Halohydrocarbon polymer mediated hard carbon material, preparation method and application thereof, and battery

Abstract

The invention discloses a halogenated hydrocarbon polymer mediated hard carbon material, a preparation method and application thereof, and a battery. The preparation method comprises the following steps: (1) sequentially carrying out pre-carbonization and ball milling on bamboo powder, and then carrying out surface oxidation treatment to obtain a bamboo powder precursor; and (2) mixing the bamboo powder precursor with a solution containing a halogenated hydrocarbon polymer, drying, and carbonizing to obtain the halogenated hydrocarbon polymer mediated hard carbon material. The preparation method disclosed by the invention is simple to operate, low in cost and easy for industrial production, and the prepared hard carbon material has a rich internal closed-pore structure and shows excellent cycle stability and high cycle efficiency when being applied to batteries.

Description

Technical Field

[0001] This invention specifically relates to a halogenated hydrocarbon polymer-mediated hard carbon material, its preparation method, applications, and batteries. Background Technology

[0002] Hard carbon, as a disordered carbon material with low graphitization, exhibits significant interlayer spacing and high defect density, making it a highly promising anode material for sodium-ion batteries and crucial for promoting the development of low-cost, large-scale energy storage technologies. Although hard carbon has become one of the preferred materials for sodium-ion battery anodes, its commercialization still faces several challenges: limited specific capacity, low cycle efficiency, and poor cycle stability.

[0003] Despite the diverse preparation pathways for hard carbon materials, most existing methods struggle to simultaneously control the closed pore structure within the hard carbon and lack adaptability to volume expansion during cycling, easily leading to interface delamination and performance degradation. Traditional pyrolytic carbonization processes often fail to precisely control pore formation, preventing the material from simultaneously achieving optimal reversible specific capacity and plateau capacity. The inherently low ionic / electronic conductivity of hard carbon materials limits their rate performance, while simple doping or coating strategies may sacrifice other properties while improving conductivity. Furthermore, during electrochemical cycling, the unstable solid electrolyte interface (SEI) continuously consumes active sodium and electrolyte, resulting in capacity decay, and most preparation methods do not pre-construct a stable interface from a material bulk design perspective. Therefore, developing low-cost strategies that can synergistically stabilize the SEI, optimize pore structure, and adapt to volume changes remains a key challenge for advancing the practical application of sodium-ion batteries. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a halogenated hydrocarbon polymer-mediated hard carbon material, its preparation method, applications, and batteries. The preparation method of this invention is not only simple and low-cost, but its sustainable waste recycling strategy also opens up a feasible path for the large-scale production of high-performance hard carbon anodes. Furthermore, it provides new insights into the synergistic regulation mechanism of hard carbon pore structure and SEI film in sodium-ion battery technology. The prepared hard carbon material possesses abundant internal closed-pore structures and exhibits excellent cycle stability and high cycle efficiency when applied to batteries.

[0005] This invention utilizes the dehalogenation of halogenated hydrocarbon polymers during pyrolysis to generate vinyl radicals and HX. Volatile HX species (e.g., HCl) effectively promote the formation of free radicals within the bamboo matrix. Vinyl radicals in the non-volatile pyrolysis products crosslink with free radicals on the bamboo powder surface, forming a dense coating (using SP). 2 (Carbon-based long-range graphitization domains), while HX triggers free radical reactions within the carbon matrix, achieving optimization of the closed-pore structure and control of pore size. Rich in SP 2The surface of carbon promotes the adsorption of electrolyte anionic groups, forming a thin, uniform, and inorganic-rich SEI, thereby improving ion conduction efficiency and cycle stability. Compared to traditional asphalt coating, the preparation method of this invention not only produces a more uniform coating layer but also optimizes the closed-cell structure.

[0006] The present invention solves the above-mentioned technical problems through the following technical solutions:

[0007] This invention provides a method for preparing a hard carbon material mediated by a halocarbon polymer, comprising the following steps:

[0008] (1) Bamboo powder is pre-carbonized and ball-milled in sequence, and then surface-oxidized to obtain bamboo powder precursor;

[0009] (2) The bamboo powder precursor is mixed with a solution containing a halogenated hydrocarbon polymer, and then dried and carbonized to obtain the hard carbon material mediated by the halogenated hydrocarbon polymer.

[0010] In this invention, according to conventional practice in the art, the pre-carbonization and the carbonization are generally carried out in an inert gas atmosphere; the inert gas can be conventional in the art, such as nitrogen or argon; the pre-carbonization and the carbonization are generally carried out in a tube furnace.

[0011] In step (1), the bamboo powder can be conventional in the art, and is preferably selected from one or more of moso bamboo powder, water bamboo powder, nan bamboo powder and purple bamboo powder. The particle size of the bamboo powder can be 50-700 mesh, for example 80 mesh, 100 mesh, 150 mesh, 200 mesh or 400 mesh.

[0012] In step (1), the pre-carbonization temperature can be 200-450℃, for example 250℃, 300℃, 350℃ or 400℃; the pre-carbonization time can be 1-6h, for example 2h, 3h or 4h.

[0013] In step (1), the diameter of the grinding balls used in the ball mill can be 5-20 mm, for example 8 mm, 10 mm or 15 mm; during the ball milling process, the ball-to-material ratio can be (5-15):1, for example 6:1, 8:1 or 10:1, where the ball-to-material ratio refers to the mass ratio of the grinding balls to the material to be milled; the rotation speed of the ball mill can be 200-600 r / min, for example 250 r / min, 300 r / min or 400 r / min; the ball milling time can be 2-24 h, for example 4 h, 6 h, 12 h or 14 h.

[0014] In step (1), the surface oxidation treatment is preferably carried out by calcination in air or by treatment with hydrogen peroxide. Surface oxidation treatment is beneficial for the formation of abundant free radicals and for achieving better chemical coating during carbonization.

[0015] The calcination in air can be carried out in a muffle furnace or a tube furnace. The calcination temperature in air can be 250-500℃, preferably 300-400℃, for example 320℃, 350℃ or 380℃; the calcination time in air can be 1-6h, for example 2h or 4h.

[0016] The hydrogen peroxide treatment used can be at a concentration of 3wt%-30wt%, such as 5wt%, 8wt%, 10wt%, 15wt%, or 20wt%, where wt% refers to the percentage of hydrogen peroxide by mass relative to the total mass of the solution. The mass ratio of bamboo powder to hydrogen peroxide volume can be 1:(10-50) g / mL, such as 1:20 g / mL, 1:25 g / mL, or 1:30 g / mL. The hydrogen peroxide treatment is generally performed at room temperature; the treatment time can be 10-30 minutes, such as 15 minutes, 20 minutes, or 25 minutes.

[0017] The hydrogen peroxide treatment preferably includes the following process: adding the ball-milled product to hydrogen peroxide and reacting under stirring.

[0018] In accordance with conventional practices in this field, the hydrogen peroxide treatment is generally followed by washing and drying. The washing typically uses deionized water; the washing is usually performed three times or more; the drying temperature is 70-100°C, for example, 80°C; and the drying time is 6-24 hours, for example, 12 hours.

[0019] In step (2), the solvent in the solution containing the halohydrocarbon polymer can be conventional in the art, generally a solvent capable of dissolving the halohydrocarbon polymer, such as DMF. The concentration of the solution containing the halohydrocarbon polymer can be 0.01-5 g / mL, for example 0.02 g / mL, 0.04 g / mL, 0.1 g / mL, 0.5 g / mL, 1 g / mL or 2 g / mL.

[0020] In step (2), the halogenated hydrocarbon polymer refers to a polymer formed by polymerization of halogenated olefin monomers or copolymerization with other monomers, in which some hydrogen atoms in the molecule are replaced by halogens. The halogen in the halogenated hydrocarbon polymer is generally one or more of fluorine, chlorine, bromine and iodine. The halogenated hydrocarbon polymer preferably includes one or more of polyvinyl chloride, polyvinylidene fluoride, polyvinylidene chloride and polytetrafluoroethylene.

[0021] The viscosity number K value of the polyvinyl chloride can be 50-80, preferably 55-70.

[0022] In step (2), the mass percentage of the halohydrocarbon polymer to the bamboo powder precursor can be 1%-100%, for example 5%, 10%, 12%, 15%, 20%, 30%, 40%, 50% or 60%.

[0023] In step (2), the drying method can be conventional in the art, such as drying or heating and evaporating under stirring; the purpose of drying is to remove the solvent.

[0024] In step (2), after drying and before carbonization, grinding is preferably required.

[0025] In step (2), the carbonization temperature can be 600-1600℃, for example 800℃, 1000℃, 1100℃, 1200℃, 1300℃, 1350℃, 1400℃ or 1500℃; the carbonization time can be 1-12h, for example 1h, 1.5h, 2h, 3h, 4h, 5h or 6h.

[0026] The present invention also provides a hard carbon material mediated by a halocarbon polymer prepared by the preparation method described above.

[0027] The present invention also provides a hard carbon material mediated by a halogenated hydrocarbon polymer, which has a core-shell structure, including a core and a shell; the core is a hard carbon particle, and the shell is a multilayer long-range graphitized carbon layer.

[0028] In this invention, the hard carbon material mediated by the halogenated hydrocarbon polymer can be a stacked graphite sheet layer with a thickness of 2-10 μm. The thickness of the multilayer long-range graphitized carbon layer can be 1.5-20 nm, preferably 1.5-10 nm, for example 2 nm, 2.5 nm, 3 nm, or 5 nm. The interlayer spacing of the hard carbon particles can be 0.38-0.45 nm, for example 0.39 nm, 0.4 nm, or 0.42 nm. The BJH pore size of the hard carbon material mediated by the halogenated hydrocarbon polymer can be 1.5-5 nm, preferably 1.8-4 nm, which is the pore size determined by nitrogen adsorption-desorption testing. The average closed-pore diameter of the hard carbon material mediated by the halogenated hydrocarbon polymer can be 9-12 Å, for example 9.3 Å, 9.53 Å, 9.8 Å, 10 Å, or 11 Å. The specific surface area of ​​the hard carbon material mediated by the halogenated hydrocarbon polymer can be 9-13 m². 2 / g, for example, 10 m 2 / g、11 m 2 / g or 12 m 2 / g.

[0029] The present invention also provides the application of the hard carbon material mediated by the halohydrocarbon polymer as described above in batteries.

[0030] The present invention also provides a battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the negative electrode comprises a hard carbon material mediated by a halogenated hydrocarbon polymer as described above.

[0031] In this invention, the battery is preferably a sodium-ion battery.

[0032] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0033] The reagents and raw materials used in this invention are all commercially available.

[0034] The positive and progressive effects of this invention are as follows:

[0035] The preparation method of this invention is not only simple to operate and low in cost, but also opens up a feasible path for the large-scale production of high-performance hard carbon anodes through a sustainable waste recycling strategy. Furthermore, it provides a new idea for the synergistic regulation mechanism of hard carbon pore structure and SEI film in sodium-ion battery technology. The hard carbon material prepared has a rich internal closed-pore structure and exhibits excellent cycle stability and high cycle efficiency when applied to batteries. Attached Figure Description

[0036] Figure 1 TEM image of the hard carbon material prepared in Example 1;

[0037] Figure 2 TEM image of the hard carbon material prepared in Comparative Example 1;

[0038] Figure 3 Here is a SEM image of the hard carbon material prepared in Example 1;

[0039] Figure 4 The graphs show the rate testing results of the hard carbon materials prepared in Example 1 and Comparative Example 1. Detailed Implementation

[0040] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0041] The bamboo powder used in the following examples and comparative examples is moso bamboo powder, purchased from Zhongxin Mineral Products Processing Plant, with a particle size of 100 mesh; polyvinyl chloride (PVC) was purchased from Aladdin, K62-60; polyvinylidene chloride (PVDC) is grade RG, brand Adamas.

[0042] Example 1

[0043] Bamboo powder was placed in a tube furnace and pre-carbonized at 300℃ for 3 hours under an argon atmosphere. The pre-carbonized product was added to an agate jar of a planetary ball mill (Nanjing University Instrument Factory, QM-3SP4), with grinding balls of 10 mm diameter and a ball-to-powder ratio of 8:1, and ball-milled at 300 r / min for 12 hours. The ball-milled product was calcined at 350℃ for 2 hours in a muffle furnace to obtain a bamboo powder precursor. 15% (by weight) of polyvinyl chloride (PVC) was dissolved in DMF solvent (0.04 g / mL) and then thoroughly mixed with the bamboo powder precursor. The mixture was then stirred at 110℃ to remove the DMF. The dried black powder was ground until homogeneous to obtain the precursor. Finally, the precursor was carbonized at 1300℃ for 3 hours under an argon atmosphere at a heating rate of 5℃ / min to obtain a hard carbon material.

[0044] Example 2

[0045] Compared with Example 1, everything else remained the same except that the mass ratio of polyvinyl chloride to bamboo powder was adjusted to 10%.

[0046] Example 3

[0047] Compared with Example 1, everything else remained the same except that the mass ratio of polyvinyl chloride to bamboo powder was adjusted to 30%.

[0048] Example 4

[0049] Compared with Example 1, everything else remained the same except that the mass ratio of polyvinyl chloride to bamboo powder was adjusted to 50%.

[0050] Example 5

[0051] Compared with Example 1, everything else remained the same except that the carbonization temperature was adjusted from 1300°C to 1100°C.

[0052] Example 6

[0053] Compared with Example 1, everything else remained the same except that the carbonization temperature was adjusted from 1300°C to 1400°C.

[0054] Example 7

[0055] Compared with Example 1, the only difference is that the carbonization time was adjusted from 3h to 1.5h.

[0056] Example 8

[0057] Compared with Example 1, the only difference is that the carbonization time was adjusted from 3 hours to 5 hours.

[0058] Example 9

[0059] Compared to Example 1, everything else remains the same except that polyvinyl chloride is replaced with polyvinylidene chloride.

[0060] Example 10

[0061] Bamboo powder was placed in a tube furnace and pre-carbonized at 300℃ for 3 hours under an argon atmosphere. The resulting pre-carbonized product was added to an agate jar of a planetary ball mill (Nanjing University Instrument Factory, QM-3SP4), with grinding balls of 10 mm diameter and a ball-to-powder ratio of 8:1, and ball-milled at 300 r / min for 12 hours. The ball-milled product was then added to 5 wt% hydrogen peroxide (the mass ratio of bamboo powder to hydrogen peroxide was 1 g: 25 mL), and mixed at room temperature and a stirring speed of 200 rpm for 20 minutes. The mixture was then washed three times with deionized water and dried at 80℃ for 12 hours to obtain the bamboo powder precursor. 15% of the bamboo powder mass of polyvinyl chloride (PVC) was dissolved in DMF solvent (0.04 g / mL), and then thoroughly mixed with the bamboo powder precursor. The mixture was then stirred at 110 °C to remove DMF. The dried black powder was ground to a uniform state to obtain the precursor. Finally, the precursor was heated to 1300 °C in an argon atmosphere at a heating rate of 5 °C / min and held for 3 h to carbonize it, thus obtaining hard carbon material.

[0062] Comparative Example 1

[0063] Bamboo powder was carbonized directly at 1300℃ for 3 hours in an argon atmosphere to obtain hard carbon material.

[0064] Effect Example

[0065] (1) Morphological and structural characterization

[0066] Figure 1 This is a TEM image of the hard carbon material prepared in Example 1, based on... Figure 1 It is known that vinyl radicals crosslink with micron-sized bamboo-derived carbon precursors to form a dense coating (multi-layered long-range graphitized region) about 2.5 nm thick; more curved graphene layers are formed inside, resulting in abundant closed nanopores with an interlayer spacing of 0.4 nm. Figure 2 The image shows a TEM image of the hard carbon material prepared in Comparative Example 1. As can be seen from the image, the sample exhibits a highly disordered carbon structure with no obvious closed pores or graphite domains and an interlayer spacing of 0.36 nm.

[0067] Figure 3 The image shows a SEM image of the hard carbon material prepared in Example 1. The hard carbon material exhibits stacked graphite sheets with a thickness of 2-10 μm.

[0068] The carbonization pyrolysis process was analyzed by TG-FTIR. The analysis results showed that in addition to the release of CO2, a characteristic absorption peak corresponding to HCl in PVC appeared at 300℃. This result indicates that PVC undergoes a dechlorination reaction during pyrolysis to generate HCl.

[0069] In addition, FT-IR analysis was performed on the samples obtained by pyrolyzing the precursor in Example 1 at 400°C for 2 hours and the sample obtained by pyrolyzing bamboo powder in Comparative Example 1 at 400°C for 2 hours. The results showed that the pure bamboo powder, after pyrolysis, could not withstand temperatures exceeding 3400 cm⁻¹. -1 A hydroxyl peak appeared at the surface, while the PVC-coated sample did not, indicating that HCl generated during PVC pyrolysis induced the dehydroxylation of surface hydroxyl groups. Raman analysis showed that the ID / IG ratio of the sample prepared in Example 1 was lower than that of Comparative Example 1, indicating that PVC can induce the formation of SP on the carbon matrix. 2 carbon.

[0070] Characterization by nitrogen adsorption-desorption showed that the pore sizes of the hard carbon materials prepared in Example 1 and Comparative Example 1 were both distributed in the range of 1.8-4 nm, and the specific surface area of ​​Example 1 was 11 m². 2 / g, Comparative Example 1 is 14 m 2 / g, due to the filling effect of molten polyvinyl chloride on the pores during pyrolysis, the specific surface area of ​​Example 1 is smaller than that of Comparative Example 1. According to SAXS test results, the specific surface area of ​​both Example 1 and Comparative Example 1 is between 0.2 and 0.3 Å. -1 The sample exhibits a rich variety of closed-pore structures. The average closed-pore diameter of Example 1 is 9.53 Å, while that of Comparative Example 1 is 8.5 Å.

[0071] The above analysis shows that the introduction of PVC can regulate the graphitization degree, closed-cell structure, defect degree and interlayer spacing of biomass-derived hard carbon.

[0072] (2) Electrochemical performance testing

[0073] The hard carbon materials prepared in Examples 1-10 and Comparative Example 1 were used as active materials for half-cell tests: First, a 1 wt% sodium alginate aqueous solution was prepared. During half-cell assembly, the mass ratio of active material, carbon black, and sodium alginate was 8.5:1:0.5. The mixture was homogenized using a homogenizer and then coated onto copper foil. The copper foil was dried at 120 °C for 24 h, cut into 12 mm diameter discs, and a mass loading of 2 mg / cm². -2 A CR2032 button cell casing was selected, with a 14 mm diameter sodium electrode as the counter electrode. The electrolyte was a 1.0 mol / L NaPF6 diethylene glycol dimethyl ether solution. The battery was assembled in an Ar atmosphere glove box, with water content controlled below 0.2 ppm and oxygen content below 1.0 ppm. The electrolyte was applied at 0.01–2.5 V (vs Na+ Within the voltage window of / Na), at a rate of 0.1 C (30 mA g), -1 Constant current cycling was performed using the LAND-CT2001A test system. Charge-discharge tests were conducted using the LAND-CT2001A test system at different current densities. Cyclic voltammograms were measured in the range of 0.01–3.0 V using a CHI760E electrochemical workstation (Shanghai Chenhua). 1 C was set to 300 mA h / g. The test results are shown in Table 1 and [Table data would be inserted here]. Figure 4 .

[0074] Table 1. First-cycle reversible specific capacity and corresponding first-efficiency of half-cell at 0.1C

[0075] sample Reversible specific capacity / (mA h / g) First effect Example 1 378.8 90.4% Example 2 372.2 88.5% Example 3 340.5 86.5% Example 4 312.6 85.8% Example 5 366.1 84.4% Example 6 375.2 89.8% Example 7 357.9 88.2% Example 8 371.3 86.2% Example 9 369.5 89.2% Example 10 382.4 91.1% Comparative Example 1 290.8 78.6%

[0076] according to Figure 4 It can be seen that Example 1 has a reversible specific capacity of 208.8 mA h / g at a high current density of 15C, while Comparative Example 1 has only 37 mA h / g.

[0077] Example 1, after 180 cycles at 0.1C, exhibited a capacity of 364.8 mA h / g and a cycle retention rate of 96.8%; while Comparative Example 1, under the same test conditions, had a capacity of 265.6 mA h / g and a cycle retention rate of 91%. Furthermore, Example 1, after 8100 cycles at 5C, exhibited a capacity of 253.2 mA h / g and a capacity retention rate of 93%.

[0078] While specific embodiments of the present invention have been described above, those skilled in the art should understand that these are merely illustrative examples, and the scope of protection of the present invention is defined by the appended claims. Those skilled in the art can make various changes or modifications to these embodiments without departing from the principles and essence of the present invention, but all such changes and modifications fall within the scope of protection of the present invention.

Claims

1. A method for preparing a hard carbon material mediated by a halohydrocarbon polymer, characterized in that, Includes the following steps: (1) Bamboo powder is pre-carbonized and ball-milled in sequence, and then surface-oxidized to obtain bamboo powder precursor; (2) The bamboo powder precursor is mixed with a solution containing a halogenated hydrocarbon polymer, and then dried and carbonized to obtain the hard carbon material mediated by the halogenated hydrocarbon polymer.

2. The method for preparing the hard carbon material mediated by the halohydrocarbon polymer as described in claim 1, characterized in that, The preparation method satisfies one or more of the following conditions: (1) The pre-carbonization temperature is 200-450℃, for example 250℃, 300℃, 350℃ or 400℃; (2) The pre-carbonization time is 1-6 hours, for example 2 hours, 3 hours or 4 hours; (3) The carbonization temperature is 600-1600℃, for example 800℃, 1000℃, 1100℃, 1200℃, 1300℃, 1350℃, 1400℃ or 1500℃; (4) The carbonization time is 1-12h, for example 1h, 1.5h, 2h, 3h, 4h, 5h or 6h.

3. The method for preparing hard carbon materials mediated by halohydrocarbon polymers as described in claim 1, characterized in that, The ball mill satisfies one or more of the following conditions: (1) The diameter of the grinding balls used in the ball mill is 5-20 mm; (2) During the ball milling process, the ball-to-material ratio is (5-15):1; (3) The rotational speed of the ball mill is 200-600 r / min; (4) The ball milling time is 2-24 hours.

4. The method for preparing hard carbon materials mediated by halohydrocarbon polymers as described in claim 1, characterized in that, The surface oxidation treatment is performed by calcination in air or by hydrogen peroxide treatment; The preferred temperature for calcination in air is 250-500℃; the preferred calcination time in air is 1-6 hours. Wherein, when hydrogen peroxide is used for treatment, the concentration of hydrogen peroxide is preferably 3wt%-30wt%; the ratio of the mass of bamboo powder to the volume of hydrogen peroxide is preferably 1:(10-50)g / mL; and the treatment time with hydrogen peroxide is preferably 10-30min.

5. The method for preparing the hard carbon material mediated by the halohydrocarbon polymer as described in claim 1, characterized in that, The preparation method satisfies one or more of the following conditions: (1) The solvent in the solution containing the halohydrocarbon polymer is a solvent that can dissolve the halohydrocarbon polymer, such as DMF; (2) The concentration of the solution containing the halohydrocarbon polymer is 0.01-5 g / mL; (3) The viscosity K value of the halohydrocarbon polymer can be 50-80; (4) The mass percentage of the halohydrocarbon polymer to the bamboo powder precursor is 1%-100%, for example 5%, 10%, 12%, 15%, 20%, 30%, 40%, 50% or 60%; (5) The bamboo powder is selected from one or more of the following: moso bamboo powder, water bamboo powder, nan bamboo powder and purple bamboo powder; (6) The particle size of the bamboo powder is 50-700 mesh.

6. A method for preparing a hard carbon material mediated by a halohydrocarbon polymer as described in any one of claims 1-5.

7. A hard carbon material mediated by a halohydrocarbon polymer, characterized in that, It has a core-shell structure, including a core and an outer shell; the core is a hard carbon particle, and the outer shell is a multilayer long-range graphitized carbon layer.

8. The hard carbon material mediated by a halohydrocarbon polymer as described in claim 7, characterized in that, The hard carbon material mediated by the halohydrocarbon polymer satisfies one or more of the following conditions: (1) The hard carbon material mediated by the halohydrocarbon polymer is a stacked graphite sheet layer with a thickness of 2-10 μm; (2) The thickness of the multilayer long-range graphitized carbon layer is 1.5-20 nm; (3) The interlayer spacing of the hard carbon particles is 0.38-0.45 nm; (4) The BJH pore size of the hard carbon material mediated by the halohydrocarbon polymer is 1.5-5 nm; (5) The specific surface area of ​​the hard carbon material mediated by the halohydrocarbon polymer is 9-13 m. 2 / g; (6) The average closed-pore diameter of the hard carbon material mediated by the halohydrocarbon polymer is 9-12 Å.

9. The application of a hard carbon material mediated by a halohydrocarbon polymer as described in any one of claims 6-8 in a battery.

10. A battery, characterized in that, It includes a positive electrode, a negative electrode, and an electrolyte, wherein the negative electrode comprises a hard carbon material mediated by a halogenated hydrocarbon polymer as described in any one of claims 6-8.

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