter 11 (2019) 9144–9148. Therefore, this treatment method can, to a certain extent, make up for the shortcomings of existing methods and become a more effective means of modifying antimony oxychloride anode materials for chloride ion batteries.

[0087] The above embodiments are not limitations of the present invention, and the present invention is not limited to the above embodiments. As long as the requirements of the present invention are met, they belong to the protection scope of the present invention.

Claims

1. A method for preparing a cobalt-doped antimony oxychloride composite negative electrode material, characterized in that The method comprises the following steps: Step (1), dispersing graphene oxide in deionized water, adjusting the pH to 0-6, and stirring in air to form a uniform graphene aqueous solution; Step (2), dissolving a certain proportion of cobalt salt and antimony salt in a certain amount of graphene aqueous solution, heating and stirring in air until the solution becomes an opaque suspension; the molar ratio of the cobalt and antimony elements is 1:100 to 1:20; Step (3), placing the solution obtained in step (2) in a hydrothermal reactor, and performing a hydrothermal reaction under certain temperature and time conditions to generate cobalt-doped antimony oxychloride with a doping amount of 1 to 5 mol%; Step (4), washing the cobalt-doped antimony oxychloride generated by the reaction in step (3) with a washing solvent, and then placing it in a vacuum oven for drying; Step (5), placing the sample prepared in step (4) in a muffle furnace and annealing it under certain temperature conditions and atmosphere; Step (6): Grind and crush the sample annealed in step (5) to obtain cobalt-doped antimony oxychloride powder.

2. The method according to claim 1, characterized in that The graphene concentration of the graphene aqueous solution in step (1) is 0.2 to 0.6 mg / mL.

3. The method according to claim 1, characterized in that The cobalt salt used in step (2) is one or more of cobalt acetate, Co(NO3)2, CoCl2, and CoSO4; the antimony salt is one or more of SbCl3, Sb(NO3)3, antimony ethanol, antimony sulfate, and antimony acetate.

4. The method according to claim 1, wherein The molar ratio of antimony to water in the solution in step (2) is 1:500 to 1:1200.

5. The method according to claim 1, characterized in that In step (2), the stirring heating temperature is 50-80° C., and the stirring time is 1-4 h.

6. The method according to claim 1, characterized in that The hydrothermal reaction temperature selected in step (3) is 120-160° C., and the reaction time is 12-24 h.

7. The method according to claim 1, characterized in that The product types of cobalt-doped antimony oxychloride generated in step (3) are SbOCl, Sb4O5Cl2, Sb8O 11 One or a mixture of Cl2.

8. The method according to claim 1, characterized in that In step (5), the calcination atmosphere is an air environment or a pure oxygen environment; the annealing temperature is 200-350° C., and the annealing time is 1-3 hours.

9. A cobalt-doped antimony oxychloride composite negative electrode material, prepared by the method according to any one of claims 1 to 8.

10. Use of the cobalt-doped antimony oxychloride composite negative electrode material according to claim 9 in aqueous chloride ion batteries.

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