Carbon fiber electrode material loaded with hierarchical porous carbon, and preparation method and application thereof

Abstract

The application discloses a kind of carbon fiber electrode materials of hierarchical porous carbon load and its preparation method and its application in supercapacitor.The preparation method is: first, activated carbon fiber CFO is prepared by ion beam treatment method, then uniform and viscous egg white and hierarchical porous carbon containing slurry is uniformly coated on the surface of activated carbon fiber CFO, and the hierarchical porous carbon modified carbon fiber material is obtained by drying, calcination carbonization, and the carbon fiber electrode material of hierarchical porous carbon load is obtained.The method has the advantages of simple process, high efficiency, strong structure and performance controllability.Based on the adhesion of egg white, hierarchical porous carbon with good porosity and large specific surface area is loaded on the surface of carbon fiber, and during calcination carbonization, the hierarchical porous carbon is sintered with carbon fiber into one body by rearranging the carbon chain of egg white, which improves the specific surface area and porosity of carbon fiber, and improves the electrochemical performance of carbon fiber electrode.

Description

Technical Field

[0001] This invention relates to the field of new energy materials, specifically to a carbon fiber electrode material with loaded hierarchical porous carbon, its preparation method, and its application in the preparation of supercapacitor electrodes. Background Technology

[0002] As a highly efficient and stable energy storage device, supercapacitors have advantages such as high power density, fast charging and discharging capabilities, and ultra-long cycle life, and have great development potential in the fields of new energy vehicles and portable smart devices.

[0003] The key to fabricating high-performance supercapacitors lies in developing electrode materials with excellent electrochemical properties. Carbon fibers not only possess excellent properties such as high strength, high modulus, low density, and high temperature resistance, but also exhibit the excellent conductivity and electrochemical stability of carbon materials, making them a potential multifunctional electrode material. However, the dense, smooth, and chemically inert surface of carbon fibers, along with their low specific surface area and few pores, results in low charge accumulation density on the carbon fiber surface and weak charge storage capacity, leading to unsatisfactory energy storage performance when used directly as electrodes.

[0004] High specific surface area and well-developed conductive pore structure are key factors for achieving charge storage and rapid charge migration in carbon fiber electrodes. Currently, there are two main methods for modifying carbon fiber electrodes: the first is etching the carbon fiber surface, and the second is loading active materials onto the carbon fiber surface. Both can significantly increase the specific surface area of ​​carbon fibers and introduce a well-developed pore structure, thereby improving energy storage performance. However, both have certain limitations. The first modification method offers limited surface area improvement, and etching the carbon fiber surface may introduce defects, leading to deterioration of mechanical properties. The second modification method, loading active materials, has higher requirements, and the preparation of active materials with well-developed pore structures and large specific surface areas often requires the participation of large amounts of acids, alkalis, and other pore-forming agents. If activation is performed after loading, it may damage the carbon fiber electrode.

[0005] Therefore, in the process of carbon fiber modification, the preparation process of active materials with well-developed pore structure and large specific surface area is carried out in separate steps with the loading process, which can effectively avoid damage to the performance of carbon fibers during the modification process. Summary of the Invention

[0006] To address the aforementioned technical problems and shortcomings in this field, the present invention provides a carbon fiber electrode material with loaded hierarchical porous carbon, its preparation method, and its application in the preparation of supercapacitor electrodes.

[0007] This method boasts advantages such as simple process, high efficiency, and strong controllability of structure and performance. Based on the adhesive properties of egg white, this invention loads hierarchical porous carbon with good porosity and large specific surface area onto the surface of carbon fibers, constructing micro-nano multi-scale modified carbon fibers. After high-temperature calcination and carbonization in an inert atmosphere, the hierarchical porous carbon and carbon fibers are sintered into a single unit through the rearrangement of the carbon chains in the egg white at high temperature. This increases the specific surface area and porosity of the carbon fibers, improves the electrochemical performance of the carbon fiber electrode, and provides technical support for the application of carbon fiber electrodes in the field of supercapacitors.

[0008] A method for preparing a carbon fiber electrode material loaded with hierarchical porous carbon includes the following steps:

[0009] (1) After desizing carbon fiber is treated with ion beam, activated carbon fiber CFO is obtained;

[0010] (2) Add graded porous carbon and egg white to deionized water, stir evenly to obtain slurry;

[0011] (3) The slurry obtained in step (2) is uniformly coated on the surface of the activated carbon fiber CFO obtained in step (1), and dried to obtain carbon fiber material modified with graded porous carbon.

[0012] (4) The carbon fiber material modified with hierarchical porous carbon obtained in step (3) is calcined and carbonized. Once the carbonization is complete, the carbon fiber electrode material loaded with hierarchical porous carbon is obtained.

[0013] The hierarchical porous carbon is an activated carbon material with macroporous (pore size > 50 nm), mesoporous (pore size 2-50 nm), and microporous (pore size < 2 nm) structures, and the pores at each level are interconnected.

[0014] The amount of deionized water used in step (2) can be adjusted within the above range according to the density and particle size of the graded porous carbon, and the deionized water is removed by drying.

[0015] The preparation method of the present invention is as follows: first, activated carbon fiber CFO is prepared by ion beam treatment; then, a uniform and viscous slurry containing egg white and hierarchical porous carbon is uniformly coated on the surface of activated carbon fiber CFO; after drying, carbon fiber material modified with hierarchical porous carbon is obtained; and then further calcined and carbonized to obtain the carbon fiber electrode material loaded with hierarchical porous carbon.

[0016] The inventive concept of this invention mainly lies in:

[0017] This invention uses activated carbon fiber (CFO) as a support carrier. During the preparation of activated carbon fiber (CFO), the desizing carbon fiber is activated by ion beam treatment, introducing active groups such as carboxyl and hydroxyl groups, which improves the hydrophilicity of the material and allows the slurry to be coated more uniformly and evenly onto the surface of the carbon fiber fabric. Furthermore, compared to activated carbon fiber prepared by nitric acid oxidation, activated carbon fiber prepared by ion beam treatment has stronger hydrophilicity, avoids the etching of carbon fiber during nitric acid oxidation, and significantly reduces the activation time.

[0018] This invention utilizes the adhesive properties of ovomucoid in egg white as a raw material for preparing a slurry. The slurry containing egg white does not drip during high-temperature calcination and carbonization, ensuring the stability of the loaded material. After carbonization, the slurry containing egg white forms porous carbon with a certain degree of conductivity. The egg white-derived carbon connects the hierarchical porous carbon and carbon fibers to form a conductive network, effectively improving the capacitance of the material.

[0019] This invention separates the synthesis and loading steps of the active material. The active material can be adjusted to an ideal structure and morphology using acids, alkalis and pore-forming agents before being loaded onto the carbon fiber surface, thus avoiding the mechanical property degradation of carbon fibers caused by etching.

[0020] Preferably, in step (1), the ion beam treatment specifically involves sputtering the desized carbon fibers with an ion beam at a bias voltage of 50–200V for 5–600s. When the voltage of the ion beam is 50–200V, active groups can be introduced onto the surface of the desized carbon fibers. Under suitable voltage conditions, when the ion beam sputtering treatment time is 5–600s, an appropriate amount of active groups can be introduced onto the surface of the desized carbon fibers.

[0021] Preferably, in step (2), the particle size of the hierarchical porous carbon is 0.05 to 0.5 μm.

[0022] Preferably, in step (2), the ratio of the amount of hierarchical porous carbon, egg white, and deionized water is 0.2g:0.2-1mL:1-3mL. The content of hierarchical porous carbon and the viscosity of the slurry are controlled by adjusting the ratio of the amount of hierarchical porous carbon, egg white, and deionized water. If the content of hierarchical porous carbon is too high, the carbon in the slurry will agglomerate, affecting the subsequent coating of the slurry and the loading of active substances, thus affecting the performance of the prepared material; if the content of hierarchical porous carbon is too low, the modification effect of the material will not be significant. If the content of added egg white is too high, the viscosity of the slurry will be too high, which is not conducive to preparing a uniform slurry that is easy to coat; if the content of added egg white is too low, the viscosity of the slurry will be too low, and the active substances on the carbon fiber surface will easily fall off. The amount of deionized water can be adjusted within the above range according to the density and particle size of the hierarchical porous carbon, and it works synergistically with the hierarchical porous carbon and egg white in the slurry to control the adhesion and uniformity of the slurry.

[0023] Preferably, the coating thickness of the slurry in step (3) is 1–20 μm. The coating thickness can be precisely controlled using a coater. The coating thickness of the slurry is positively correlated with the electrochemical performance, but if the coating thickness is too thick, the carbon layer will easily peel off in large quantities when bent.

[0024] Preferably, in step (4), the calcination carbonization specifically involves heating the carbon fiber material modified with hierarchical porous carbon to 400–600°C under inert gas protection at a rate of 1–20°C / min, and holding it at that temperature for 1–3 hours. When the calcination carbonization temperature is too high, it will damage the structure of the hierarchical porous carbon material, causing a decrease in the electrochemical performance of the prepared modified carbon fiber; when the calcination carbonization temperature is too low, the egg white cannot be completely carbonized to form a conductive network, affecting the capacitance of the modified carbon fiber.

[0025] The present invention also provides a carbon fiber electrode material with loaded hierarchical porous carbon prepared by the preparation method described above.

[0026] The present invention also provides the application of the aforementioned carbon fiber electrode material with loaded hierarchical porous carbon in the preparation of supercapacitor electrodes.

[0027] The beneficial effects of this invention are at least reflected in:

[0028] 1. A method for loading graded porous carbon onto the surface of carbon fibers;

[0029] 2. This method is simple, easy to operate, and does not involve toxic or harmful reagents;

[0030] 3. Loading graded porous carbon particles onto the surface of carbon fibers can increase the specific surface area and porosity of carbon fibers, thereby improving their electrochemical performance.

[0031] 4. By separating the synthesis and loading steps of the active material, the active material can be adjusted to the ideal structure and morphology using acids, alkalis and pore-forming agents before loading, thus avoiding the degradation of mechanical properties of carbon fibers caused by etching.

[0032] 5. Based on the adhesiveness of egg white, egg white is used as the slurry composition. The slurry will not drip during the high-temperature calcination and carbonization process, which ensures the stability of the load material. After carbonization, it can form porous carbon with certain conductivity, connecting the carbon material and carbon fiber to form a conductive network, which effectively improves the capacitance of the material.

[0033] 6. The coating thickness can be precisely controlled with the help of a coater, which ensures the electrochemical performance of the material while effectively avoiding the problem of excessive carbon layer peeling off when bending due to excessive coating thickness.

[0034] 7. This invention has excellent versatility and can be used for various types of hierarchical porous carbon. With the emergence of carbon materials with higher electrochemical performance, the electrochemical performance of carbon fiber electrodes can be improved in tandem.

[0035] 8. This invention obtains activated carbon fiber (CFO) by ion beam treatment of desized carbon fiber, introducing active groups such as carboxyl and hydroxyl groups, which improves the hydrophilicity of the material and allows the slurry to be coated more uniformly and evenly on the surface of the carbon fiber cloth. Furthermore, the activated carbon fiber prepared by ion beam treatment has stronger hydrophilicity than that prepared by nitric acid oxidation, avoids the etching of carbon fiber during nitric acid oxidation, and significantly reduces the activation time. Attached Figure Description

[0036] Figure 1 Photograph of the carbon fiber electrode material with loaded hierarchical porous carbon prepared in Example 2. Detailed Implementation

[0037] The present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0038] It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Operating methods not specifically described in the following embodiments are generally performed under conventional conditions or as recommended by the manufacturer.

[0039] Example 1

[0040] Desized carbon fibers are sputtered with an ion beam at a bias voltage of 100V for 120s to introduce active groups such as carboxyl and hydroxyl groups on the surface of the carbon fibers, thus obtaining activated carbon fiber CFO.

[0041] Weigh 0.2g of commercial activated carbon YP-80F and grind it in an agate mortar for 0.5-1h (controlling the particle size to 0.05-0.5μm). Add 0.2mL of egg white and about 1mL of deionized water and stir thoroughly until a slurry with uniform texture and certain adhesion is obtained.

[0042] The slurry is evenly coated on the surface of the carbon fiber cloth and placed in a forced-air drying oven to dry at 80°C for about 4 hours.

[0043] The carbon fibers modified with YP-80F were arranged in a tube furnace for calcination and carbonization. Under inert gas protection, the temperature was raised to 500℃ and held for 2 hours at a heating rate of 20℃ / min. After natural cooling to room temperature, carbon fibers loaded with commercial activated carbon YP-80F (YP-80F@CF) were obtained.

[0044] The carbon fibers loaded with commercially available activated carbon YP-80F prepared in this embodiment were used as electrodes for supercapacitors. Their electrochemical performance was tested in a two-electrode electrochemical testing system using an ionic liquid electrolyte. The areal capacitance of the modified carbon fiber electrode obtained in Example 1 is shown in Table 1, i.e., at a current density of 0.5 mA / cm². 2 At that time, the areal capacitance can reach 113 mF / cm². 2 .

[0045] Example 2

[0046] Desized carbon fibers are sputtered with an ion beam at a bias voltage of 100V for 120s to introduce active groups such as carboxyl and hydroxyl groups on the surface of the carbon fibers, thus obtaining activated carbon fiber CFO.

[0047] 0.5 g of HCCP and 1.08 g of 4,4'-dihydroxydiphenyl sulfone (BPS) were weighed and added to a reactor, followed by 100 mL of THF and 5 mL of TEA. The reactor was immediately sealed and sonicated for 1.5 h, then allowed to stand for 1.5 h. The reactor was then extracted with acetonitrile for 12 h and vacuum dried to obtain polyphosphazene nanotubes (PZSNT). The PZSNT was then calcined and carbonized in a tube furnace under inert gas protection. The temperature was raised to 500 °C and held for 5 h, then raised to 800 °C and held for 2 h at a heating rate of 20 °C / min. After natural cooling to room temperature, polyphosphazene carbon nanotubes (CPZSNT) were obtained. CPZSNT was mixed with KOH at a mass ratio of 1:3 and placed in a tube furnace under inert gas protection. The temperature was raised to 600 °C and held for 2 h at a heating rate of 20 °C / min. After natural cooling to room temperature, activated polyphosphazene carbon nanotubes (ACPZSNT) were obtained.

[0048] Weigh 0.2g of ACPZSNT and grind it in an agate mortar for 0.5-1h (controlling the particle size to 0.05-0.5μm). Add 0.2mL of egg white and about 1mL of deionized water and stir thoroughly until a slurry with a uniform texture and a certain degree of adhesion is obtained.

[0049] The slurry is evenly coated on the surface of the carbon fiber cloth and placed in a forced-air drying oven to dry at 80°C for about 4 hours.

[0050] ACPZSNT-modified carbon fibers were arranged in a tube furnace for calcination and carbonization. Under inert gas protection, the temperature was raised to 500℃ and held for 2 hours at a heating rate of 20℃ / min. After natural cooling to room temperature, ACPZSNT-loaded carbon fiber-1 (ACPZSNT@CF-1) was obtained. Figure 1 Photograph of the carbon fiber electrode material with loaded hierarchical porous carbon prepared in Example 2.

[0051] The ACPZSNT-loaded carbon fiber prepared in this embodiment was used as a supercapacitor electrode. Its electrochemical performance was tested in a two-electrode electrochemical testing system with an ionic liquid electrolyte. The areal capacitance of the modified carbon fiber electrode obtained in Example 2 is shown in Table 1, i.e., at a current density of 0.5 mA / cm². 2 At that time, the areal capacitance can reach 400mF / cm². 2 Under the same test conditions, the areal capacitance of desized carbon fiber and activated carbon fiber (CFO) is almost negligible.

[0052] Comparative Example 1

[0053] The difference between Comparative Example 1 and Example 2 is that the preparation and loading processes of activated polyphosphazene carbon nanotubes (ACPZSNT) were not carried out in separate steps.

[0054] Desized carbon fibers are sputtered with an ion beam at a bias voltage of 100V for 120s to introduce active groups such as carboxyl and hydroxyl groups on the surface of the carbon fibers, thus obtaining activated carbon fiber CFO.

[0055] Weigh 0.5 g of HCCP (hexachlorotriphosphazene) and 1.08 g of 4,4'-dihydroxydiphenyl sulfone (BPS), and add a 4 cm × 4 cm piece of activated carbon fiber cloth to a reactor. Then add 100 mL of THF and 5 mL of TEA. Seal immediately and sonicate for 1.5 h. Let stand for 1.5 h, extract with acetonitrile for 12 h, and vacuum dry to obtain carbon fiber cloth (CPZSNT@CF) modified with polyphosphazene nanotubes.

[0056] CPZSNT@CF was placed in a tube furnace for calcination and carbonization. Under inert gas protection, the temperature was raised to 500℃ and held for 5 hours, then raised to 800℃ and held for 2 hours. The heating rate was 20℃ / min. After natural cooling to room temperature, carbon fibers (CPZSNT@CF) loaded with polyphosphazene nanotubes were obtained.

[0057] CPZSNT@CF was soaked in 6 mol KOH overnight, dried, and then placed in a tube furnace. The temperature was raised to 500℃ and held for 2 hours. The temperature was increased at a rate of 20℃ / min. After natural cooling to room temperature, carbon fiber-2 (ACPZSNT@CF-2) loaded with polyphosphazene nanotubes was obtained.

[0058] After removal, it can be observed that a large number of polyphosphazene carbon nanotubes on the surface of the carbon fiber have fallen off, and the carbon fiber itself has also been etched and damaged.

[0059] The ACPZSNT@CF prepared in this embodiment was used as a supercapacitor electrode. Its electrochemical performance was tested in a two-electrode electrochemical testing system with an ionic liquid electrolyte. The areal capacitance of the modified carbon fiber electrode obtained in Comparative Example 1 is shown in Table 1, i.e., at a current density of 0.5 mA / cm². 2 At that time, the areal capacitance was 50 mF / cm². 2 .

[0060] Comparative Example 2

[0061] The only difference between Comparative Example 2 and Example 2 is that the egg white in the slurry composition is replaced with polyvinylidene fluoride (PVDF).

[0062] Desized carbon fibers are sputtered with an ion beam at a bias voltage of 100V for 120s to introduce active groups such as carboxyl and hydroxyl groups on the surface of the carbon fibers, thus obtaining activated carbon fiber CFO.

[0063] Weigh 0.5g HCCP and 1.08g 4,4'-dihydroxydiphenyl sulfone (BPS) and add them to the reactor, then add 100mL THF and 5mL TEA. Seal immediately, sonicate for 1.5h, let stand for 1.5h, extract with acetonitrile for 12h, and vacuum dry to obtain polyphosphazene nanotubes (PZSNT).

[0064] Polyphosphazene nanotubes were placed in a tube furnace for calcination and carbonization. Under inert gas protection, the temperature was raised to 500℃ and held for 5 hours, then raised to 800℃ and held for 2 hours. The heating rate was 20℃ / min. After natural cooling to room temperature, polyphosphazene carbon nanotubes (CPZSNT) were obtained.

[0065] CPZSNT and KOH were mixed at a mass ratio of 1:3 and placed in a tube furnace. Under inert gas protection, the temperature was raised to 600℃ and held for 2 hours at a heating rate of 20℃ / min. After natural cooling to room temperature, activated polyphosphazene carbon nanotubes (ACPZSNT) were obtained.

[0066] Weigh 0.2g of ACPZSNT and grind it in an agate mortar for 0.5–1 hour (controlling the particle size to 0.05–0.5 μm). Add 0.025g of polyvinylidene fluoride (PVDF) and approximately 5mL of N-methylpyrrolidone (NMP) to dissolve the PVDF. Stir thoroughly until a homogeneous slurry with good adhesion is obtained. Coat the slurry evenly onto the surface of carbon fiber cloth and dry it in an oven.

[0067] Carbon fibers coated with ACPZSNT were arranged in a tube furnace for calcination and carbonization. Under inert gas protection, the temperature was raised to 500℃ and held for 2 hours at a heating rate of 20℃ / min. After natural cooling to room temperature, carbon fiber-3 loaded with ACPZSNT (ACPZSNT@CF-3) was obtained.

[0068] The ACPZSNT-modified carbon fibers prepared in this embodiment were used as electrodes for supercapacitors. Their electrochemical performance was tested in a two-electrode electrochemical testing system using an ionic liquid electrolyte. The areal capacitance of the modified carbon fiber electrode obtained in Comparative Example 2 is shown in Table 1, i.e., at a current density of 0.5 mA / cm². 2 At that time, the area capacitance was 15 mF / cm². 2 .

[0069] Comparative Example 3

[0070] The only difference between Comparative Example 3 and Example 2 is that the loading process involves coating egg white first and then coating with ground ACPZSNT toner.

[0071] Desized carbon fibers are sputtered with an ion beam at a bias voltage of 100V for 120s to introduce active groups such as carboxyl and hydroxyl groups on the surface of the carbon fibers, thus obtaining activated carbon fiber CFO.

[0072] Weigh 0.5g HCCP and 1.08g 4,4'-dihydroxydiphenyl sulfone (BPS) and add them to the reactor, then add 100mL THF and 5mL TEA. Seal immediately, sonicate for 1.5h, let stand for 1.5h, extract with acetonitrile for 12h, and vacuum dry to obtain polyphosphazene nanotubes (PZSNT).

[0073] Polyphosphazene nanotubes were placed in a tube furnace for calcination and carbonization. Under inert gas protection, the temperature was raised to 500℃ and held for 5 hours, then raised to 800℃ and held for 2 hours. The heating rate was 20℃ / min. After natural cooling to room temperature, polyphosphazene carbon nanotubes (CPZSNT) were obtained.

[0074] CPZSNT and KOH were mixed at a mass ratio of 1:3 and placed in a tube furnace. Under inert gas protection, the temperature was raised to 600℃ and held for 2 hours at a heating rate of 20℃ / min. After natural cooling to room temperature, activated polyphosphazene carbon nanotubes (ACPZSNT) were obtained.

[0075] Weigh 0.2g of ACPZSNT and grind it in an agate mortar for 0.5-1h (controlling the particle size to 0.05-0.5μm). Coat the surface of the carbon fiber cloth evenly with egg white, then sprinkle the ground carbon powder evenly on the surface of the carbon fiber cloth and place it in a forced-air drying oven at 80℃ for about 4h.

[0076] Carbon fibers coated with ACPZSNT were arranged in a tube furnace for calcination and carbonization. Under inert gas protection, the temperature was raised to 500℃ and held for 2 hours at a heating rate of 20℃ / min. After natural cooling to room temperature, carbon fiber-4 loaded with ACPZSNT (ACPZSNT@CF-4) was obtained.

[0077] The ACPZSNT-modified carbon fibers prepared in this embodiment were used as electrodes for supercapacitors. Their electrochemical performance was tested in a two-electrode electrochemical testing system using an ionic liquid electrolyte. The areal capacitance of the modified carbon fiber electrode obtained in Comparative Example 3 is shown in Table 1, i.e., at a current density of 0.5 mA / cm². 2 At that time, the area capacitance was 37 mF / cm². 2 .

[0078] Table 1. Aspect-to-capacitance ratio of modified carbon fiber electrodes

[0079]

[0080] Furthermore, it should be understood that after reading the above description of the present invention, those skilled in the art can make various alterations or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A method for preparing a carbon fiber electrode material loaded with hierarchical porous carbon, characterized in that, Including steps: (1) After desizing carbon fiber is treated with ion beam, activated carbon fiber CFO is obtained; the ion beam treatment is specifically: the desizing carbon fiber is sputtered with ion beam under a bias voltage of 50~200 V for 5~600 s; (2) Add graded porous carbon and egg white to deionized water, stir evenly to obtain slurry; (3) The slurry obtained in step (2) is uniformly coated on the surface of the activated carbon fiber CFO obtained in step (1), and dried to obtain carbon fiber material modified with graded porous carbon. (4) The carbon fiber material modified with hierarchical porous carbon obtained in step (3) is calcined and carbonized. Once the carbonization is completed, the carbon fiber electrode material loaded with hierarchical porous carbon is obtained. The calcination and carbonization specifically involves heating the carbon fiber material modified with hierarchical porous carbon to 400~600℃ under inert gas protection at a rate of 1~20℃ / min and holding it at that temperature for 1~3h.

2. The method for preparing carbon fiber electrode material with loaded hierarchical porous carbon according to claim 1, characterized in that, In step (2), the particle size of the hierarchical porous carbon is 0.05~0.5μm.

3. The method for preparing carbon fiber electrode material with loaded hierarchical porous carbon according to claim 1, characterized in that, In step (2), the ratio of the amount of graded porous carbon, egg white and deionized water is 0.2 g : 0.2~1 mL : 1~3 mL.

4. The method for preparing carbon fiber electrode material with loaded hierarchical porous carbon according to claim 1, characterized in that, The coating thickness of the slurry in step (3) is 1~20 μm.

5. The carbon fiber electrode material with loaded hierarchical porous carbon prepared by the preparation method according to any one of claims 1 to 4.

6. The application of the carbon fiber electrode material with loaded hierarchical porous carbon as described in claim 5 in the preparation of supercapacitor electrodes.

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