WO2023087148A1

WO2023087148A1 - Sulfide composite material for metal-ion battery, preparation method therefor, and application thereof

Info

Publication number: WO2023087148A1
Application number: PCT/CN2021/130980
Authority: WO
Inventors: 唐永炳; 潘庆广; 仝兆鹏
Original assignee: 中国科学院深圳先进技术研究院; 深圳中科瑞能实业有限公司
Priority date: 2021-11-16
Filing date: 2021-11-16
Publication date: 2023-05-25

Abstract

Disclosed is a sulfide composite material for a metal-ion battery, a preparation method therefor, and an application thereof. According to the present invention, a bismuth source, a molybdenum source, and a sulfur source are used as raw materials; a nitrogen-doped carbon-coated metal sulfide heterostructure p-MoS₂/n-Bi₂S₃@NC composite material is prepared by means of a hydrothermal reaction and a calcination process; a built-in electric field of a heterojunction in the material can effectively improve the diffusion kinetics and electronic conductivity of metal ions, thereby improving battery rate performance; and a coating carbon layer can significantly improve the structural stability of the material. A metal-ion battery prepared using the method has high rate performance, high specific capacity performance, and stable long cycling performance. Further disclosed is a battery comprising the sulfide composite material for a metal-ion battery.

Description

A kind of metal ion battery sulfide composite material and its preparation method and application

technical field

The invention relates to the technical field of battery materials, in particular to a metal ion battery sulfide composite material and a preparation method and application thereof.

Background technique

In recent years, rechargeable lithium-ion batteries have been widely used in 3C electronic products and electric vehicles because of their advantages such as no memory effect, high energy density and long cycle life. However, lithium-ion batteries cannot meet the greatly increased energy storage demand of the economy and society due to the limited resources of key materials for the positive electrode (lithium, cobalt, etc.) and the rising cost. Therefore, the development of a new generation of energy storage devices is of great significance for sustainable energy storage and conversion in the post-lithium era. In the study, it was found that potassium ions (-2.93V vs. standard hydrogen electrode), sodium ions (-2.71V vs. standard hydrogen electrode), magnesium ions (-2.37V vs. standard hydrogen electrode), calcium ions (-2.86V vs. .Standard hydrogen electrode), aluminum ion (-1.66V vs. standard hydrogen electrode), etc. have higher reduction potential than lithium ion (-3.04V vs. standard hydrogen electrode), and its metal reserves are abundant and cheap. As for the dual-ion battery, the positive electrode material can be selected from environmentally friendly and cheap graphite materials, and has the advantages of high voltage and high safety. For this reason, combined with their advantages, potassium-based, lithium-based, sodium-based, calcium-based, magnesium-based, aluminum-based dual-ion batteries have potential promotion prospects in the field of large-scale energy storage.

However, metal ions such as potassium, sodium, calcium, magnesium, and aluminum have larger radii than lithium ions, and their ion diffusion kinetics are slow and cause structural expansion of the host material, resulting in attenuation of battery capacity, unsatisfactory rate conversion performance, and short cycle life. And other issues. For this reason, finding suitable energy storage materials is of great significance for the further development of dual-ion batteries.

In the prior art, a variety of metal sulfides have been tried to be used for metal ion storage, such as: sulfides of intercalation metals Fe, Co, Ni, Mo, W, etc., conversion and alloying metals Sn, Sb, Bi , In and other sulfides. However, after these single materials store metal ions, they generally have poor conductivity, slow reaction kinetics, volume expansion, and pulverization, which cause problems such as difficulty in increasing battery capacity, poor rate performance, and short cycle life (Energy Storage Mater.2019 , 22, 66-95). In order to improve the practicability of metal sulfides as metal ion storage materials, the composite design of metal sulfides, and then used for metal ion storage has become the research direction of researchers, for example: carbon-based materials for molybdenum disulfide and ferrous disulfide Coating can alleviate volume expansion, enhance structural stability and improve electrical conductivity, which greatly improves cycle stability, but the improvement of reaction kinetics still needs to be improved (Adv.Funct.Mater.2020, 30, 2001484; Energy Storage Mater.2019 , 22, 228-234). Construction of heterojunctions by metal sulfides and metal sulfides or oxides, such as MoS ₂ /SnS (Nanoscale 2020, 12, 14689-14698) or Bi ₂ S ₃ /Bi ₂ O ₃ (ACS Appl.Mater.Interfaces 2018, 10,7201-7207), etc., using the built-in electric field formed by it can effectively improve ion diffusion and electronic conductivity, thereby improving the battery rate performance.

The document "Improving compactness and reaction kinetics of MoS ₂ @C anodes by introducing Fe ₉ S ₁₀ core for superior volumetric sodium/potassium storage" (Energy Storage Mater.2020, 24, 208-219) reported a carbon-coated MoS ₂ / Fe ₉ S ₁₀ heterojunction is used for sodium/potassium ion storage. Thanks to the synergy between the built-in electric field of the heterojunction and the carbon coating, the electrode material achieves excellent sodium/potassium ion storage performance, but it only Sodium/potassium-ion half cells were tested, full cells such as dual-ion cells were not tested.

In the patent "a bismuth tungstate/bismuth sulfide/molybdenum disulfide heterojunction ternary composite material and its preparation method and application" (patent publication number: CN111203239A) discloses a bismuth tungstate/bismuth sulfide/molybdenum disulfide A preparation method and application of a molybdenum sulfide heterojunction ternary composite material, the material is composed of ordered bismuth tungstate/bismuth sulfide/molybdenum disulfide layers. Among them, Bi ₂ WO ₆ is an orthorhombic crystal system, Bi ₂ S ₃ is a semiconductor with exposed (130) crystal plane, MoS ₂ is a layered transition metal sulfide with exposed (002) crystal plane, and the average particle size of the entire composite is It is a spherical structure of 2.4-2.6 microns, and the overall size is relatively large. This structure is mainly used for the application of photocatalytic reduction of Cr(VI), and its application in metal-ion batteries and dual-ion batteries has not been seen.

Existing negative electrode materials for dual-ion batteries mainly include intercalated graphite or carbon materials, alloy metals and conversion transition metal oxides and sulfides, and some organic substances. Among them, after metal ions are inserted into carbon materials, it is easy to cause its structure to expand and pulverize, resulting in low Coulombic efficiency, poor battery stability and rate performance; for a single metal oxide or sulfide, due to poor electronic conductivity and storage Metal ion reaction kinetics is slow and other problems, resulting in low energy storage rate performance; for conventional metal tin, antimony, bismuth and other negative electrodes, due to serious volume expansion during the cycle, it is easy to cause electrode pulverization, which leads to poor cycle performance. However, the reported organic materials have problems such as few active sites, low theoretical capacity and poor stability.

Contents of the invention

In view of the above background technology, the purpose of the present invention is to provide a metal ion battery sulfide composite material and its preparation method and application, to solve the problem of low rate performance of metal sulfide electrodes in the prior art, and to improve the stability and cycle performance of the electrodes. Life, improve the rate performance and energy storage capacity of the battery.

To achieve the above object, the present invention adopts technical scheme as follows:

The first aspect of the present invention provides a method for preparing a metal ion battery sulfide composite material, comprising the following steps:

(1) dissolving polyvinylpyrrolidone, bismuth source and first sulfur source in solvent I, and preparing precursor I (Bi ₂ S ₃ ) through hydrothermal reaction;

(2) Dissolve the precursor I (Bi ₂ S ₃ ), the molybdenum source and the second sulfur source obtained in step (1) in solvent II, and perform a hydrothermal reaction to obtain the precursor II (p-MoS ₂ /n-Bi ₂ S ₃ );

(3) Dissolve the precursor II (p-MoS ₂ /n-Bi ₂ S ₃ ) and dopamine hydrochloride obtained in step (2) in the buffer solution, and stir to obtain the carbon-coated precursor III (p-MoS ₂ /n -Bi ₂ S ₃ @C);

(4) Put the carbon-coated precursor III obtained in step (3) and the third sulfur source in a nitrogen atmosphere and keep warm to obtain a metal ion battery sulfide composite material (p-MoS ₂ /n-Bi ₂ S ₃ @ NC).

As a preferred embodiment, in step (1), the temperature of the hydrothermal reaction is 120-200°C, preferably 150°C; the time of the hydrothermal reaction is 6-24h, preferably 12h;

In some specific embodiments, in step (1), the temperature of the hydrothermal reaction is 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C or any temperature in between.

Preferably, in step (1), the solvent I is water;

Preferably, in step (1), the bismuth source is a bismuth-containing compound, and the bismuth-containing compound is selected from any one or more of bismuth oxide, bismuth chloride, bismuth sulfate and bismuth nitrate pentahydrate, more preferably Bismuth chloride;

Preferably, in step (1), the first sulfur source is a sulfur-containing compound, and the sulfur-containing compound is selected from any one or more of sodium thiosulfate, sulfur powder, thiourea and carbon disulfide, more preferably is sodium thiosulfate;

Preferably, in step (1), the molar ratio of the bismuth element and the sulfur element of the bismuth source and the first sulfur source is 0.1-2:1, more preferably 0.4:1;

In some specific embodiments, in step (1), the molar ratio of the bismuth element and the sulfur element of the bismuth source and the first sulfur source is 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2.0:1 or any ratio between them .

Preferably, step (1) also includes washing, centrifugation and drying, and the washing includes deionized water washing and ethanol washing; the rotational speed of the centrifugation is preferably 7000-10000 rpm, more preferably 9000 rpm; The centrifugation time is preferably 6-12 minutes, more preferably 10 minutes; the drying temperature is preferably 60-90°C, more preferably 70°C; the drying time is preferably 12-48h, more preferably 24h;

Preferably, in step (1), the polyvinylpyrrolidone, the bismuth source and the first sulfur source are sequentially dissolved in the solvent I, and in the technical solution of the present invention, the sequential dissolution can make them uniformly mixed.

In the technical scheme of the present invention, the mass ratio of polyvinylpyrrolidone and bismuth source does not have too big influence on product, generally it is limited to 1～5:1, for example 1:1, 2:1, 3:1 1, 4:1, 5:1 or any ratio between them.

As a preferred embodiment, in step (2), the temperature of the hydrothermal reaction is 180-220°C, preferably 200°C; the time of the hydrothermal reaction is 12-48h, preferably 24h;

In some specific embodiments, in step (2), the temperature of the hydrothermal reaction is 180°C, 190°C, 200°C, 210°C, 220°C or any temperature between them.

Preferably, in step (2), the solvent II is a mixed solution of water and an organic solvent; the organic solvent is selected from any one of ethanol, ethylene glycol, glycerol or N,N dimethylformamide One or more, preferably ethylene glycol; the volume ratio of water and organic solvent in the mixed solution is 0.2 to 5:1, preferably 1:1;

Preferably, in step (2), the molybdenum source is a molybdenum-containing compound, and the molybdenum-containing compound is selected from any one or more of molybdenum chloride, molybdic acid, sodium molybdate dihydrate and ammonium molybdate; More preferably sodium molybdate dihydrate;

Preferably, in step (2), the second sulfur source is a sulfur-containing compound, and the sulfur-containing compound is selected from any one or more of sodium thiosulfate, sulfur powder, thiourea and carbon disulfide, more preferably is thiourea;

Preferably, in step (2), the molar ratio of the bismuth element of the precursor 1, the molybdenum element of the molybdenum source and the sulfur element of the second sulfur source is 0.5～5:1:2～10, more preferably 1.5: 1:6.

Preferably, step (2) also includes washing, centrifugation and drying, and the washing includes deionized water washing and ethanol washing; the rotational speed of the centrifugation is preferably 7000-10000 rpm, more preferably 9000 rpm; The centrifugation time is preferably 6-12 minutes, more preferably 10 minutes; the drying temperature is preferably 60-90°C, more preferably 70°C; the drying time is preferably 12-48h, more preferably 24h;

Preferably, in step (2), the precursor I, the molybdenum source and the second sulfur source are sequentially dissolved in the solvent II, and the sequential dissolution can make the precursor I and the molybdenum source fully mixed, and then add the second sulfur source, The molybdenum source can be epitaxially grown on the surface of the precursor I, and the prepared material has better performance. In order to speed up the dissolution, ultrasound or stirring can be used.

As a preferred embodiment, in step (3), the mass ratio of the carbon-coated precursor III to dopamine hydrochloride is 2 to 10:1, more preferably 10:3;

Preferably, the pH of the buffer solution in step (3) is 7-13, more preferably a 0.01M Tris-HCl buffer solution with a pH of 8.5;

Preferably, in step (3), the stirring speed is 100-800 rpm, preferably 400 rpm; the stirring time is 3-24 h, preferably 12 h, which can be controlled by controlling the stirring time The thickness of the carbon coating;

In some specific embodiments, in step (3), the stirring speed is 100 rpm, 200 rpm, 300 rpm, 400 rpm, 500 rpm, 600 rpm , 700 rpm, 800 rpm or any speed between them.

Preferably, step (3) also includes washing, centrifugation and drying, and the washing includes deionized water washing and ethanol washing; the rotational speed of the centrifugation is preferably 7000-10000 rpm, more preferably 9000 rpm; The centrifugation time is preferably 6-12 minutes, more preferably 10 minutes; the drying temperature is preferably 60-90°C, more preferably 70°C; the drying time is preferably 12-48h, more preferably 24h;

Preferably, in step (3), the precursor II is dissolved in the buffer solution, and then dopamine hydrochloride is added, and the sequential dissolution can make the precursor II evenly dispersed in the buffer solution, and then dopamine hydrochloride is added to make the carbon evenly coated on the surface of Precursor II.

As a preferred embodiment, in step (4), the temperature of the heat preservation is 400-800°C, preferably 600°C; the time of the heat preservation is 1-6h, preferably 2h;

In some specific embodiments, in step (4), the temperature of the heat preservation is 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C or one of them any temperature in between.

Preferably, in step (4), the heating rate of the heat preservation is 1-10°C/min, preferably 5°C/min;

In some specific embodiments, in step (4), the heating rate of the heat preservation is 1°C/min, 2°C/min, 3°C/min, 4°C/min, 5°C/min, 6°C/min min, 7°C/min, 8°C/min, 9°C/min, 10°C/min or any heating rate between them.

Preferably, in step (4), the third sulfur source is a sulfur-containing compound, and the sulfur-containing compound is selected from any one or more of sodium thiosulfate, sulfur powder, thiourea and carbon disulfide, more preferably is thiourea;

Preferably, in step (4), the mass ratio of the third sulfur source to the carbon-coated precursor III is 5-30, more preferably 20.

The second aspect of the present invention provides the metal ion battery sulfide composite material obtained by the above preparation method.

The third aspect of the present invention provides the application of the above-mentioned metal ion battery sulfide composite material in the preparation of batteries.

As a preferred embodiment, the battery is a potassium-based, lithium-based, sodium-based, calcium-based, magnesium-based, or aluminum-based dual-ion battery.

In the technical solution of the present invention, the built-in electric field of the heterojunction in the metal ion battery sulfide composite material can effectively improve the diffusion kinetics and electronic conductivity of metal ions, thereby improving the battery rate performance, and the coated carbon layer can significantly Improve the structural stability of the material.

The fourth aspect of the present invention provides a battery comprising the above metal-ion battery sulfide composite material.

In the technical solution of the present invention, the battery includes a positive electrode, a negative electrode, a separator and an electrolyte.

As a preferred embodiment, the battery is a potassium-based, lithium-based, sodium-based, calcium-based, magnesium-based, aluminum-based dual-ion battery;

Preferably, the active material of the positive electrode is expanded graphite, and the active material of the negative electrode is the above-mentioned metal ion battery sulfide composite material.

As a preferred embodiment, the positive electrode is prepared as follows: after mixing expanded graphite, a conductive agent, and a binder, nitrogen methyl pyrrolidone is added, ground into a slurry, coated on an aluminum foil, dried, and cut into pole pieces;

Preferably, the mass ratio of the expanded graphite, conductive agent and binder is 5-8:1-4:1;

Preferably, the drying is vacuum drying, the drying temperature is 60-90° C., and the drying time is 12-48 hours.

As a preferred embodiment, the negative electrode is prepared according to the following method: after mixing the above-mentioned metal ion battery sulfide composite material, conductive agent, and binder, adding nitrogen methyl pyrrolidone, grinding it into a slurry, and coating it on the copper foil, Dry and cut into pole pieces;

Preferably, the mass ratio of the metal ion battery sulfide composite material, conductive agent, and binder is 5-8:1-4:1;

As a preferred embodiment, the electrolyte is electrolyte salts dissolved in organic solvents, the electrolyte salts include inorganic salts and organic salts, specifically potassium salts, lithium salts, sodium salts, calcium salts, magnesium salts and at least one of aluminum salts;

Preferably, the potassium salt is selected from KPF ₆ , K ₂ SO ₄ , KBH ₄ , KBF ₄ , KClO ₄ , potassium bistrifluoromethylsulfonimide (KTFSI) and potassium bisfluorosulfonimide (KFSI) One or more of them, preferably KPF ₆ .

The concentration of potassium salt in the electrolyte will affect the ion transmission performance. If the concentration is too low, the conductivity will be low, resulting in poor ion transmission performance; if the concentration is too high, the viscosity of the electrolyte will be too high, which will also cause low conductivity, so it contains potassium salt The concentration of potassium ions in the electrolyte is preferably 0.5-5 mol/L, more preferably 0.8 mol/L.

Preferably, the organic solvent is selected from one or more of esters, sulfones, ethers, and nitriles.

Commonly used organic solvents include propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), fluoroethylene carbonate (FEC), ethylene glycol dimethyl ether (DME), vinylene carbonate (VC), diethylene glycol dimethyl ether, dimethyl sulfoxide, dimethyl ether, etc.

According to the above potassium salt and organic solvent, preferably KPF ₆ with a concentration of 0.8 mol/L is dissolved in EC/DMC/EMC with a volume ratio of 4:3:2 as the electrolyte.

As a preferred embodiment, the diaphragm is made of glass fiber.

The above technical solution has the following advantages or beneficial effects:

The present invention combines the dual strategies of metal sulfide heterostructure construction and carbon layer coating, constructing p-type MoS ₂ and n-type Bi ₂ S ₃ into a pn heterojunction for the first time, and then preparing nitrogen-doped carbon-coated pn heterojunction Plasma junction (p-MoS ₂ /n-Bi ₂ S ₃ @NC) electrode material, and its application in the preparation of a variety of ion batteries, all exhibit excellent electrochemical performance.

The composite material provided by the present invention has the following advantages: (1) the composite material provided by the present invention has excellent electrochemical properties, and is cheap and environmentally friendly; (2) the composite material provided by the present invention is rich in abundant energy storage active sites, Higher energy storage capacity can be provided; (3) the composite material provided by the invention can accelerate charge migration through the built-in electric field of the heterostructure interface, thereby improving reaction kinetics and enhancing rate performance; (4) the invention introduces metal vulcanization The material heterojunction and carbon layer are used as supports, which is beneficial to the transport kinetics of metal ions and electrons such as potassium ions, lithium ions, magnesium ions, sodium ions, calcium ions, aluminum ions, etc., and enhances electrical conductivity. At the same time, the coated carbon layer The material further improves the conductivity and structural stability of the sulfide composite structure, and effectively alleviates the structural pulverization caused by the volume expansion of the electrode during the cycle, thereby comprehensively improving the energy storage performance; (5) the present invention uses bismuth sources, The molybdenum source and the sulfur source are used as raw materials, organic liquids such as alcohols are used as solvents, and the composite material is prepared through hydrothermal reaction and calcination process, and the process flow is simple.

Description of drawings

Fig. 1 is the X-ray diffraction (XRD) test and X-ray photoelectron spectroscopy (XPS) analysis of the composite material in embodiment 1 and comparative example 1, comparative example 2, wherein Fig. 1 (a) is X-ray diffraction (XRD) , Figure 1b-Figure 1d are X-ray photoelectron spectroscopy (XPS).

Fig. 2 is the transmission electron micrograph (TEM) and the energy spectrum (EDS) of the electrode material in embodiment 1 and comparative example 1, comparative example 2, wherein Fig. 2a-Fig. 2c is scanning electron micrograph (SEM), Fig. 2d-Figure 2e is a transmission electron microscope image (TEM), and Figure 2f is an energy spectrum image (EDS).

FIG. 3 is the charge and discharge curves of the potassium-based double-ion battery in Example 1 at different current densities (1C=100 mA·g ⁻¹ ).

Fig. 4 is a test chart of the long-term cycle performance of the potassium-based double-ion battery in Example 1 under the condition of a current density of 200 mA g ^-1 .

Detailed ways

The following embodiments are only some of the embodiments of the present invention, not all of them. Therefore, the detailed description in the embodiments of the invention provided below is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making creative efforts belong to the protection scope of the present invention.

In the present invention, unless otherwise specified, all equipment and raw materials can be purchased from the market or commonly used in this industry. The methods in the following examples, unless otherwise specified, are conventional methods in the art.

Example 1:

The composite material in this example is a nitrogen-doped carbon-coated metal sulfide heterojunction composite material (p-MoS ₂ /n-Bi ₂ S ₃ @NC, MBSNC), and the preparation steps are as follows:

(1) Weigh 220mg of polyvinylpyrrolidone, add it into 160mL of deionized water and continue to stir and dissolve it. After 10 minutes, add 0.4mmol of bismuth chloride into it and continue to stir and dissolve it. After 10 minutes, add 1mmol of sodium thiosulfate pentahydrate and continue Stir for 10 minutes to dissolve it, transfer the reaction solution to a 200mL polytetrafluoroethylene-lined hydrothermal reaction kettle, seal it, put it in an oven and react at a constant temperature of 150°C for 12 hours, and wait for the reaction kettle to drop to room temperature;

(2) Transfer the reaction liquid to a centrifuge tube and centrifuge at a speed of 9000 rpm for 10 minutes, separate and remove the supernatant, wash the precipitate with deionized water and absolute ethanol and centrifuge at a speed of 9000 rpm Three times for 10 minutes each, dry in a vacuum oven at 70°C for 24 hours;

(3) Measure 30mL of ethylene glycol and 30mL of deionized water and continue to stir for more than 10 minutes, weigh 386mg of the dried product of step (1) and add it, after ultrasonication for 10 minutes, stir for 5 minutes, and add 0.5mmol dihydrate Sodium molybdate was stirred for 5 minutes, 3 mmol thiourea was added thereto and stirred for 5 minutes, the reaction solution was transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal reaction kettle, sealed, and put into an oven to react at a constant temperature of 200°C 24 hours, until the reactor was down to room temperature;

(4) Transfer the reaction solution to a centrifuge tube, centrifuge at a speed of 9000 rpm for 10 minutes, separate and remove the supernatant, wash the precipitate with deionized water and absolute ethanol, and centrifuge at a speed of 9000 rpm Centrifuge three times for 10 minutes each, and dry in a vacuum oven at 70°C for 24 hours;

(5) Measure the Tris buffer solution of pH=8.5 of 100mL and keep stirring in the beaker, add the product of 300mg step (4) in the beaker and keep stirring, ultrasonic 30 minutes, add 0.5mmol dopamine hydrochloride, keep stirring for 12 hours, Transfer the reaction solution to a centrifuge tube, centrifuge at 9,000 rpm for 10 minutes, separate and remove the supernatant, wash the precipitate with deionized water and absolute ethanol, and centrifuge at 9,000 rpm for 10 minutes , repeated three times, and dried in a vacuum oven at 70°C for 24 hours;

(6) take by weighing 6g thiourea and the product of 0.3g step (5) and fill respectively in two magnetic boats, two magnetic boats are placed in the upstream and downstream of the air flow in the quartz tube, connect the nitrogen and communicate with the gas path, the tube The tube furnace was raised to 600 °C at a heating rate of 5 °C/min and then kept at a constant temperature for 2 hours. The sample was taken out after the tube furnace dropped to room temperature, and finally the p-MoS ₂ /n-Bi ₂ S ₃ @NC nanocomposite was obtained.

Assemble a potassium-based dual-ion battery:

Preparation of negative electrode: p-MoS ₂ /n-Bi ₂ S ₃ @NC nanomaterials, conductive carbon black, and polyvinylidene fluoride (PVDF) were evenly mixed together in a mass ratio of 7:2:1, hand-milled for 30 minutes, and N -Methylpyrrolidone (NMP) is made into a paste slurry, and then the slurry is evenly coated on the copper foil, followed by vacuum drying at 70°C; after the dried copper foil is rolled, cut into a diameter of 10mm The disc is then used as a negative electrode.

Preparation of positive electrode: Expanded graphite material, conductive carbon black, and PVDF are evenly mixed together according to the mass ratio of 8:1:1, ground for 30 minutes, and NMP is added to make a paste slurry, and then the slurry is evenly coated on the aluminum foil. Then vacuum-dry at 70° C. for 24 hours; roll the dried aluminum foil, cut it into discs with a diameter of 12 mm, and use it as a positive electrode for later use.

Preparation of the separator: the glass fiber membrane was cut into discs with a diameter of 16 mm and used as a separator for later use.

Preparation of electrolyte solution: Weigh 7.2mmol of electrolyte potassium salt KPF ₆ , measure 4mL of ethylene carbonate (EC), 3mL of dimethyl carbonate (DMC) and 2mL of ethyl methyl carbonate (EMC) and mix them evenly. Potassium salt was added to the solvent, stirred until KPF ₆ was completely dissolved, and the concentration was 0.8mol/L, and it was used as the electrolyte after being fully stirred evenly.

Assembly: In a glove box protected by an inert gas, the above-mentioned positive electrode, separator, and negative electrode were stacked closely in sequence, and the electrolyte was added dropwise to completely infiltrate the separator, and then the above-mentioned stacked part was packaged into a button-type housing to complete the potassium-based double electrode. Assembly of ion batteries.

In this embodiment, the assembly of the battery is carried out in a glove box where the contents of water and oxygen are both less than 0.1 ppm.

Comparative example 1:

The composite material in this comparative example is a nitrogen-doped carbon layer coated bismuth trisulfide nanomaterial (Bi ₂ S ₃ @NC nanomaterial, BSNC), and the preparation steps are as follows:

(1) Weigh 220 mg of polyvinylpyrrolidone, add it into 160 mL of deionized water and continue to stir and dissolve it. After 10 minutes, add 0.4 mmol of bismuth chloride to it and continue to stir and dissolve it. Then, after 10 minutes, add 1 mmol of sodium thiosulfate pentahydrate , continue to stir for 10 minutes to dissolve, transfer the reaction solution to a 200mL polytetrafluoroethylene-lined hydrothermal reaction kettle, seal it, put it in an oven and react at a constant temperature of 150°C for 12 hours, and wait for the reaction kettle to drop to room temperature .

(3) Measure the Tris buffer solution of pH=8.5 of 100mL in the beaker and keep stirring, add the product of 300mg step (2) in the beaker and keep stirring, ultrasonic 30 minutes, add 0.5mmol dopamine hydrochloride, keep stirring for 12 hours, Transfer the reaction solution to a centrifuge tube, centrifuge at 9,000 rpm for 10 minutes, separate and remove the supernatant, wash the precipitate with deionized water and absolute ethanol, and centrifuge at 9,000 rpm for 10 minutes , repeated three times, and dried in a vacuum oven at 70°C for 24 hours;

(4) take by weighing 6g thiourea and the product of 0.3g step (5) and be contained in two magnetic boats respectively, two magnetic boats are placed in the upstream and downstream of the air flow in the quartz tube, connect nitrogen and communicate with the gas path, the tube The tube furnace was raised to 600 °C at a heating rate of 5 °C/min and then kept at a constant temperature for 2 hours. After the tube furnace dropped to room temperature, the samples were taken out, and finally the Bi ₂ S ₃ @NC composite anode material was obtained.

The battery in this comparative example is the same as in Example 1, except that the p-MoS ₂ /n-Bi ₂ S ₃ @NC nanomaterial is replaced by the Bi ₂ S ₃ @NC nanomaterial.

This comparative example is to prepare Bi ₂ S ₃ coated with a single nitrogen-doped carbon layer. This material has poor structural stability, unsatisfactory battery cycle stability, and rapid battery capacity decay.

Comparative example 2

The composite material in this comparative example is a nitrogen-doped carbon layer coated molybdenum disulfide nanomaterial (MoS ₂ @NC nanomaterial, MSNC), and the preparation steps are as follows:

(1) Measure 30mL ethylene glycol and 30mL deionized water and continue to stir for more than 10 minutes, weigh 0.5mmol sodium molybdate dihydrate and stir for 5 minutes, add 3mmol thiourea and stir for 5 minutes, transfer the reaction solution to 100mL In a polytetrafluoroethylene-lined hydrothermal reaction kettle, seal it, put it in an oven and react at a constant temperature of 200°C for 24 hours, and wait for the reaction kettle to drop to room temperature.

(2) Transfer the reaction solution to a centrifuge tube, centrifuge at a speed of 9000 rpm for 10 minutes, separate and remove the supernatant, wash the precipitate with deionized water and absolute ethanol and centrifuge at a speed of 9000 rpm Centrifuge three times for 10 minutes each, and dry in a vacuum oven at 70°C for 24 hours;

(3) Measure the Tris buffer solution of pH=8.5 of 100mL in the beaker and keep stirring, add the product of 300mg step (4) in the beaker and keep stirring, ultrasonic 30 minutes, add 0.5mmol dopamine hydrochloride, keep stirring for 12 hours, Transfer the reaction solution to a centrifuge tube, centrifuge at 9,000 rpm for 10 minutes, separate and remove the supernatant, wash the precipitate with deionized water and absolute ethanol, and centrifuge at 9,000 rpm for 10 minutes , repeated three times, and dried in a vacuum oven at 70°C for 24 hours;

(4) take by weighing 6g thiourea and the product of 0.3g step (3) and fill in two magnetic boats respectively, two magnetic boats are placed in the upstream and downstream of the air flow in the quartz tube, connect nitrogen and communicate with the gas path, the tube The tube furnace was raised to 600 °C at a heating rate of 5 °C/min, and then the temperature was kept constant for 2 hours. After the tube furnace dropped to room temperature, the samples were taken out, and finally the MoS ₂ @NC composite anode material was obtained.

The battery in this comparative example is the same as in Example 1, except that the p-MoS ₂ /n-Bi ₂ S ₃ @NC nanomaterial is replaced by MoS ₂ @NC nanomaterial.

This comparative example is to prepare MoS ₂ coated with a single nitrogen-doped carbon layer, which has a low potassium storage capacity and poor coulombic efficiency.

Material Characterization:

Do X-ray diffraction (XRD) test and X-ray photoelectron spectroscopy (XPS) analysis to the composite material in embodiment 1 (MBSNC) and comparative example 1 (BSNC), comparative example 2 (MSNC), its spectrogram is shown in Fig. 1a and Figure 1b-1d are shown.

It can be seen from Figure 1a that the diffraction peaks in MoS ₂ @NC (MSNC) are dominated by wrapping peaks, corresponding to the standard PDF card No.37-1492 of MoS ₂ . The MBSNC sample has many characteristic peaks, near the main characteristic peaks such as 15.801°, 17.582°, 22.393°, 23.720°, 24.928°, 28.605°, 31.796°, 39.892°, 46.458° and 52.616°, which are similar to the Bi ₂ S ₃ standard PDF card No.17-0320 matches well, proving the existence _of _Bi2S3 . At the same time, the content of _MoS2 and carbon layer is less, and the diffraction peaks are weaker, therefore, in MBSNC, no obvious _MoS2 diffraction peaks appear. As shown in Figure 1b, the doped N content is about 7%, mainly in the form of pyridinic nitrogen, pyrrolic nitrogen, and graphitic nitrogen. At the same time, the binding energies of Bi 4f orbital, Mo 3d orbital and S 2p orbital in MBSNC heterojunction correspond to Bi ³⁺ , Mo ⁴⁺ and S ^2- respectively, and they are smaller than those of single sulfide (Fig. 1c-d) , demonstrating the formation of a heterojunction.

Subsequently, SEM and TEM analyzes were performed on BSNC, MSNC and MBSNC. As shown in Figure 2a–c, BSNC, MSNC, and MBSNC are nanorod, nanosheet, and nanobamboo sheet-like structures, respectively. As shown in Figure 2d, 3.75 and

The lattice fringe spacing of Bi ₂ S ₃ (130) and MoS ₂ (002) are matched with the interplanar spacing of Bi 2 S 3 (130) and MoS 2 (002), and the two crystal planes are closely combined, which indicates that the two sulfides form a heterostructure interface, and at the same time The thickness of the coated carbon layer is about 5nm. In Figure 2f, it can be seen from the X-ray energy spectrum analysis that the five elements of Bi, Mo, S, C, and N are evenly distributed.

Electrochemical performance test - potassium ion half-cell performance test:

The battery cells in Example 1 and Comparative Examples 2 and 3 were charged and discharged at a charge and discharge rate of 3C (1C=100mA·g ^-1 ), and the charge and discharge test was carried out under the condition of a voltage range of 3 to 5V. The charge and discharge of the battery The test is carried out on Xinwei battery test system.

The test results are shown in Table 1:

Table 1. Example 1 and comparative example 1-2 battery test data

Figure 3 shows the charge and discharge curves of the battery in Example 1 at different current densities (100, 200, 300 and 500mA·g ^-1 ), as can be seen from Figure 3, the electrode material prepared in Example 1 The samples had apparently similar potassium storage and potassium removal platforms.

FIG. 4 is a cycle curve showing the current density of the battery in Example 1 at 200 mA·g ⁻¹ . It can be seen from Figure 4 that the MBSNC sample exhibits good long-range cycle performance, and the Coulombic efficiency is greater than 92%.

Example 2-7

Change bismuth source: in embodiment 1, the bismuth chloride in step (1) is changed into bismuth oxide (embodiment 2), bismuth sulfate (embodiment 3), bismuth nitrate (embodiment 4), molar ratio 1: 1 bismuth chloride and bismuth oxide (embodiment 5), bismuth chloride of mol ratio 1:1:1: bismuth sulfate: bismuth nitrate (embodiment 6), bismuth chloride of mol ratio 1:1:1:1 : bismuth oxide: bismuth sulfate: bismuth nitrate (embodiment 7).

The charge-discharge test was carried out under the condition of a voltage range of 3-5V with a charge-discharge rate of 3C (1C=100mA·g-1).

The test results are shown in Table 2:

Table 2. Battery test data of embodiment 1 and embodiment 2-7

Example 8-19

Change the mol ratio of the first sulfur source or bismuth source and the first sulfur source: with embodiment 1, sodium thiosulfate pentahydrate in step (1) is changed into sulfur powder (embodiment 8), thiourea (embodiment 9 ), carbon disulfide (embodiment 10), sodium thiosulfate pentahydrate in mol ratio 1:1: thiourea (embodiment 11), or with embodiment 1, the mole of bismuth source and the first sulfur source in step (1) The ratio is changed from 0.4 to 0.1 (Example 12), 0.8 (Example 13), 1 (Example 14), 1.3 (Example 15), 1.6 (Example 16), and 2 (Example 17).

Using a charge-discharge rate of 3C (1C=100mA·g ^-1 ), the charge-discharge test was carried out under the condition of a voltage range of 3-5V, and the test results are shown in Table 3:

Table 3. Battery test data of embodiment 1 and embodiment 8-17

Examples 18-23

Change step (1) reaction temperature or time, change reaction temperature 150 ℃ into 120 ℃ (embodiment 18), 180 ℃ (embodiment 19), 200 ℃ (embodiment 20), or change reaction time 12 hours into 6 hours (Example 21), 18 hours (Example 22) or 24 hours (Comparative Example 23).

Using a charge-discharge rate of 3C (1C=100mA·g ^-1 ), the charge-discharge test was carried out under the condition of a voltage range of 3-5V, and the test results are shown in Table 4:

Table 4. Battery test data of embodiment 1 and embodiment 18-23

Examples 24-31

Change organic solvent: change ethylene glycol into ethanol (embodiment 24), glycerol (embodiment 25), N,N dimethylformamide (embodiment 26), acetone in embodiment 1, step (3) (Example 27), or change the volume of ethylene glycol and deionized water into 10mL and 50mL (Example 28), 20 and 40mL (Example 29), 40 and 20mL (Example 30), 50 and 10mL ( Example 31).

Using the charge and discharge rate of 3C (1C=100mA·g ^-1 ) for the battery cell of the above example, the charge and discharge test was carried out under the condition of a voltage range of 3 to 5V, and the test results are as follows:

Table 5. Battery test data of embodiment 1 and embodiment 26-31

Examples 32-42

Change molybdenum source: with embodiment 1, in step (3), sodium molybdate dihydrate is changed into molybdenum chloride (embodiment 32), molybdic acid (embodiment 33), ammonium molybdate (embodiment 34), molar ratio 1 : 1 sodium molybdate dihydrate: molybdic acid (embodiment 35), sodium molybdate dihydrate molybdate in a mol ratio of 1:1:1: molybdic acid: ammonium molybdate (embodiment 36), or step (2) product And the molar ratio 1.5 of molybdenum source is changed into 0.5 (embodiment 37), 1 (embodiment 38), 2 (embodiment 39), 3 (embodiment 40), 4 (embodiment 41), 5 (embodiment 42)

Using a charge-discharge rate of 3C (1C=100mA·g ^-1 ), the charge-discharge test was carried out under the condition of a voltage range of 3-5V, and the test results are shown in Table 6:

Table 6. Battery Test Data of Example 1 and Examples 32-42

Examples 43-51

Change the mol ratio of the second sulfur source or the second sulfur source and molybdenum source: with embodiment 1, in step (3), thiourea is changed into sulfur powder (embodiment 43), sodium thiosulfate pentahydrate (embodiment 44) , carbon disulfide (embodiment 45), sulfur powder of mol ratio 1:1: thiourea (embodiment 46), sodium thiosulfate pentahydrate in mol ratio 1:1: thiourea (embodiment 47), or change the second The molar ratio of sulfur source to molybdenum source is 2:1 (Example 48), 4:1 (Example 49), 8:1 (Example 50), 10:1 (Example 51).

Using a charge-discharge rate of 3C (1C=100mA·g ^-1 ), the charge-discharge test was carried out under the condition of a voltage range of 3-5V, and the test results are shown in Table 7:

Table 7. Battery test data of embodiment 1 and embodiment 43-51

Examples 52-56

Change step (3) reaction temperature or time in embodiment 1, change reaction temperature 200 ℃ into 180 ℃ (embodiment 52, 220 ℃ (embodiment 53), perhaps change reaction time 24 hours into 12 hours (embodiment 54 ), 18 hours (Example 55) or 48 hours (Example 56).

Using a charge-discharge rate of 3C (1C=100mA·g ^-1 ), the charge-discharge test was carried out under the condition of a voltage range of 3-5V, and the test results are shown in Table 8:

Table 8. Battery test data of Example 1 and Examples 52-56

Examples 57-60

Change the mass ratio of step (4) product and dopamine hydrochloride in embodiment 1, change 10:3 into 2:1 (embodiment 57), 5:1 (embodiment 58), 7.5:1 (embodiment 59), 10:1 (Example 60).

Using a charge-discharge rate of 3C (1C=100mA·g ^-1 ), the charge-discharge test was carried out under the condition of a voltage range of 3-5V, and the test results are shown in Table 9:

Table 9. Battery test data of embodiment 1 and embodiment 57-60

Examples 61-65

Change in embodiment 1, the stirring time of step (5), change time 12 hours into 3 hours (embodiment 61), 6 hours (embodiment 62), 15 hours (embodiment 63), 18 hours (embodiment 64 ) or 24 hours (Example 65).

Using a charge-discharge rate of 3C (1C=100mA·g ^-1 ), the charge-discharge test was carried out under the condition of a voltage range of 3-5V, and the test results are shown in Table 10:

Table 10. Example 1 and Example 61-65 battery test data

Examples 66-77

Change the centrifugation and drying conditions of steps (2) (3) and (5) in Example 1, change the rotating speed to 7000 rpm (embodiment 66), 8000 rpm (embodiment 67) or 10000 rpm minute (embodiment 68), the time is changed into 6 minutes (embodiment 69), 8 minutes (embodiment 70) or 12 minutes (embodiment 71), or change drying temperature 60 ℃ (embodiment 72), 80 ℃ (implementation Example 73) or 90° C. (Example 74), or changing the drying time to 12 hours (Example 75), 36 hours (Example 76) or 48 hours (Example 77).

Using a charge-discharge rate of 3C (1C=100mA·g ^-1 ), the charge-discharge test was carried out under the condition of a voltage range of 3-5V, and the test results are shown in Table 11:

Table 11. Example 1 and Example 66-77 battery test data

Examples 78-84

Change in embodiment 1, the mass ratio of the 3rd sulfur source of step (6) or the 3rd sulfur source and step (5) product, change thiourea into sulfur powder (embodiment 78), sodium thiosulfate pentahydrate ( Embodiment 79), carbon disulfide (embodiment 80), mass ratio is changed into 5 (embodiment 81), 10 (embodiment 82), 25 (embodiment 83), 30 (embodiment 84).

Using a charge-discharge rate of 3C (1C=100mA·g ^-1 ), the charge-discharge test was carried out under the condition of a voltage range of 3-5V, and the test results are shown in Table 12:

Table 12. Example 1 and Example 78-84 battery test data

Examples 85-95:

In changing embodiment 1, the heat treatment temperature and the time of step (6), change the heating rate into 1 ℃/minute (embodiment 85), 3 ℃/minute (embodiment 86), 8 ℃/minute (embodiment 87) Or 10 DEG C/min (embodiment 88), perhaps change constant temperature temperature into 400 DEG C (embodiment 89), 500 DEG C (embodiment 90), 700 DEG C (embodiment 91) or 800 DEG C (embodiment 92), or The constant temperature time was changed to 1 hour (Example 93), 4 hours (Example 94) or 6 hours (Example 95).

Using a charge-discharge rate of 3C (1C=100mA·g-1), the charge-discharge test was carried out under the condition of a voltage range of 3-5V. The test results are shown in Table 13:

Table 13. Example 1 and Example 85-95 battery test data

Examples 96-100:

The electrode material p-MoS ₂ /n-Bi ₂ S ₃ @NC composite negative electrode material prepared in Example 1 was used as a lithium dual-ion battery (electrolyte: 4M LiPF ₆ dissolved in EMC+2wt.%VC, Example 96 ), sodium double-ion battery (electrolyte: 1M NaPF ₆ dissolved in EC/DMC/EMC with a volume ratio of 4:3:2, Example 97), calcium double-ion battery (electrolyte: 0.8M Ca(PF ₆ ) ₂ dissolved in EC/PC/DMC/EMC with a volume ratio of 2:2:3:3, Example 98), magnesium double-ion battery (electrolyte: 0.4M Mg(TFSI) ₂ dissolved in ionic liquid (Pyr ₁₄ TFSI ), Example 99) and an aluminum double-ion battery (electrolyte: a molar ratio of 1.3:1 of AlCl and ₁ -ethyl-3-methylimidazole chloride ([EMIm]Cl) mixed solution, Example 100) , which exhibited excellent battery performance.

Using a charge-discharge rate of 3C (1C=100mA·g ^-1 ), the charge-discharge test was carried out under the condition of a voltage range of 3-5V, and the test results are shown in Table 14:

Table 14. Example 1 and Example 96-100 battery test data

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the patent scope of the present invention. All equivalent transformations made using the content of the description of the present invention, or directly or indirectly used in other related technical fields, are all included in the same principle. Within the scope of patent protection of the present invention.

Claims

A kind of preparation method of metal ion battery sulfide composite material, it is characterized in that, comprises the steps:

(1) dissolving polyvinylpyrrolidone, bismuth source and first sulfur source in solvent I, and preparing precursor I through hydrothermal reaction;

(2) Dissolving the precursor I, the molybdenum source and the second sulfur source obtained in step (1) in the solvent II, and performing a hydrothermal reaction to obtain the precursor II;

(3) dissolving the precursor II and dopamine hydrochloride obtained in step (2) in a buffer solution, and stirring to obtain the carbon-coated precursor III;

(4) Put the carbon-coated precursor III obtained in step (3) and the third sulfur source in a nitrogen atmosphere and keep warm to obtain a metal ion battery sulfide composite material.
The preparation method according to claim 1, characterized in that, in step (1), the temperature of the hydrothermal reaction is 120-200°C, preferably 150°C; the time of the hydrothermal reaction is 6-24h, Preferably 12h.
According to the preparation method according to claim 1, it is characterized in that, in step (1), the solvent I is water.
According to the claim, the preparation method according to claim 1 is characterized in that, in step (1), the bismuth source is a bismuth-containing compound, and the bismuth-containing compound is selected from bismuth oxide, bismuth chloride, bismuth sulfate and pentasmuth Any one or more of bismuth nitrate hydrate, more preferably bismuth chloride.
According to the claim, the preparation method according to claim 1 is characterized in that, in step (1), the first sulfur source is a sulfur-containing compound, and the sulfur-containing compound is selected from sodium thiosulfate, sulfur powder, sulfur Any one or more of urea and carbon disulfide, more preferably sodium thiosulfate.
According to the claim, the preparation method according to claim 1, is characterized in that, in step (1), the molar ratio of the bismuth element and the sulfur element of the bismuth source and the first sulfur source is 0.1～2:1, more preferably is 0.4:1.
According to the preparation method according to claim 1, it is characterized in that step (1) also includes washing, centrifuging and drying.
The preparation method according to claim 1, characterized in that, in step (1), the polyvinylpyrrolidone, bismuth source and first sulfur source are dissolved in solvent I in sequence.
The preparation method according to claim 1, characterized in that, in step (2), the temperature of the hydrothermal reaction is 180-220°C, preferably 200°C; the time of the hydrothermal reaction is 12-48h, Preferably 24h.
preparation method according to claim 1, is characterized in that, in step (2), described solvent II is the mixed solution of water and organic solvent; Described organic solvent is selected from ethanol, ethylene glycol, glycerol and N, Any one or more of N-dimethylformamide, preferably ethylene glycol; the volume ratio of water and organic solvent in the mixed solution is 0.2-5:1, preferably 1:1.
The preparation method according to claim 1, wherein in step (2), the molybdenum source is a molybdenum-containing compound, and the molybdenum-containing compound is selected from molybdenum chloride, molybdic acid, sodium molybdate dihydrate and molybdenum Any one or more of ammonium acid; more preferably sodium molybdate dihydrate.
The preparation method according to claim 1, characterized in that, in step (2), the second sulfur source is a sulfur-containing compound, and the sulfur-containing compound is selected from sodium thiosulfate, sulfur powder, thiourea and carbon disulfide Any one or more of them, more preferably thiourea.
preparation method according to claim 1, is characterized in that, in step (2), the molar ratio of the bismuth element of described precursor 1, the molybdenum element of molybdenum source and the sulfur element of the second sulfur source is 0.5～5: 1:2-10, more preferably 1.5:1:6.
The preparation method according to claim 1, characterized in that step (2) further comprises washing, centrifuging and drying.
The preparation method according to claim 1, characterized in that, in step (2), the precursor I, the molybdenum source and the second sulfur source are sequentially dissolved in the solvent II.
The preparation method according to claim 1, characterized in that, in step (3), the mass ratio of the carbon-coated precursor III to dopamine hydrochloride is 2-10:1, more preferably 10:3.
The preparation method according to claim 1, characterized in that the buffer solution in step (3) has a pH of 7-13, more preferably a 0.01M Tris-HCl buffer solution with a pH of 8.5.
The preparation method according to claim 1, characterized in that, in step (3), the stirring speed is 100-800 rpm, preferably 400 rpm; the stirring time is 3-24h, Preferably 12h.
The preparation method according to claim 1, characterized in that step (3) further comprises washing, centrifuging and drying.
The preparation method according to claim 1, characterized in that, in step (3), the precursor II is dissolved in a buffer solution, and then dopamine hydrochloride is added.
The preparation method according to claim 1, characterized in that, in step (4), the temperature of the heat preservation is 400-800°C, preferably 600°C; the time of the heat preservation is 1-6h, preferably 2h.
The preparation method according to claim 1, characterized in that, in step (4), the heating rate of the heat preservation is 1-10°C/min, preferably 5°C/min.
The preparation method according to claim 1, wherein in step (4), the third sulfur source is a sulfur-containing compound, and the sulfur-containing compound is selected from sodium thiosulfate, sulfur powder, thiourea and carbon disulfide Any one or more of them, more preferably thiourea.
The preparation method according to claim 1, characterized in that, in step (4), the mass ratio of the third sulfur source and carbon-coated precursor III is 5-30, more preferably 20.
The metal ion battery sulfide composite material obtained according to the preparation method described in any one of claims 1-24.
Application of the metal ion battery sulfide composite material according to claim 25 in preparing batteries.
A battery comprising the metal ion battery sulfide composite material of claim 25.
The battery according to claim 27, wherein the battery is a potassium-based, lithium-based, sodium-based, calcium-based, magnesium-based, or aluminum-based dual-ion battery.