Preparation method of supercapacitor composite electrode material

Abstract

This invention provides a method for preparing a supercapacitor composite electrode material, relating to the field of supercapacitor technology. The method includes the following steps: Step S1, three-dimensional interpenetrating network structure design and material synthesis; Step S11, injecting a pretreated matrix into the interior of a pretreatment device for pre-carbonization treatment, followed by chemical activation treatment to obtain a carbon framework; Step S12, in-situ growth of a metal-organic framework precursor on the carbon framework using a hydrothermal method, placing the carbon framework in a metal salt; Step S13, converting the metal-organic framework into porous transition metal phosphides using a low-temperature vapor-phase phosphating process. This integrated one-step hydrothermal-vapor-phase phosphating-pulse electrodeposition process allows for precise control of material composition and microstructure under low-temperature conditions, resulting in high specific capacitance, ultra-long cycle life, and environmentally friendly characteristics, providing a solution for the development of high-performance supercapacitors.

Description

Technical Field

[0001] This invention relates to the field of supercapacitor technology, and in particular to a method for preparing a supercapacitor composite electrode material. Background Technology

[0002] Supercapacitors, as highly efficient electrochemical energy storage devices, have shown significant application potential in fields such as new energy storage, smart grids, electric vehicles, and portable electronic devices due to their advantages such as high power density, rapid charge and discharge capabilities, and long cycle life. However, their core performance indicator—energy density—remains significantly lower than that of secondary batteries due to limitations in the energy storage mechanism and structural design of electrode materials, becoming a key bottleneck restricting their large-scale commercial application.

[0003] Traditional electrode material systems mainly rely on single or simple composite systems of double-layer capacitive carbon materials and pseudocapacitive metal oxides or conductive polymers, but these systems generally have inherent defects in practical applications. While carbon-based materials possess high specific surface area and excellent conductivity, their pure double-layer energy storage mechanism results in low specific capacity, and performance degradation is easily triggered under high voltage or high frequency conditions due to sluggish ion adsorption / desorption kinetics. Although metal oxides can provide high pseudocapacitance through surface redox reactions, most materials have poor intrinsic conductivity and long ion diffusion paths, leading to insufficient utilization of active sites. Furthermore, the severe volume expansion effect during repeated charge-discharge cycles easily causes material pulverization and structural collapse, significantly reducing cycle stability.

[0004] Some studies have attempted to improve the ion accessibility and structural stability of electrode materials by introducing metal-organic frameworks to derive porous materials or constructing three-dimensional hierarchical structures. However, metal-organic framework derivatives are prone to pore collapse and active component aggregation during high-temperature carbonization or phosphating. Furthermore, the construction of three-dimensional structures often relies on template methods or vapor deposition techniques, which have problems such as poor process repeatability and difficulty in template removal. Further research is needed on how to achieve effective coupling between high active site density and highly conductive substrate.

[0005] Therefore, it is necessary to provide a method for preparing supercapacitor composite electrode materials to solve the above-mentioned technical problems. Summary of the Invention

[0006] This invention provides a method for preparing a supercapacitor composite electrode material, which solves the problem in related technologies that requires further research on how to achieve effective coupling between high active site density and a highly conductive substrate.

[0007] To solve the above-mentioned technical problems, the present invention provides a method for preparing a supercapacitor composite electrode material, comprising the following steps:

[0008] Step S1: Design and material synthesis of three-dimensional interpenetrating network structure;

[0009] Step S11: The pretreated matrix is ​​injected into the interior of the pretreatment device for pre-carbonization treatment, and then chemically activated to obtain a carbon skeleton.

[0010] Step S12: In situ, metal-organic framework precursors are grown on the carbon skeleton by hydrothermal method. The carbon skeleton is placed in a metal salt, and the molar ratio of metal salt to carbon skeleton organic ligand is controlled to be 1:2 to 1:5.

[0011] Step S13: The metal-organic framework is converted into a porous transition metal phosphide through a low-temperature gas-phase phosphating process. The nickel nodes in the MOF are converted into Ni2P nanosheets by temperature control in a mixed gas with a PH3 / Ar volume ratio of 1:3-10.

[0012] Step S2: Controllable coating of conductive polymer interface layer. A porous transition metal phosphide is used as the working electrode and placed in an electrolyte. A pulse electrodeposition method is used in an electrolyte containing aniline monomer. The pulse voltage range is -0.5V to 1.2V and the pulse frequency is 10 to 50Hz to form a continuous polymer coating layer with a thickness of 10 to 50nm.

[0013] Preferably, the pretreated matrix can be any one of biomass-derived carbon, grapefruit peel, coconut shell, and cellulose.

[0014] Preferably, the pre-carbonization temperature in step S11 is controlled at 400~800℃, and the holding time is 1~4 hours.

[0015] Preferably, in step S11, KOH is used as the activator for chemical activation, with a mass ratio of 1:1 to 1:3, to obtain a carbon skeleton with a specific surface area of ​​1200 to 2000 m² / g.

[0016] Preferably, in the hydrothermal stage of step S12, the hydrothermal reaction temperature is 80~150℃ and the reaction time is 4~12 hours.

[0017] Preferably, the concentration of the metal salt is 0.1~0.5 mol / L and the reaction time is [not specified].

[0018] Preferably, the phosphating temperature range of step S13 is 200~400℃, and the holding time is 1~3 hours.

[0019] Preferably, the heating rate is 2~5℃ / min.

[0020] Preferably, the electrodeposition time in step S2 is 10~60 min.

[0021] Preferably, the pretreatment device includes:

[0022] Support frame;

[0023] A rolling conveying assembly includes a feed hood, a discharge hood, a roller, and a feeding device. The feed hood and the discharge hood are respectively fixedly installed on the top of the support frame. The roller is rotatably installed between the feed hood and the discharge hood. The feeding device includes a first driving member, a conveying pipe, and a spiral conveying rod. The first driving member is fixedly installed on the feed hood. The conveying pipe is fixedly installed inside the feed hood. The bottom of the feeding pipe passes through the feed hood and communicates with the conveying pipe. The spiral conveying rod is rotatably installed inside the conveying pipe. One end of the spiral conveying rod passes through the conveying pipe and the feed hood and is fixedly connected to the drive shaft of the first driving member. The other end of the spiral conveying rod is fixedly provided with a connecting slide rod.

[0024] A heat treatment assembly, which is sleeved on the roller and fixed on the support frame;

[0025] A switch assembly, comprising a telescopic member and a switch disk, wherein the fixed part of the telescopic member is fixedly disposed on the discharge hood, the switch disk is slidably mounted between the roller and the discharge hood, and the telescopic end of the telescopic member passes through the discharge hood and is fixedly connected to the switch disk;

[0026] A paving assembly includes a support shaft, a movable bushing, and a rotating scraper. One end of the support shaft is fixed to the discharge hood, and the other end of the support shaft extends into the interior of the roller. One end of the movable bushing is sleeved on the support shaft and rotatably connected to the switch disk. A mating groove is provided on the movable bushing, and one end of the connecting slide rod is inserted into the mating groove. The rotating scraper is fixedly installed on the movable bushing.

[0027] A rotating assembly for driving the roller to rotate and adjust;

[0028] When the switch disk is inserted into the drum, the connecting slide rod is inserted into the docking groove; when the switch disk is removed from the drum, the connecting slide rod separates from the docking groove.

[0029] Compared with related technologies, the preparation method of supercapacitor composite electrode material provided by the present invention has the following beneficial effects:

[0030] By in-situ loading MOF-derived transition metal phosphide nanosheets onto a nitrogen-doped porous carbon framework and coupling them with a conductive polymer interface coating, a synergistic enhancement of ion / electron transport pathways and structural stability is achieved. Simultaneously, an integrated process of one-step hydrothermal-vapor phase phosphating-pulse electrodeposition is employed to precisely control the material composition and microstructure under low-temperature conditions, resulting in a product that combines high specific capacitance, ultra-long cycle life, and environmental friendliness, providing a solution for the development of high-performance supercapacitors. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0032] Figure 1 A three-dimensional diagram of a first embodiment of a preprocessing apparatus provided by the present invention;

[0033] Figure 2 for Figure 1 A schematic diagram of the cross-sectional structure of section AA shown;

[0034] Figure 3 for Figure 2 A magnified view of part B shown;

[0035] Figure 4 for Figure 2 The schematic diagram of the rotating scraper section shown is as follows: Figure 4 (a) in the middle is Figure 2 Left view of the entire rotating scraper. Figure 4 (b) in the middle is Figure 4 (a) A magnified view of a portion of the image;

[0036] Figure 5 for Figure 2 A three-dimensional structural schematic diagram of the distribution of the braking components shown;

[0037] Figure 6 This is a schematic diagram of a first embodiment of a pretreatment apparatus provided by the present invention, wherein, Figure 6 (a) is a schematic diagram of the switch panel in the off state. Figure 6 (b) is a schematic diagram of the switch panel in the open state;

[0038] Figure 7 for Figure 6 The enlarged view shown below, in which, Figure 7 (a) in the middle is Figure 6 The location diagram of the locked disk in state (a) is shown. Figure 7 (b) in the middle is Figure 6 The location diagram of the locked disk in state (b) is shown. Figure 7 (c) in the middle is Figure 6 The position diagram of the telescopic plate in state (a) is shown. Figure 7 (d) in the middle is Figure 6 The position diagram of the telescopic plate in state (b) is shown.

[0039] Figure 8 A three-dimensional diagram of a second embodiment of a preprocessing apparatus provided by the present invention.

[0040] Explanation of icon numbers:

[0041] 1. Support frame;

[0042] 2. Rolling conveyor assembly; 21. Feed hood; 22. Discharge hood; 23. Roller; 24. Feeding device; 241. First drive component; 242. Conveying pipe; 2421. Feeding pipe; 243. Screw conveyor; 2431. Connecting slide bar;

[0043] 3. Heat treatment components; 31. Combustion chamber; 311. Smoke exhaust port; 32. Feeding hopper; 33. Ignition device;

[0044] 4. Switch assembly; 41. Telescopic component; 42. Switch panel;

[0045] 5. Paving components; 51. Support shaft; 511. Rotating shaft; 512. Transmission component; 52. Movable bushing; 521. Connecting groove; 522. Movable hole; 53. Rotating scraper; 531. Rotating frame; 532. Telescopic plate;

[0046] 6. Braking assembly; 61. Locking disc; 62. Locking block;

[0047] 7. Rotating component; 71. Second drive component; 72. Gear ring; 73. Gear; 711. Synchronous shaft.

[0048] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0049] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0050] This invention provides a method for preparing a supercapacitor composite electrode material.

[0051] Please see Figure 1 The present invention discloses a method for preparing a supercapacitor composite electrode material, comprising the following steps:

[0052] Step S1: Design and material synthesis of three-dimensional interpenetrating network structure;

[0053] Step S11: The pretreated matrix is ​​injected into the interior of the pretreatment device for pre-carbonization treatment, and then chemically activated to obtain a carbon skeleton.

[0054] Step S12: In situ, metal-organic framework precursors are grown on the carbon skeleton by hydrothermal method. The carbon skeleton is placed in a metal salt, and the molar ratio of metal salt to carbon skeleton organic ligand is controlled to be 1:2 to 1:5.

[0055] Step S13: The metal-organic framework is converted into a porous transition metal phosphide through a low-temperature gas-phase phosphating process. The nickel nodes in the MOF are converted into Ni2P nanosheets by temperature control in a mixed gas with a PH3 / Ar volume ratio of 1:3-10.

[0056] Step S2: Controllable coating of conductive polymer interface layer. A porous transition metal phosphide is used as the working electrode and placed in an electrolyte. A pulse electrodeposition method is used in an electrolyte containing aniline monomer. The pulse voltage range is -0.5V to 1.2V and the pulse frequency is 10 to 50Hz to form a continuous polymer coating layer with a thickness of 10 to 50nm.

[0057] By in-situ loading MOF-derived transition metal phosphide nanosheets onto a nitrogen-doped porous carbon framework and coupling them with a conductive polymer interface coating, a synergistic enhancement of ion / electron transport pathways and structural stability is achieved. Simultaneously, an integrated process of one-step hydrothermal-vapor phase phosphating-pulse electrodeposition is employed to precisely control the material composition and microstructure under low-temperature conditions, resulting in a product that combines high specific capacitance, ultra-long cycle life, and environmental friendliness, providing a solution for the development of high-performance supercapacitors.

[0058] Specifically, the pretreatment matrix can be any one of biomass-derived carbon, grapefruit peel, coconut shell, and cellulose.

[0059] Specifically, the pre-carbonization temperature in step S11 is controlled at 400~800℃, and the holding time is 1~4 hours.

[0060] In an optional embodiment of this example, in step S11, KOH is used as the activator for chemical activation at a mass ratio of 1:1 to 1:3, resulting in a carbon skeleton with a specific surface area of ​​1200 to 2000 m² / g.

[0061] In another optional embodiment of this example, in step S11, H3PO4 is used as the activator for chemical activation at a mass ratio of 1:1 to 1:3, resulting in a carbon skeleton with a specific surface area of ​​1200 to 2000 m². 2 / g.

[0062] The effect of the treatment is that the nitrogen doping amount is 1.5~5 at%, and the pore size distribution is a coexistence of micropores and mesopores.

[0063] Specifically, in step S12, the hydrothermal stage involves a reaction temperature of 80-150°C and a reaction time of 4-12 hours. Metal salts such as Co... 2+ Ni 2+ .

[0064] Specifically, the concentration of the metal salt is 0.1~0.5 mol / L and the reaction time is [not specified].

[0065] Specifically, the phosphating temperature range of step S13 is 200~400℃, and the holding time is 1~3 hours.

[0066] Specifically, the heating rate is 2~5℃ / min.

[0067] The final product is a metal phosphide such as CoP, Ni2P, or CoNiP with a thickness of 5-20 nm. X Its quality accounts for 30-60%.

[0068] Specifically, the electrodeposition time is 10~60 min.

[0069] The material is prepared efficiently using a three-step integrated process: hydrothermal synthesis, low-temperature phosphating, and pulse electrodeposition.

[0070] During the hydrothermal stage, the uniform distribution of MOF nanocrystals on the carbon framework is ensured by precisely controlling the metal salt concentration (0.1~0.5 mol / L) and reaction time.

[0071] The phosphating stage is carried out in an inert atmosphere at a low heating rate of 2~5℃ / min to avoid pore collapse caused by high temperature. The resulting phosphide has a specific surface area of ​​800~1500m² / g and a grain size of 5~30nm.

[0072] During the electrodeposition stage, the thickness and conductivity of the conductive polymer layer are precisely controlled by optimizing the pulse parameter duty cycle to 30-70%.

[0073] The final composite electrode achieved a specific capacitance of 600~900F / g at a current density of 1 A / g, a capacity retention of over 80% at a high rate of 20 A / g, and a capacity retention of over 90% after 10,000 cycles, with an energy density of 35~50Wh / kg, representing a significant breakthrough compared to traditional electrode materials.

[0074] Beneficial effects:

[0075] This process achieves ordered growth of polymer molecular chains by dynamically adjusting the redox potential during deposition, ensuring a uniform and dense coating layer that forms chemical bonds with the phosphide interface, thereby reducing the interfacial charge transfer resistance to 0.5~2 Ω·cm. 2At the same time, it effectively buffers volume changes during charging and discharging, and controls the volume expansion rate to below 5%.

[0076] Case 1.

[0077] Preparation and performance of NPC@CoP / PEDOT composite electrode.

[0078] In this case, grapefruit peel was used as a biomass precursor. After pre-carbonization at 600℃ for 2 hours, nitrogen-doped porous carbon was prepared using KOH activator at a mass ratio of 1:2. The specific surface area reached 1600 m² / g, the nitrogen doping amount was 3 at%, and the pore size distribution was mainly micropores with some mesoporous channels.

[0079] Subsequently, ZIF-67 type MOF precursors were grown in situ on the carbon framework by hydrothermal method: Co(NO3)2 and 2-methylimidazole were dissolved in an aqueous solution at a molar ratio of 1:3 and hydrothermally reacted at 120℃ for 8 hours to form uniformly distributed MOF nanocrystals.

[0080] In the low-temperature phosphating stage, the material is placed in a tube furnace and a PH3 / Ar mixed gas with a volume ratio of 1:5 is introduced. The temperature is raised to 350℃ at a rate of 5℃ / min and held for 2 hours. The cobalt nodes in the MOF are transformed into porous CoP nanosheets, which account for 45% of the mass and have a grain size of 10~15nm.

[0081] Finally, using pulsed electrochemical deposition technology, a PEDOT:PSS conductive polymer layer with a thickness of 25 nm and a mass percentage of 10% was coated on the CoP surface in an electrolyte containing EDOT monomers with a pulse voltage range of -0.2V to 1.0V, a frequency of 30Hz, and a deposition time of 30 minutes, forming a stable three-dimensional interpenetrating network structure.

[0082] Table 1: Performance test results of Case 1;

[0083] Test Project Test conditions result Specific capacitance 1A / g 820F / g Ratio performance 20A / g 85% capacity retention Cyclic stability After 10,000 cycles 94% capacity retention Energy density Power density 1kW / kg 43Wh / kg Volume expansion rate charging and discharging process <4%

[0084] .

[0085] The high pseudocapacitive activity of CoP and the fast charge transport of PEDOT work synergistically to make it suitable for fast charging and discharging scenarios in electric vehicles.

[0086] Case 2.

[0087] Preparation and performance of NPC@Ni2P / polyaniline composite electrode.

[0088] This case study uses coconut shell-derived carbon as raw material. After pre-carbonization at 500℃ for 3 hours, nitrogen-doped porous carbon is prepared using H3PO4 as an activator at a mass ratio of 1:1.5, with a specific surface area of ​​1400 m². 2 / g, nitrogen content is 2.5at%, and mesoporous content is significant.

[0089] MIL-53 (Ni) type MOF precursor was loaded onto a carbon framework by hydrothermal method: NiCl2 and terephthalic acid were mixed at a molar ratio of 1:4 and hydrothermally reacted at 100°C for 10 hours to form a uniform MOF layer.

[0090] During the low-temperature phosphating process, in a PH3 / Ar mixed gas with a volume ratio of 1:8, the nickel nodes in the MOF are converted into Ni2P nanosheets at 350℃ for 2 hours, accounting for 50% by mass, with a grain size of 8~12nm.

[0091] In the conductive polymer coating stage, a pulsed electrodeposition method is used to form a 30nm thick polyaniline layer with a mass ratio of 12% in an electrolyte containing aniline monomers, at a voltage range of 0~0.8V, a frequency of 20Hz and a deposition time of 40 minutes, effectively suppressing volume expansion.

[0092] Table 2: Performance test results for Case 2;

[0093] Test Project Test conditions result Specific capacitance 1 A / g 750 F / g Ratio performance 20 A / g 88% capacity retention Cyclic stability After 10,000 cycles 96% capacity retention Energy density Power density 0.8 kW / kg 38 Wh / kg Volume expansion rate charging and discharging process <3%

[0094] .

[0095] The high structural stability of Ni2P combined with the flexible buffering effect of polyaniline makes it suitable for long-cycle demand such as grid energy storage.

[0096] Case 3.

[0097] Preparation and performance of NPC@FeP / polypyrrole composite electrode.

[0098] In this case, cellulose was used as a biomass precursor. After pre-carbonization at 700℃ for 1.5 hours, nitrogen-doped porous carbon was prepared using KOH activator at a mass ratio of 1:2.5. The specific surface area was as high as 1800 m² / g, the nitrogen content was 4 at%, and the mesoporous structure was well developed.

[0099] MIL-100 (Fe) type MOF precursor was loaded onto a carbon framework by hydrothermal method: FeCl3 and pyromellitic acid were mixed at a molar ratio of 1:2 and hydrothermally reacted at 150°C for 6 hours to form a stable MOF structure.

[0100] In the low-temperature phosphating stage, the iron nodes in the MOF are converted into FeP nanoparticles at 350℃ for 3 hours in a PH3 / Ar mixed gas with a volume ratio of 1:10. The FeP nanoparticles account for 35% of the total mass and have a grain size of 15~20nm.

[0101] The conductive polymer coating is achieved using pulsed electrodeposition technology. In an electrolyte containing pyrrole monomers, a 15nm thick polypyrrole layer is formed with a voltage range of -0.5V to 0.5V, a frequency of 40 Hz, and a deposition time of 20 minutes, accounting for 8% of the mass, which significantly improves the interfacial conductivity.

[0102] Table 3: Performance test results for Case 3.

[0103] Test Project Test conditions result Specific capacitance 1 A / g 680 F / g Ratio performance 20 A / g 82% capacity retention Cyclic stability After 10,000 cycles 92% capacity retention Energy density Power density 1.2 kW / kg 32 Wh / kg Volume expansion rate charging and discharging process <5%

[0104] .

[0105] FeP's low cost and polypyrrole's rapid redox properties make it suitable for low-cost, high-throughput scenarios such as industrial energy storage systems.

[0106] By in-situ loading of transition metal phosphide nanosheets onto a nitrogen-doped porous carbon framework and coupling them with a conductive polymer interface coating, a synergistic energy storage mechanism combining double-layer capacitance and pseudocapacitance was achieved.

[0107] In terms of material design, the three-dimensional structure balances high conductivity, rapid ion transport, and structural stability; in terms of process, low-temperature vapor phase phosphating and pulse electrodeposition technologies significantly reduce energy consumption and require no toxic solvents, making them green and efficient.

[0108] In this embodiment, the CoP / PEDOT system is adapted to high-power fast charging scenarios, the Ni2P / polyaniline combination is optimized for long-cycle energy storage, and the FeP / polypyrrole system is aimed at low-cost industrial applications. All three have broken through the limitations of traditional materials in terms of energy density, cycle life and economy, through flexible control of composition and process.

[0109] This invention allows for the customization of electrode material properties for different application scenarios, combining the advantages of high specific capacitance, long lifespan, and low cost, demonstrating its customizability advantage and providing new solutions for electric vehicles, smart grids, and industrial energy storage.

[0110] The present invention also provides a pretreatment device for pre-carbonization treatment of the substrate during the preparation method of the supercapacitor composite electrode material.

[0111] First embodiment:

[0112] Please refer to the following: Figures 1 to 4 In this invention, a pretreatment apparatus includes:

[0113] Support frame 1;

[0114] A rolling conveying assembly 2 includes a feed hood 21, a discharge hood 22, a roller 23, and a feeding device 24. The feed hood 21 and the discharge hood 22 are respectively fixedly installed on the top of the support frame 1. The roller 23 is rotatably installed between the feed hood 21 and the discharge hood 22. The feeding device 24 includes a first driving member 241, a conveying pipe 242, and a spiral conveying rod 243. The first driving member 241 is fixedly installed on the feed hood 21. The conveying pipe 242 is fixedly installed inside the feed hood 21. The bottom of the feeding pipe 2421 passes through the feed hood 21 and communicates with the conveying pipe 242. The spiral conveying rod 243 is rotatably installed inside the conveying pipe 242. One end of the spiral conveying rod 243 passes through the conveying pipe 242 and the feed hood 21 and is fixedly connected to the drive shaft of the first driving member 241. The other end of the spiral conveying rod 243 is fixedly provided with a connecting slide rod 2431.

[0115] Heat treatment assembly 3, which is sleeved on the roller 23 and fixed on the support frame 1;

[0116] The switch assembly 4 includes a telescopic member 41 and a switch disk 42. The fixed part of the telescopic member 41 is fixed on the discharge cover 22. The switch disk 42 is slidably installed between the roller 23 and the discharge cover 22. The telescopic end of the telescopic member 41 passes through the discharge cover 22 and is fixedly connected to the switch disk 42.

[0117] The paving assembly 5 includes a support shaft 51, a movable bushing 52, and a rotating scraper 53. One end of the support shaft 51 is fixed to the discharge hood 22, and the other end of the support shaft 51 extends into the interior of the roller 23. One end of the movable bushing 52 is sleeved on the support shaft 51 and rotatably connected to the switch disk 42. A docking groove 521 is provided on the movable bushing 52, and one end of the connecting slide rod 2431 is inserted into the docking groove 521. The rotating scraper 53 is fixedly installed on the movable bushing 52.

[0118] Rotating component 7, which is used to drive the roller 23 to rotate and adjust;

[0119] When the switch disk 42 is inserted into the roller 23, the connecting slide rod 2431 is inserted into the docking groove 521; when the switch disk 42 is disengaged from the roller 23, the connecting slide rod 2431 is separated from the docking groove 521.

[0120] In an optional embodiment of this example, the cross-section of the connecting slide rod 2431 is rectangular, and the docking groove 521 is a rectangular groove.

[0121] In this embodiment, the roller 23 connects the feed hood 21 and the discharge hood 22, and the output end of the roller 23 is inclined toward the discharge hood 22. This allows the roller 23 to slowly transport the internal material toward the discharge hood 22 during continuous rotation.

[0122] In this embodiment, the feed hood 21 is provided with an exhaust pipe for conveying the exhaust gas generated during the heat treatment process inside the drum 23 to the subsequent flue gas treatment process.

[0123] In this embodiment, the heat treatment component 3 is used to provide heating conditions for the roller 23.

[0124] Material conveying principle:

[0125] The material requiring heat treatment enters the conveying range of the screw conveyor 243 through the feeding pipe 2421. The screw conveyor 243 feeds the material into the drum 23. When the drum 23 rotates, it drives the internal material to rotate and be transported from the direction of the feed hood 21 towards the direction of the discharge hood 22. Since the switch 42 is in the closed state during heat treatment, the material is kept within the range of the drum 23 to facilitate continuous heat treatment. When it is necessary to discharge the material, the switch 42 is opened, and the material is transported from the direction of the discharge hood 22.

[0126] In this embodiment, the switch panel 42 includes two operating states:

[0127] In the off state, such as Figure 6 As shown in (a), the switch disk 42 is inserted into the range of the roller 23 to block the discharge hood 22; the movable bushing 52 is inserted into the connecting slide rod 2431 through the docking groove 521 to facilitate the continuous heat treatment of the material in the roller 23, and at the same time facilitates the rotation adjustment of the rotating scraper 53 by the spiral conveying rod 243.

[0128] Open state, such as Figure 6 As shown in (b), the switch plate 42 is disengaged from the range of the roller 23, the discharge hood 22 is opened, and the movable bushing 52 is separated from the connecting slide rod 2431, which facilitates the discharge of materials after heat treatment.

[0129] In this embodiment, the connection between the switch disk 42 and the roller 23 is slidably sealed, so that materials will not pass through the switch disk 42 when it is closed.

[0130] Working principle:

[0131] When continuous feeding and heat treatment of the material inside the drum 23 are required, the drum 23 is first preheated by the heat treatment component 3. After the temperature is raised to the required temperature, the material is controlled to enter the interior of the drum 23 by the feeding pipe 2421 and the screw conveyor 243. The drum 23 is controlled to rotate by the rotating component 7, so that the material is rotated and conveyed inside the drum 23, but will not pass through the switch plate 42 and enter the discharge hood 22.

[0132] At the same time, the spiral conveyor 243 also drives the rotating scraper 53 to rotate as a whole, so that the rotating scraper 53 and the drum 23 rotate in opposite directions, forming a uniform spreading and scraping of the material in the drum 23, avoiding material accumulation, and making the material heat treatment more uniform.

[0133] When material needs to be discharged, to maintain the continuous operation of the equipment, the telescopic component 41 is activated. The telescopic component 41 drives the switch plate 42 to move. The switch plate 42 retracts to the range of the discharge hood 22 and moves away from the inside of the roller 23. As the roller 23 rotates, the material inside the roller 23 is transported toward the discharge hood 22 and then discharged from below the discharge hood 22 to the next process.

[0134] Please refer to the following: Figure 2 and Figure 4 Specifically, the heat treatment assembly 3 includes a combustion chamber 31, a feeding chamber 32, and an ignition device 33. The combustion chamber 31 is sleeved on the roller 23 and fixedly connected to the support frame 1. The feeding chamber 32 is fixedly installed at the bottom of the combustion chamber 31. The ignition device 33 is installed on the combustion chamber 31 and is aligned with the output end of the feeding chamber 32. The top of the combustion chamber 31 is provided with a smoke exhaust port 311.

[0135] In this embodiment, the bottom of the combustion chamber 31 is also provided with an air inlet for the input of air and oxygen to ensure a stable combustion environment.

[0136] The exhaust port 311 is used to discharge smoke and flames.

[0137] In this embodiment, the feeding bin 32 can be injected into the combustion bin 31 with combustible fuel (combustible gas, such as natural gas), and then ignited by the ignition device 33 to create a combustion environment, which heats the drum 23 within the range of the combustion bin 31.

[0138] Please refer to the following: Figures 3 to 5 The movable bushing 52 is also provided with a movable hole 522, and a rotating shaft 511 is rotatably installed at the other end of the support shaft 51. The rotating shaft 511 is hinged to one end of the transmission component 512.

[0139] The rotating scraper 53 includes a rotating frame 531 and a telescopic plate 532. The rotating frame 531 is fixedly installed on the movable bushing 52, and the telescopic plate 532 is slidably installed on the rotating frame 531. The other end of the transmission member 512 passes through the movable hole 522 and is hinged to the telescopic plate 532.

[0140] The pretreatment device also includes a braking assembly 6, which includes a locking disc 61 and a locking block 62. The locking disc 61 is fixed to one end of the movable bushing 52 and is rotatably connected to the switch disc 42. The locking block 62 is fixed inside the discharge hood 22 and is aligned with the movement range of the locking disc 61.

[0141] When the switch panel 42 is in the closed state, the connecting slide rod 2431 is inserted into the docking groove 521, and the transmission component 512 controls the telescopic plate 532 to retract, in order to maintain the stability of the rotating frame 531 driving the telescopic plate 532 to rotate and spread.

[0142] During the process of switching the switch panel 42 from the closed state to the open state, it can not only simultaneously drive the movable bushing 52 to separate from the connecting slide rod 2431, but also push the telescopic plate 532 to extend relative to the rotating frame 531 through the transmission component 512 while the movable bushing 52 moves, so that the telescopic plate 532 is close to the surface of the telescopic plate 531.

[0143] Simultaneously, the locking disc 61 on the movable bushing 52 moves toward the locking block 62. When the switch disc 42 is opened, the locking disc 61 locks onto the surface of the locking block 62 to lock the movable bushing 52. This allows the surface of the telescopic plate 532 to stably adhere to the inner surface of the roller 23 when the roller 23 rotates, facilitating the scraping and maintenance of the inner surface of the roller 23, reducing material adhesion, and ensuring the stability of material conveying and discharging.

[0144] Please refer to it again. Figure 1 The rotating assembly 7 includes a second driving member 71, a gear ring 72, and a gear 73. The second driving member 71 is fixed on the support frame 1, the gear ring 72 is fixed on the roller 23, and the gear 73 is fixed on the driving end of the second driving member 71. The gear 73 meshes with the gear ring 72.

[0145] In an optional embodiment of this example, the second driving component 71 can be a motor structure used to directly drive the roller 23 to rotate.

[0146] The rotation principle of the roller 23:

[0147] The second drive unit 71 is activated, which drives the gear 73 to rotate clockwise. The gear 73 drives the gear ring 72 to rotate counterclockwise, and the gear ring 72 drives the roller 23 to rotate counterclockwise, so as to facilitate the rolling and conveying of the material entering the roller 23. During the conveying process, the material is pre-carbonized by the heat treatment component 3.

[0148] The working principle of the pretreatment device provided in this embodiment is as follows:

[0149] Let's define it as follows: In the initial state, the switch panel 42 is in the closed state, the movable bushing 52 is inserted into the connecting slide rod 2431, and the telescopic plate 532 is retracted onto the rotating frame 531, which facilitates the rotation and spreading of the material in the roller 23 and avoids material accumulation.

[0150] A1, after the material inside the drum 23 has been heat-treated, the drum 23 is kept rotating continuously, and the telescopic component 41 is activated. The telescopic component 41 controls the switch plate 42 to switch from the closed state to the open state, so as to facilitate the opening of the discharge hood 22 and facilitate the internal material to be transported towards the discharge hood 22 when the drum 23 rotates.

[0151] A2, during the state switching of the switch panel 42, the movable bushing 52 moves to the right, which on the one hand controls the movable bushing 52 to separate from the connecting slide rod 2431, and on the other hand controls the locking disc 61 to engage with the locking block 62, so that the movable bushing 52, the rotating frame 531 and the telescopic plate 532 are locked as a whole and cannot be rotated or adjusted.

[0152] On the one hand, during the rightward movement of the movable bushing 52, the transmission component 512 adaptively pushes the telescopic plate 532 to extend relative to the rotating frame 531. After the telescopic plate 532 extends, it adheres to the inner surface of the roller 23, so as to achieve cleaning and maintenance of the inner surface of the roller 23 while the roller 23 is conveying and discharging materials, reduce the adhesion of materials, and extend the service life of the equipment.

[0153] A3, after the material in the drum 23 is discharged, the telescopic component 41 is activated. The telescopic component 41 drives the switch disk 42 to return from the open state to the closed state. At the same time, the locking disk 61 separates from the locking block 62, one end of the movable bushing 52 contacts the locking limit, and the other end of the movable bushing 52 is sleeved on the connecting slide rod 2431 through the docking groove 521. At the same time, the transmission component 512 adaptively controls the telescopic plate 532 to retract onto the rotating frame 531.

[0154] When the spiral conveyor 243 rotates, it can synchronously drive the rotating scraper 53 to rotate as a whole through the movable bushing 52. The rotation direction of the rotating scraper 53 is opposite to the rotation direction of the drum 23, which facilitates the spreading and transmission of materials entering the drum 23 and avoids material accumulation.

[0155] A4, material is injected into the conveying range of the screw conveyor 243 through the feeding pipe 2421, the first driving component 241 is activated, the first driving component 241 drives the screw conveyor 243 to rotate, so that the material in the conveying pipe 242 enters the interior of the drum 23.

[0156] By providing an adjustable switch 42 in the output direction of the discharge hood 22, the material can be continuously heat-treated in the drum 23, and the rotating scraper 53 can be rotated as a whole during the feeding process of the spiral conveyor 243, so as to achieve the spreading and separation of the material and avoid material accumulation.

[0157] During the process of switching the switch panel 42 from the closed state to the open state, the movable bushing 52 is simultaneously separated from the connecting slide rod 2431, and the movable bushing 52 is locked and the telescopic plate 532 is extended to facilitate the cleaning and maintenance of the inner surface of the roller 23.

[0158] Second embodiment:

[0159] Please see Figure 8 Based on the preprocessing apparatus provided in the first embodiment of the present invention, the second embodiment of the present invention proposes another preprocessing apparatus. The second embodiment is merely a preferred embodiment of the first embodiment, and the implementation of the second embodiment will not affect the separate implementation of the first embodiment.

[0160] Specifically, the difference in the pretreatment device provided in the second embodiment of the present invention is that the second driving member 71 is a transmission structure, one end of the second driving member 71 is connected to the gear 73 through a synchronous shaft 711, the synchronous shaft 711 is rotatably mounted on the feed hood 21, and the other end of the second driving member 71 is connected to the driving end of the first driving member 241.

[0161] The second driving component 71 is a transmission sprocket assembly, which is connected to the synchronous shaft 711 and the driving end of the first driving component 241.

[0162] The transmission sprocket assembly includes two sprockets and a chain. One sprocket is fixed to the driving end of the first driving member 241, and the other sprocket is fixed to the synchronous shaft 711. The chain drives the two sprockets, so that while the first driving member 241 controls the rotation of the spiral conveyor rod 243, it also drives the synchronous shaft 711 to rotate.

[0163] In this embodiment, the synchronous shaft 711 is stably rotated on the feed shroud 21, while maintaining a stable meshing connection between the gear 73 and the gear ring 72.

[0164] During the process of the first driving member 241 driving the spiral conveyor rod 243 to rotate counterclockwise for feeding, the first driving member 241 not only drives the movable bushing 52 and the rotating scraper 53 to rotate counterclockwise as a whole through the connecting slide rod 2431; it also drives the synchronous shaft 711 to rotate through the second driving member 71. The synchronous shaft 711 drives the gear 73 to rotate counterclockwise, and the gear 73 drives the roller 23 to rotate clockwise through the gear ring 72. The roller 23 and the rotating scraper 53 form a counterclockwise rotation trend, so as to evenly spread and convey the material entering the roller 23 and avoid the accumulation of material.

[0165] Ultimately, under the driving action of the first driving component 241, the spiral feeding of the spiral conveyor rod 243 is realized, the overall rotation and spreading of the rotating scraper 53 is realized, and the reverse rolling heat treatment of the roller 23 is also realized.

[0166] The working principle of a pretreatment device provided in this embodiment is as follows:

[0167] When the switch panel 42 is in the closed state, the first drive unit 241 is activated. The first drive unit 241 drives the spiral conveying rod 243 to rotate within the range of the conveying pipe 242, and rotates and conveys the material entering the conveying pipe 242, so that the material can enter the interior of the drum 23 from the conveying pipe 242.

[0168] On the other hand, the first driving member 241 also drives the synchronous shaft 711 to rotate synchronously through the second driving member 71, and the synchronous shaft 711 drives the gear ring 72 and the roller 23 to rotate in opposite directions through the gear 73;

[0169] During the reverse rotation of the drum 23, the spiral conveying rod 243 also drives the connecting slide rod 2431 and the rotating scraper 53 to rotate, so that the rotating scraper 53 as a whole and the drum 23 form a reverse rotation motion.

[0170] Ultimately, under the control of the same first driving component 241, the material is simultaneously fed in, the roller 23 rotates in the opposite direction and the rotating scraper 53 spreads the material.

[0171] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made under the concept of the present invention using the contents of the present invention specification and drawings, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A method for preparing a supercapacitor composite electrode material, characterized in that, Includes the following steps: Step S1: Design and material synthesis of three-dimensional interpenetrating network structure; Step S11: The pretreated matrix is ​​injected into the interior of the pretreatment device for pre-carbonization treatment, and then chemically activated to obtain a carbon skeleton. Step S12: In situ, metal-organic framework precursors are grown on the carbon skeleton by hydrothermal method. The carbon skeleton is placed in a metal salt, and the molar ratio of metal salt to carbon skeleton organic ligand is controlled to be 1:2 to 1:

5. Step S13: The metal-organic framework is converted into a porous transition metal phosphide through a low-temperature gas-phase phosphating process. The nickel nodes in the MOF are converted into Ni2P nanosheets by temperature control in a mixed gas with a PH3 / Ar volume ratio of 1:3-10. Step S2: Controllable coating of conductive polymer interface layer. A porous transition metal phosphide is used as the working electrode and placed in an electrolyte. A pulse electrodeposition method is used in an electrolyte containing aniline monomer. The pulse voltage range is -0.5V to 1.2V and the pulse frequency is 10 to 50Hz to form a continuous polymer coating layer with a thickness of 10 to 50nm.

2. The method according to claim 1, wherein the method comprises the steps of: mixing the activated carbon, the conductive agent, the binder and the electrolyte to form a mixture; and coating the mixture on a substrate to form the supercapacitor composite electrode material. The pretreatment matrix can be any one of biomass-derived carbon, grapefruit peel, coconut shell, and cellulose.

3. The method for preparing a supercapacitor composite electrode material according to claim 2, characterized in that, The pre-carbonization temperature in step S11 is controlled at 400~800℃, and the holding time is 1~4 hours.

4. The method for preparing a supercapacitor composite electrode material according to claim 3, characterized in that, In step S11, chemical activation uses KOH as the activator at a mass ratio of 1:1 to 1:3, resulting in a carbon skeleton with a specific surface area of ​​1200 to 2000 m² / g.

5. The method for preparing a supercapacitor composite electrode material according to claim 1, characterized in that, In the hydrothermal stage of step S12, the hydrothermal reaction temperature is 80~150℃ and the reaction time is 4~12 hours.

6. The method for preparing a supercapacitor composite electrode material according to claim 5, characterized in that, The concentration of the metal salt is 0.1~0.5 mol / L and the reaction time is [not specified].

7. The method for preparing a supercapacitor composite electrode material according to claim 1, characterized in that, The phosphating temperature range of step S13 is 200~400℃, and the holding time is 1~3 hours.

8. The method for preparing a supercapacitor composite electrode material according to claim 7, characterized in that, The heating rate is 2~5℃ / min.

9. The method for preparing a supercapacitor composite electrode material according to claim 1, characterized in that, The electrodeposition time in step S2 is 10~60 min.

10. The method for preparing a supercapacitor composite electrode material according to claim 1, characterized in that, The pretreatment device includes: Support frame; A rolling conveying assembly includes a feed hood, a discharge hood, a roller, and a feeding device. The feed hood and the discharge hood are respectively fixedly installed on the top of the support frame. The roller is rotatably installed between the feed hood and the discharge hood. The feeding device includes a first driving member, a conveying pipe, and a spiral conveying rod. The first driving member is fixedly installed on the feed hood. The conveying pipe is fixedly installed inside the feed hood. The bottom of the feeding pipe passes through the feed hood and communicates with the conveying pipe. The spiral conveying rod is rotatably installed inside the conveying pipe. One end of the spiral conveying rod passes through the conveying pipe and the feed hood and is fixedly connected to the drive shaft of the first driving member. The other end of the spiral conveying rod is fixedly provided with a connecting slide rod. A heat treatment assembly, which is sleeved on the roller and fixed on the support frame; A switch assembly, comprising a telescopic member and a switch disk, wherein the fixed part of the telescopic member is fixedly disposed on the discharge hood, the switch disk is slidably mounted between the roller and the discharge hood, and the telescopic end of the telescopic member passes through the discharge hood and is fixedly connected to the switch disk; A paving assembly includes a support shaft, a movable bushing, and a rotating scraper. One end of the support shaft is fixed to the discharge hood, and the other end of the support shaft extends into the interior of the roller. One end of the movable bushing is sleeved on the support shaft and rotatably connected to the switch disk. A mating groove is provided on the movable bushing, and one end of the connecting slide rod is inserted into the mating groove. The rotating scraper is fixedly installed on the movable bushing. A rotating assembly for driving the roller to rotate and adjust; When the switch disk is inserted into the drum, the connecting slide rod is inserted into the docking groove; when the switch disk is removed from the drum, the connecting slide rod separates from the docking groove.

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