High-entropy nonmetal-doped three-dimensional ordered mesoporous carbon sphere composite material as well as preparation method and application thereof

Abstract

The invention discloses a high-entropy nonmetal-doped three-dimensional ordered mesoporous carbon sphere composite material as well as a preparation method and application thereof, and belongs to the field of materials. The three-dimensional ordered mesoporous carbon sphere composite material contains a high-entropy non-metal doping element; the high-entropy nonmetal doping elements comprise nitrogen, sulfur, phosphorus, boron and fluorine; the three-dimensional ordered mesoporous carbon sphere composite material has a radial gradient aperture structure. The composite material is stable in structure and shows excellent electrochemical performance; the method is simple in production process, environment-friendly, high in product yield and easy to industrially amplify, and commercialization is realized.

Description

Technical Field

[0001] The present application relates to a high-entropy non-metal-doped three-dimensional ordered mesoporous carbon sphere composite material and its preparation method and application, belonging to the field of materials. Background Art

[0002] Sodium-based hybrid-ion capacitors (SIHCs) stand out due to their unique "battery-capacitor" composite energy storage mechanism. They have the advantages of high energy density of sodium-ion batteries and high power density and ultra-long cycle life of supercapacitors, showing broad prospects in large-scale energy storage, electric vehicles and smart grids. Compared with lithium-based systems, SIHCs rely on the abundant reserves and cost advantages of sodium resources, which are more in line with the strategic needs of sustainable development. However, the practical application of SIHCs is still subject to the mismatch between the positive and negative electrode kinetic behaviors: the positive electrode is based on a fast surface capacitance reaction, while the traditional negative electrode (such as hard carbon) relies on slow sodium ion insertion / extraction reactions, resulting in increased polarization during charge and discharge, decreased energy efficiency and cycle life attenuation. Therefore, the development of negative electrode materials with high rate, high capacity and long cycle stability is the key to breaking through the performance bottleneck of SIHCs.

[0003] Carbon materials are considered to be ideal candidates for the negative electrode of SIHCs due to their high conductivity, structural adjustability and low cost. Porous carbons such as hard carbon and graphene can achieve a reversible sodium storage capacity of 200-350 mAh / g by regulating the interlayer spacing and defect engineering. However, existing carbon-based negative electrodes still face three major bottlenecks: (1) Kinetic hysteresis: sodium ions The radius is larger than that of lithium ions The diffusion energy barrier between carbon layers is high, resulting in insufficient rate performance; (2) Low first coulombic efficiency: irreversible surface adsorption and excessive growth of the solid electrolyte interface (SEI) film cause the first cycle coulombic efficiency (ICE) to be generally less than 80%; (3) Poor long-term cycle stability: repeated insertion of sodium ions causes the carbon skeleton to expand in volume (>10%) and collapse in structure, and the capacity decay rate exceeds 30% after 100 cycles. In addition, although single element doping (such as nitrogen and sulfur) can improve the contribution of surface pseudocapacitance, the singleness of the doping site and the concentration limitation lead to low utilization of active sites, making it difficult to achieve synergistic optimization of kinetic performance and capacity. In response to the above problems, it is urgent to construct a high-entropy, multi-active site carbon-based negative electrode through multi-element synergistic doping and microstructure innovation to break through the sodium storage kinetics limitation and promote the practical application of SIHCs technology. Summary of the Invention

[0004] According to the first aspect of the present application, a high-entropy non-metal-doped three-dimensional ordered mesoporous carbon sphere composite material is provided. A three-dimensional ordered mesoporous carbon sphere (HE-GPC) doped with a high-entropy non-metal element and having a gradient porous structure is constructed. In terms of structural design, the gradient porous carbon accelerates ion interface and bulk transport and reduces the diffusion energy barrier through the multi-level pore size distribution and structural synergistic effect of micropores-mesopores-macroporosities; the elastic skeleton of the gradient pore wall can buffer the volume expansion caused by the insertion of sodium ions, inhibit the structural collapse during the cycle, and improve the cycle stability.

[0005] A high-entropy non-metal-doped three-dimensional ordered mesoporous carbon sphere composite material, wherein the three-dimensional ordered mesoporous carbon sphere composite material contains a high-entropy non-metal doping element;

[0006] The high entropy non-metallic doping elements include nitrogen, sulfur, phosphorus, boron and fluorine;

[0007] The three-dimensional ordered mesoporous carbon sphere composite material has a radial gradient pore size structure.

[0008] Optionally, the high entropy non-metallic doping elements are nitrogen, sulfur, phosphorus, boron and fluorine.

[0009] Optionally, the radial gradient pore structure is a multi-level pore system in which the internal pore size, porosity or pore arrangement of the carbon material presents a continuous gradient change along the radial direction.

[0010] In this application, gradient porous carbon refers to a multi-level pore system in which the pore size, porosity or pore arrangement of the carbon material presents a continuous gradient change along a specific direction.

[0011] Optionally, the three-dimensional ordered mesoporous carbon sphere composite material has a diameter of 250 to 350 nm and a pore size of about 2 to 10 nm.

[0012] According to the second aspect of the present application, a method for preparing a high-entropy non-metal-doped three-dimensional ordered mesoporous carbon sphere composite material is provided. First, dopamine monomer is dispersed in an ethanol / water composite solvent containing a soft template and an expander, and emulsion polymerization is carried out. Then, the precursor powder (dopamine nanospheres) is obtained by centrifugation and drying. The precursor powder is then uniformly mixed with a non-metal source (nitrogen / N, sulfur / S, boron / B, phosphorus / P, fluorine / F), and placed in a mixed atmosphere of hydrogen and argon for high-temperature sintering. Finally, the five-element inorganic non-metallic element-doped high-entropy gradient nano-carbon sphere composite material is naturally cooled.

[0013] High-entropy non-metal-doped ordered gradient mesoporous carbon spheres were constructed using a high-entropy strategy. A three-dimensional hierarchical polymer precursor was synthesized via soft template-assisted emulsion polymerization. This precursor was then blended with nitrogen, sulfur, phosphorus, boron, and fluorine sources to prepare a high-entropy non-metal-doped ordered gradient mesoporous carbon sphere composite. This method is simple, environmentally friendly, has high product yields, and is easily scaled up for commercialization.

[0014] The method for preparing the three-dimensional ordered mesoporous carbon sphere composite material comprises at least the following steps:

[0015] S1: placing polymer monomers in an ethanol / water composite solution system containing a soft template and an expansion agent to obtain a precursor solution A;

[0016] S2 adds a pH regulator to the precursor solution A, reacts, separates, and dries to obtain a precursor B;

[0017] S3: uniformly mix the precursor B with a nitrogen source, a sulfur source, a phosphorus source, a boron source, and a fluorine source, place the mixture in a reducing atmosphere, and calcine the mixture to obtain the three-dimensional ordered mesoporous carbon sphere composite material.

[0018] Optionally, in step S1, the polymer monomer is selected from at least one of dopamine, resorcinol / formaldehyde, glucose, sucrose, lignin, cellulose, pyrrole, acrylonitrile, and aniline.

[0019] Glucose, sucrose, lignin, and cellulose are biomass carbon sources. Dopamine is self-polymerized to form polydopamine, and resorcinol / formaldehyde is self-polymerized to form resorcinol-formaldehyde resin, which serves as a carbon source.

[0020] Optionally, in step S1, the soft template is selected from an amphiphilic block copolymer;

[0021] Optionally, the amphiphilic block copolymer is selected from at least one of Pluronic series, polystyrene-polyoxyethylene series, and polyacrylic acid series block copolymers;

[0022] Optionally, the Pluronic series is selected from at least one of F127 and P123;

[0023] The polystyrene-polyethylene oxide is selected from PS-b-PEO;

[0024] The polyacrylic acid block copolymer is selected from at least one of PAA-b-PS and PEO-b-PMA.

[0025] Optionally, in step S1, the swelling agent is selected from at least one of trimethylbenzene, xylene, chlorobenzene, and cyclohexane. The key function of the swelling agent is to regulate the physical and chemical properties of the precursor solution and the self-assembly behavior of the soft template, thereby optimizing the formation and expansion of the pore structure. The boiling point, polarity, volatility, and compatibility with the template agent should be comprehensively considered.

[0026] Optionally, in step S1, the mass ratio of the polymer monomer to the soft template is 1:0.5-1.5.

[0027] Optionally, in step S1, the mass ratio of the polymer monomer to the soft template is 1:1.0-1.5.

[0028] Optionally, in step S1, in the precursor solution A, the volume ratio of water, ethanol and swelling agent is 1:0.5 to 1:0.01 to 0.2.

[0029] Optionally, in step S1, in the precursor solution A, the volume ratio of water, ethanol and swelling agent is 1:0.8 to 1:0.05 to 0.15.

[0030] Optionally, the mass volume ratio of the polymer monomer to the ethanol / water composite solution is 1-5 g:200 mL.

[0031] Optionally, in step S2, the pH regulator is selected from at least one of ammonia water, sodium hydroxide, tris-hydrochloric acid buffer (Tris-HCl), Na2CO3 / NaHCO3 (sodium carbonate / sodium bicarbonate) buffer, ethanolamine, diethanolamine, and phosphate-sodium hydroxide buffer (PBS-NaOH).

[0032] Optionally, in step S2, the reaction temperature is 25-35° C., and the reaction time is 0.5-5 h.

[0033] Optionally, in step S3, the nitrogen source is selected from at least one of melamine, urea, and ammonium chloride;

[0034] The sulfur source is selected from at least one of sublimed sulfur powder, thiourea, thioacetamide, and cysteine;

[0035] The phosphorus source is selected from at least one of borophytic acid, triphenyl phosphate, phosphoric acid, sodium dihydrogen phosphate, and disodium hydrogen phosphate;

[0036] The boron source is selected from at least one of boric acid, boron nitride, phenylboric acid, and trimethyl borate;

[0037] The fluorine source is selected from at least one of polytetrafluoroethylene, polyvinylidene fluoride, ammonium fluoride and hydrofluoric acid.

[0038] Optionally, in step S3, the usage ratio of precursor B, nitrogen source, sulfur source, boron source, phosphorus source and fluorine source is 1:0.5-6:0.5-6:0.5-6:1-12:1-12.

[0039] Optionally, in step S3, the usage ratio of precursor B, nitrogen source, sulfur source, boron source, phosphorus source and fluorine source is 1:0.5~3:0.5~3:0.5~3:0.5~6:0.5~6.

[0040] Optionally, in step S3, the calcination temperature is 600-900° C., and the calcination time is 0.5-5 h.

[0041] Optionally, in step S3, the reducing atmosphere includes hydrogen.

[0042] Optionally, in step S3, the reducing atmosphere is a mixture of hydrogen and argon.

[0043] According to a third aspect of the present application, a negative electrode material is provided.

[0044] A negative electrode material comprises the three-dimensional ordered mesoporous carbon sphere composite material described above.

[0045] According to the fourth aspect of the present application, a sodium ion hybrid capacitor is provided. In terms of material composition, the thiophene-like sulfur configuration mediates the dynamic redox process, realizing the pseudocapacitive storage of sodium ions and anions; at the same time, the fluorine functional group induces the formation of a NaF-rich solid electrolyte interface (SEI) with self-healing properties, thereby ensuring long-cycle stability; the synergistic effect of the NBP three-component system effectively enhances the electronic conductivity and accurately controls the ion adsorption energy by constructing a multi-level defect network, which greatly improves its electrochemical performance as a sodium-based hybrid ion capacitor material.

[0046] A sodium ion hybrid capacitor, comprising a negative electrode material, a positive electrode material, an electrolyte, a diaphragm, and a battery shell;

[0047] The negative electrode material is the negative electrode material described above.

[0048] The beneficial effects of this application include:

[0049] The high entropy non-metal doped three-dimensional ordered mesoporous carbon sphere composite material provided in this application, and its preparation method and application, by constructing a three-dimensional ordered mesoporous carbon sphere (HE-GPC) doped with a high entropy non-metal element and having a gradient porous structure, studies have shown that the thiophene-like sulfur configuration mediates the dynamic redox process, realizing the pseudocapacitive storage of sodium ions and anions; at the same time, the fluorine functional group induces the formation of a NaF-rich solid electrolyte interface (SEI) with self-healing properties, thereby ensuring long-cycle stability. The synergistic effect of the NBP three-component system effectively enhances the electronic conductivity and accurately controls the ion adsorption energy by constructing a multi-level defect network, which greatly improves its electrochemical performance as a sodium-based mixed ion capacitor material. The structure of the composite material is stable and exhibits excellent electrochemical properties; this method has a simple production process, is environmentally friendly, has a high product yield, is easy to industrially scale up, and realizes commercialization. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 is the X-ray diffraction pattern of the product obtained in Example 1.

[0051] Figure 2 These are field emission scanning electron microscope images of the product obtained in Example 1, wherein Figure a is a low magnification SEM image, and Figure b is a medium magnification SEM image.

[0052] Figure 3 These are transmission electron microscope images of the product obtained in Example 1, Figure a is a TEM image, Figure b is a high-resolution TEM image, Figure c is a contour map of the carbon grain interplanar spacing, and Figure d is a TEM dark field image and element distribution map.

[0053] Figure 4 This is a graph showing the electrochemical sodium storage cycle performance of the electrode material prepared from the product obtained in Example 1.

[0054] Figure 5 This is a graph showing the cyclic performance of a sodium-based hybrid ion capacitor using an electrode material prepared from the product obtained in Example 1. DETAILED DESCRIPTION

[0055] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0056] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0057] Unless otherwise specified, conventional methods were used for testing, and instrument settings were those recommended by the manufacturer.

[0058] The analysis method in the examples of this application is as follows:

[0059] The instrument model for X-ray diffraction pattern analysis is: Japan Rigaku desktop X-ray diffractometer (Miniflex 600).

[0060] The instrument model for field emission scanning electron microscopy analysis is: scanning electron microscope Hitachi, Japan (SU-8020).

[0061] The instrument model for transmission electron microscopy analysis is a field emission transmission electron microscope (Tecnai F20) produced by FEI Company, USA.

[0062] Example 1

[0063] 1) 4g F127 and 3g dopamine were dissolved in a mixture of 200mL ethanol and 200mL water and magnetically stirred at room temperature for 15 minutes until completely dissolved. Subsequently, 20mL of mesitylene was slowly added dropwise to the solution under continuous stirring to form a nanoemulsion system. Subsequently, 10mL of ammonia solution was added dropwise to initiate the self-polymerization reaction of the dopamine molecules. After the reaction was continued for 5 hours, a dark brown solid powder precursor, namely the mesoporous dopamine microspheres, was obtained through centrifugation, washing, and drying.

[0064] 2) The black solid powder precursor (dopamine microspheres) obtained in step 1) was mixed with a doping source (melamine, sublimed sulfur, boric acid, ammonium dihydrogen phosphate, polytetrafluoroethylene) in a mass ratio of 1:3:3:3:6:6, placed in a tube furnace with a mixed atmosphere of hydrogen and argon, and heated to 800°C at a heating rate of 3°C / min. The mixture was kept warm for 2 hours. After the reaction was complete, the mixture was naturally cooled to room temperature to obtain the high entropy non-metal-doped ordered gradient mesoporous carbon sphere composite material, which was recorded as HEC.

[0065] Comparative Example 1

[0066] The operation is the same as that of Example 1, except that in step 2), only melamine is used as the doping source to obtain nitrogen-doped carbon, which is recorded as NC.

[0067] Figure 1 The following is the X-ray diffraction pattern of the product obtained in Example 1, where NC represents nitrogen-doped carbon and HEC represents the high-entropy non-metallic element-doped carbon obtained in Example 1. It can be seen that two broad, blunt diffraction peaks appear at approximately 21.7° and 43°, corresponding to the (002) and (100) crystal planes of the graphite-like domains in the amorphous structure, respectively. It is worth noting that compared to the NC sample, the position of the (002) diffraction peak of the HEC sample shifts toward lower angles, indicating an expansion of the graphite interlayer spacing. Using the Bragg formula, the interplanar spacing of the HEC sample is 0.407 nm, which is larger than the interplanar spacing of the NC sample (0.381 nm).

[0068] Figure 2This is a field emission scanning electron micrograph of the product obtained in Example 1. Figure a is a TEM image of HEC, which shows good monodispersity and uniform spherical morphology with an average particle size of approximately 250 nm. The enlarged image (Figure b) further reveals that the surface of the carbon sphere is covered with a large number of open mesoporous structures, and the overall surface features are similar to those of a golf ball.

[0069] Figure 3 Figure 1 is a transmission electron micrograph of the product obtained in Example 1. Figure a is a low-magnification TEM image, Figure b is a high-resolution TEM image, Figure c is a contour map of the carbon grain interplanar spacing, and Figure d is a TEM dark-field image and elemental distribution map. It can be seen that a large number of gradient-distributed mesopores are uniformly distributed within the HEC, forming an open multi-cavity mesoporous structure. The high-resolution TEM image shows that the HEC composite material is primarily composed of a highly disordered and structurally distorted graphite-like structure, with an interlayer spacing of approximately 0.407 nm on the (002) crystal plane. The TEM dark-field image and its corresponding elemental distribution map show that the five non-metallic elements (N, S, P, B, and F) are uniformly distributed throughout the HEC composite material, indicating that the high-entropy non-metallic doping strategy has been successfully implemented.

[0070] The product obtained in Example 1 was used as an electrode material to test its electrochemical sodium storage cycle performance. HEC composite powder, a binder (sodium carboxymethyl cellulose, CMC), and a conductive agent (acetylene black) were uniformly ground at a mass ratio of 8:1:1. A small amount of deionized water was added to form a slurry. The slurry was applied to copper foil using a scraper and then incubated at 80°C in a vacuum drying oven for 24 hours. The dried electrode sheet was then cut into 12 mm diameter sheets using a microtome. Finally, in a glove box, button cells were assembled using this material as the working electrode, sodium metal as the reference and counter electrodes, 1M NaPF6 as the electrolyte (solvent: ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) in a 1:1:1 volume ratio), and Celard 3501 as the separator. Electrochemical performance was then tested using a Wuhan LAND-CT2001 electrochemical workstation.

[0071] Figure 4 As shown in the electrochemical sodium storage cycle performance diagram, it can be seen that at 5Ag -1 Under constant current density conditions, the HEC anode exhibits excellent cycling stability and can still maintain 301 mAh g after 6500 cycles. -1 The reversible specific capacity of the NC anode is as high as 98.2%, while the capacity retention rate is as high as 98.2%. In contrast, the NC anode shows significant capacity decay, retaining only 93 mAh g -1 The specific capacity of the battery is only 30%.

[0072] The product obtained in Example 1 was used as the negative electrode material and assembled with the positive electrode material, electrolyte, separator, and battery shell to form a sodium-based mixed ion capacitor. The specific process was as follows: 1) the negative electrode sheet was prepared as described above; 2) the positive electrode sheet was prepared: commercial sodium vanadium phosphate positive electrode powder was uniformly ground with a binder (polyvinylidene fluoride PVDF) and a conductive agent (acetylene black) in a mass ratio of 8:1:1, and a small amount of deionized water was added to form a slurry. The slurry was applied to aluminum foil using a scraper, and then kept at 80°C in a vacuum drying oven for 24 hours. The dried electrode sheet is then cut into electrode sheets with a diameter of 12 mm using a slicer; 3) the electrolyte solute is 1 mol / L sodium hexafluorophosphate, and the solvent is a mixed solvent of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) in a volume ratio of 1:1:1; 4) in a glove box, the prepared negative electrode material, positive electrode material, electrolyte, glass fiber separator, positive and negative battery shells are assembled in a certain order, and finally packaged to realize the preparation of sodium-based mixed ion capacitors and test their electrochemical properties.

[0073] Figure 5 The cyclic performance diagram of sodium-based hybrid ion capacitor shows that the prepared sodium-based hybrid ion capacitor has a high cycling performance at 1Ag. -1 After running 9000 cycles at a current density of 100 nm, it can achieve an ultra-stable cycle life with a capacity retention rate of up to 88.2%.

[0074] The above descriptions are merely a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application discloses the preferred embodiments as above, they are not intended to limit the present application. Any technical personnel familiar with the present profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A high entropy non-metal-doped three-dimensional ordered mesoporous carbon sphere composite material, characterized in that: The three-dimensional ordered mesoporous carbon sphere composite material contains a high-entropy non-metallic doping element; The high entropy non-metallic doping elements include nitrogen, sulfur, phosphorus, boron and fluorine; The three-dimensional ordered mesoporous carbon sphere composite material has a radial gradient pore size structure.

2. The three-dimensional ordered mesoporous carbon sphere composite material according to claim 1, characterized in that: The radial gradient pore size structure is a multi-level pore system in which the internal pore size, porosity or pore arrangement of the carbon material presents a continuous gradient change along the radial direction.

3. The three-dimensional ordered mesoporous carbon sphere composite material according to claim 1, characterized in that: The diameter of the three-dimensional ordered mesoporous carbon sphere composite material is 250-350 nm, and the pore size is about 2-10 nm.

4. The method for preparing the three-dimensional ordered mesoporous carbon sphere composite material according to any one of claims 1 to 3, characterized in that: At least the following steps are included: S1: placing polymer monomers in an ethanol / water composite solution system containing a soft template and an expansion agent to obtain a precursor solution A; S2 adds a pH regulator to the precursor solution A, reacts, separates, and dries to obtain a precursor B; S3: uniformly mix the precursor B with a nitrogen source, a sulfur source, a phosphorus source, a boron source, and a fluorine source, place the mixture in a reducing atmosphere, and calcine the mixture to obtain the three-dimensional ordered mesoporous carbon sphere composite material.

5. The preparation method according to claim 4, characterized in that In step S1, the polymer monomer is selected from at least one of dopamine, resorcinol / formaldehyde, glucose, sucrose, lignin, cellulose, pyrrole, acrylonitrile, and aniline; Preferably, in step S1, the soft template is selected from amphiphilic block copolymers; Preferably, the amphiphilic block copolymer is selected from at least one of the Pluronic series, polystyrene-polyoxyethylene series, and polyacrylic acid series block copolymers; Preferably, the Pluronic series is selected from at least one of F127 and P123; The polystyrene-polyethylene oxide is selected from PS-b-PEO; The polyacrylic acid block copolymer is selected from at least one of PAA-b-PS and PEO-b-PMA; Preferably, in step S1, the expansion agent is selected from at least one of trimethylbenzene, xylene, chlorobenzene, and cyclohexane; Preferably, in step S1, the mass ratio of the polymer monomer to the soft template is 1:0.5-1.5; Preferably, in step S1, the volume ratio of water, ethanol and expansion agent in the precursor solution A is 1:0.5 to 1:0.01 to 0.2; The mass volume ratio of the polymer monomer and the ethanol / water composite solution is 1-5 g:200 mL.

6. The preparation method according to claim 4, characterized in that In step S2, the pH adjuster is selected from at least one of ammonia water, sodium hydroxide, tris-hydrochloric acid buffer, sodium carbonate / sodium bicarbonate buffer, ethanolamine, diethanolamine, and phosphate-sodium hydroxide buffer; Preferably, in step S2, the reaction temperature is 25-35° C., and the reaction time is 0.5-5 h.

7. The preparation method according to claim 4, characterized in that In step S3, the nitrogen source is selected from at least one of melamine, urea, and ammonium chloride; The sulfur source is selected from at least one of sublimed sulfur powder, thiourea, thioacetamide, and cysteine; The phosphorus source is selected from at least one of borophytic acid, triphenyl phosphate, phosphoric acid, sodium dihydrogen phosphate, and disodium hydrogen phosphate; The boron source is selected from at least one of boric acid, boron nitride, phenylboric acid, and trimethyl borate; The fluorine source is selected from at least one of polytetrafluoroethylene, polyvinylidene fluoride, ammonium fluoride, and hydrofluoric acid; Preferably, in step S3, the mass ratio of the precursor B, the nitrogen source, the sulfur source, the boron source, the phosphorus source, and the fluorine source is 1:0.5-6:0.5-6:0.5-6:1-12:1-12.

8. The preparation method according to claim 4, characterized in that In step S3, the calcination temperature is 600-900°C and the calcination time is 0.5-5h; Preferably, in step S3, the reducing atmosphere comprises hydrogen.

9. A negative electrode material, characterized in that The negative electrode material comprises the three-dimensional ordered mesoporous carbon sphere composite material according to any one of claims 1 to 3.

10. A sodium ion hybrid capacitor, characterized in that: The sodium ion hybrid capacitor includes a negative electrode material, a positive electrode material, an electrolyte, a separator, and a battery shell; The negative electrode material is the negative electrode material according to claim 9.

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