CN111739740A - Porous carbon-based composite material and preparation method thereof - Google Patents

Porous carbon-based composite material and preparation method thereof Download PDF

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CN111739740A
CN111739740A CN202010610660.7A CN202010610660A CN111739740A CN 111739740 A CN111739740 A CN 111739740A CN 202010610660 A CN202010610660 A CN 202010610660A CN 111739740 A CN111739740 A CN 111739740A
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porous carbon
composite material
based composite
carbon
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CN111739740B (en
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贺艳兵
谢伟森
宋学文
陈振
游从辉
王翠翠
吕伟
康飞宇
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Shenzhen International Graduate School of Tsinghua University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/40—Fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention provides a porous carbon-based composite material and a preparation method thereof. The method is based on the process of high-frequency disturbance control prepolymer polymerization deposition and spray drying, a porous carbon-based composite material is prepared, the growth of a conductive polymer with controllable speed and the compounding of a carbon material are carried out, in the process of high-frequency disturbance control prepolymer polymerization deposition and spray drying, the mechanically soft carbon material is used as a buffer substrate, the stress in a conjugated polymer can be released, and even if the doped conjugated polymer is broken, fragments can still be anchoredThe composite material is fixed on a substrate without disintegration, and the specific capacitance of the composite material is up to 1039F/cm through testing3And the specific capacitance of 96.5 percent is still kept after 1000 times of circulation, and the cycle performance of the composite material is obviously superior to that of the existing carbon material/polymer composite material. The porous carbon-based composite pseudocapacitance material is suitable for high-stability long-circulation capacitance use occasions.

Description

Porous carbon-based composite material and preparation method thereof
Technical Field
The invention relates to the technical field of materials, in particular to a porous carbon-based composite material and a preparation method thereof.
Background
The cycle stability is a key index for measuring the electrode performance of the super capacitor, and is a measure for quantifying the capacitance retained after a certain working time and charge-discharge cycle times. Materials with excellent capacitance and rate capability have little utility if their useful life is limited. With the continuous development of scientific technology and the continuous increase of population, the problems of energy exhaustion and environmental pollution become more serious, so that the development of an environment-friendly and high-energy-efficiency energy storage device and energy conversion gradually attract people's attention. Among a plurality of energy storage devices, a super capacitor (electrochemical battery) is a high-performance energy storage element with high energy density and power density, long cycle life and rapid charging and discharging, and has wide application prospects in the fields of aerospace, energy sources, electric vehicles and the like. The formation mechanism of the super capacitor can be divided into two types: electric double layer capacitance and faraday pseudocapacitance. The double electric layer capacitor is formed on the contact surface of the electrode and the electrolyte, and the electrolyte and the electrode surface gather the same amount of different charges due to the applied voltage; the Faraday pseudocapacitance is an energy storage element which realizes charge storage and release by the highly reversible oxidation-reduction reaction of electrode active substances on the surface of an electrode or on a two-dimensional space in a bulk phase. The super capacitor electrode is composed of a current collector and a surface active substance, so the specific surface area of the material and the conductivity of the electrode greatly influence the performance of the electrode.
The undesirable cycling stability often masks the large capacitance inherent in pseudocapacitive materials. These defects are due to the complexity associated with the structural integrity, electronic performance and electrochemical behavior of the pseudocapacitive material. The way charge is stored by binding, intercalating and intercalating guest species often fails due to structural instability. Similar to the battery material, the absorption and release of the guest substance is accompanied by expansion and contraction, respectively, of the host material. This repeated volume deformation can create internal osmotic stresses that can crack, crush, and detach the active material. Conjugated polymers are typical pseudocapacitive materials that suffer from structural collapse.
Disclosure of Invention
In view of the above, there is a need to provide an improved method for preparing porous carbon-based composites.
The technical scheme provided by the invention is as follows: a preparation method of a porous carbon-based composite material comprises the following steps:
1) preparing porous carbon hydrogel;
2) pre-polymerization mixing: dispersing a monomer of a conductive polymer into the porous carbon hydrogel, adding a dopant solution containing an oxidative polymerization agent to perform monomer prepolymerization for 1-15 minutes to obtain a prepolymer/porous carbon composite semi-finished product;
3) high-frequency disturbance control of prepolymer polymerization deposition and spray drying: transferring the prepolymer/porous carbon composite semi-finished product into an organic solvent within 10 minutes, adding a processing aid, feeding into a spray dryer for spray drying, carrying out ultrasonic treatment with 20KHz-50KHz for 10-120 minutes during feeding, carrying out polymerization reaction while spraying, and depositing the conductive polymer on the surface and pores of the porous carbon after the size of the conductive polymer is gradually increased after the polymerization reaction is completed to obtain the porous carbon-based composite material.
Further, the porous carbon hydrogel is dispersed in deionized water through a porous carbon material, and is prepared into a swelling state through a hydrothermal reaction; the porous carbon material comprises one of reduced graphene oxide sheets, graphene oxide, graphite foil, etched carbon fibers, carbon nanotubes and carbon aerogel.
Further, the step of dispersing the monomer of the conductive polymer into the porous carbon hydrogel is to disperse the monomer of the conductive polymer and a silicon-based negative electrode material into the porous carbon hydrogel, wherein the silicon-based negative electrode material comprises a silicon simple substance or/and silica, and the particle size of the silicon simple substance or the silica is 5nm-50 μm.
Further, the monomer of the conductive polymer comprises pyrrole or/and thiophene; the oxidative polymerization agent comprises ammonium persulfate or/and ferric chloride; the dopant solution comprises sodium p-toluenesulfonate or/and hydrochloric acid.
Further, the molar ratio of the monomer of the conductive polymer to the oxidative polymerization agent is 4: 1.
Further, the processing aid in the step 3) comprises a sodium carboxymethylcellulose mixture, polyacrylic resin, epoxy resin, sodium alginate or polyvinyl alcohol; the organic solvent comprises at least one of ethanol, acetone, isopropanol, n-butanol and cyclohexane.
Further, the inlet temperature of the spray dryer in the step 3) is controlled to be 160 ℃, the outlet temperature is controlled to be 80 ℃, and the feeding rate is set to be 100-1000 mL/h.
Furthermore, an ultrasonic emitter is installed on a feeding pipeline of the spray dryer, the sound wave regulation range is 20KHz-50KHz, and the working time is 10-120 minutes.
Further, the median particle size of the porous carbon-based composite material is 10-100 microns.
The invention also provides the porous carbon-based composite material prepared by the method.
The undesirable cycling stability often masks the large capacitance inherent in pseudocapacitive materials. The present invention is directed to firmly grasp the pain spot and to a great deal of work andand (5) carrying out experiments. Compared with the prior art, the invention prepares the porous carbon-based composite material based on the process of controlling the polymerization deposition and the spray drying of the prepolymer by high-frequency disturbance, the growth of the conductive polymer with controllable speed and the compounding of the carbon material in the polymerization deposition and the spray drying of the prepolymer by high-frequency disturbance are carried out, the mechanically soft carbon material is used as a buffer substrate, the stress in the conjugated polymer can be released, even if the doped conjugated polymer is broken, the fragments can be anchored on the substrate without disintegration, and the tested composite material has the highest specific capacitance up to 1039F/cm3And the specific capacitance of 96.5 percent is still kept after 1000 times of circulation, and the cycle performance of the composite material is obviously superior to that of the existing carbon material/polymer composite material. The porous carbon-based composite pseudocapacitance material is suitable for high-stability long-circulation capacitance use occasions.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a flow chart illustrating a process for preparing a porous carbon-based composite material according to an embodiment of the present invention.
The following detailed description further illustrates embodiments of the invention in conjunction with the above-described figures.
Detailed Description
So that the manner in which the above recited objects, features and advantages of embodiments of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings. In addition, the features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth to provide a thorough understanding of embodiments of the invention, and the described embodiments are merely a subset of embodiments of the invention, rather than a complete embodiment. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the embodiments of the present invention.
"sodium carboxymethylcellulose mixture" as used herein refers to a combination of sodium carboxymethylcellulose of two or more molecular weights, or a combination of sodium carboxymethylcellulose and other substances, such as microcrystalline cellulose and sodium carboxymethylcellulose, among others.
In unsaturated compounds, three or more P orbitals parallel to each other form large pi bonds, and such systems are called conjugated compounds. Conjugated compounds are compounds of very high molecular weight formed by one or more structural units linked together by covalent bonds, and are referred to herein as "conjugated polymers".
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the present invention belong. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the invention.
Referring to fig. 1, the present invention provides a method for preparing a porous carbon-based composite material, comprising the following steps:
1) and (3) preparing the porous carbon hydrogel.
Specifically, a porous carbon material is dispersed in deionized water, and a swelling state is prepared through a hydrothermal reaction; the porous carbon material comprises one of reduced graphene oxide sheets, graphene oxide, graphite foil, etched carbon fibers, carbon nanotubes and carbon aerogel.
2) Pre-polymerization mixing: dispersing a monomer of a conductive polymer into the porous carbon hydrogel, adding a dopant solution containing an oxidative polymerization agent to perform monomer prepolymerization for 1-15 minutes to obtain a prepolymer/porous carbon composite semi-finished product.
Specifically, in the step of dispersing the monomer of the conductive polymer into the porous carbon hydrogel, the monomer of the conductive polymer and the silicon-based negative electrode material may be dispersed into the porous carbon hydrogel, the silicon-based negative electrode material includes a silicon simple substance or/and silica, and the particle size of the silicon simple substance or the silica is 5nm to 50 μm. The monomer of the conductive polymer comprises pyrrole or/and thiophene; the oxidative polymerization agent comprises ammonium persulfate or/and ferric chloride; the dopant solution comprises sodium p-toluenesulfonate or/and hydrochloric acid. The molar ratio of the monomers of the conductive polymer to the oxidative polymerization agent is 4: 1.
3) High-frequency disturbance control of prepolymer polymerization deposition and spray drying: transferring the prepolymer/porous carbon composite semi-finished product into an organic solvent within 10 minutes, adding a processing aid, feeding into a spray dryer for spray drying, carrying out ultrasonic treatment with 20KHz-50KHz for 10-120 minutes during feeding, carrying out polymerization reaction while spraying, and depositing the conductive polymer on the surface and pores of the porous carbon after the size of the conductive polymer is gradually increased after the polymerization reaction is completed to obtain the porous carbon-based composite material.
Specifically, the processing aid comprises a sodium carboxymethylcellulose mixture, polyacrylic resin, epoxy resin, sodium alginate or polyvinyl alcohol; the organic solvent comprises at least one of ethanol, acetone, isopropanol, n-butanol and cyclohexane. The inlet temperature of the spray dryer is controlled to be 160 ℃, the outlet temperature is controlled to be 80 ℃, and the feeding rate is set to be 100-1000 mL/h. The spray dryer was fed with a peristaltic pump. The feeding pipeline of the spray dryer is provided with an ultrasonic emitter, the sound wave regulation and control range is 20KHz-50KHz, and the working time is 10-120 minutes. The porous carbon-based composite material has a median particle size of 10-100 microns; wherein the feed conduit is sufficiently long. The inlet temperature and the outlet temperature can be adjusted according to the actual production, for example, the inlet temperature is set to 140 ℃, 120 ℃ and the like, the outlet temperature is set to 100 ℃ and the like, and other parameters can be adjusted according to the parameters.
And controlling the polymerization deposition and spray drying process of the prepolymer based on high-frequency disturbance to prepare the porous carbon-based composite material, and performing rate-controllable conductive polymer growth and carbon material compounding. The high-frequency disturbance controls the polymerization deposition of the prepolymer and the spray drying treatment, and the mechanically soft carbon material is used as a buffer substrate to release the stress in the conjugated polymer. Even if the doped conjugated polymer is broken, the fragments can still be anchored on the substrate without disintegration, and the pseudocapacitance material is tested to have the specific capacitance up to 1039F/cm3And the specific capacitance of 96.5 percent is still kept after 1000 times of circulation, and the cycle performance of the composite material is obviously superior to that of the existing carbon material/polymer composite material. The porous carbon-based composite pseudocapacitance material is suitable for high stability,Long cycle capacitor applications.
In order to further explain the technical scheme of the invention, the invention is concretely explained by using graphite oxide powder as a raw material and controlling the total polymerization reaction time to be 150min to prepare a target product.
Example 1
Step 1): weighing 0.12kg of graphite oxide powder and 10kg of deionized water, pouring the graphite oxide powder and the deionized water into an ultrasonic cell crusher, carrying out ultrasonic dispersion for 4 hours at an ultrasonic frequency of 25KHz, and taking out the graphene oxide dispersion liquid. Weighing 10L of dispersion liquid, placing the dispersion liquid in a hydrothermal reaction kettle, and keeping the temperature at 170 ℃ for 8 hours to obtain the three-dimensional self-assembled graphene hydrogel.
Step 2): soaking the graphene hydrogel in 1mol/L hydrochloric acid solution, adding 60mL of aniline monomer into the hydrochloric acid solution, and soaking for 12 h: dissolving 36g of ammonium persulfate in 2000mL of hydrochloric acid solution, transferring the graphene hydrogel adsorbed with the aniline monomer into the hydrochloric acid solution dissolved with ammonium persulfate, and carrying out prepolymerization for 1 minute: taking out the reacted hydrogel;
and 3) immediately transferring the semi-finished product obtained in the step 2) into ethanol, wherein the mass ratio of the ethanol to the semi-finished product is 50:1, adding and dissolving polyvinyl alcohol accounting for 5% of the total mass of the semi-finished product, uniformly stirring, feeding by a peristaltic pump at a feeding rate of 100mL/h, arranging an ultrasonic emitter in a feeding pipeline of the spray dryer with a sound wave regulation range of 50KHz for 120 minutes, performing polymerization reaction during high-frequency disturbance and spray drying, wherein the total reaction time is 150 minutes, and depositing on the surface and pores of the porous carbon base after the polymerization size of the prepolymer is gradually increased to obtain the porous carbon base composite material.
Example 2
Example 2 prepolymerization time 8 minutes compared to example 1, other conditions were kept unchanged.
Example 3
Example 3 prepolymerization time 15 minutes compared to example 1, other conditions were kept unchanged.
Example 4
Example 4 prepolymerization time 15 minutes compared to example 1, other conditions of ultrasound frequency 20KHz were kept unchanged.
Example 5
Compared with example 1, example 5 prepolymerizing time 15 minutes, ultrasonic frequency 35KHz other conditions were kept unchanged.
Example 6
In comparison to example 1, example 6 pre-polymerization time 15 minutes, sonication time 10 minutes, other conditions were kept constant.
Example 7
In contrast to example 1, example 7 pre-polymerization time 15 minutes, sonication time 65 minutes, other conditions were kept constant.
Example 8
In contrast to example 1, example 8 prepolymerisation time 15 minutes, feed rate 500mL/h, other conditions were kept constant.
Example 9
Example 9 prepolymerization time 15 minutes, feed rate 1000mL/h, other conditions were maintained as compared to example 1.
Example 10
Compared with the example 1, the example 10 is that the silicon-based composite material with the mass fraction of 1 percent is added into the semi-finished dispersion liquid before the spray drying and is uniformly mixed, and other conditions are kept unchanged.
Table 1: examples 1-10 are tables of data relating to experimental parameters.
Figure BDA0002560832390000091
Comparative example 1
Step 1): weighing 0.12kg of graphite oxide powder and 10kg of deionized water, pouring the graphite oxide powder and the deionized water into an ultrasonic cell crusher, carrying out ultrasonic dispersion for 4 hours at an ultrasonic frequency of 25KHz, and taking out the graphene oxide dispersion liquid. Weighing 10L of dispersion liquid, placing the dispersion liquid in a hydrothermal reaction kettle, and keeping the temperature at 170 ℃ for 8 hours to obtain the three-dimensional self-assembled graphene hydrogel.
Step 2): soaking the graphene hydrogel in 1mol/L hydrochloric acid solution, adding 60mL of aniline monomer into the hydrochloric acid solution, and soaking for 12 h: dissolving 36g of ammonium persulfate in 2000mL of hydrochloric acid solution, transferring the graphene hydrogel adsorbed with the aniline monomer into the hydrochloric acid solution dissolved with the ammonium persulfate, and controlling the total reaction time for 150 minutes; taking out the reacted hydrogel, baking and drying at 80 ℃, and then crushing to ensure that the median particle size of the composite material is 30 microns. As a control group. The comparative example did not undergo the high frequency perturbation control prepolymer polymerization deposition and spray drying treatment.
Electrochemical cycling performance was tested using the following method: taking the samples prepared in examples 1 to 9 and the active material provided in comparative example 1, the active material, the conductive carbon black Super P and the binder PTFE (5 wt.%) were mixed in the following ratio of 90: 5: 5 proportion in ethanol for 30 min. Stainless steel mesh was used as the current collector. And (3) preparing the uniformly mixed slurry into a circular electrode pole piece in a coating mode, and pressing the pole piece onto a current collector by using a tablet press under the pressure of 10 Mpa. The model of the super capacitor electrode shell is CR2032, the super capacitor is assembled according to the sequence of the negative electrode shell, the spring piece, the gasket, the electrode, the diaphragm, the electrode and the positive electrode shell, the electrolyte adopts 1mol/L dilute sulfuric acid, after a certain amount of electrolyte is dripped, the super capacitor with symmetrical electrodes can be obtained by sealing under the pressure of 55Mpa by a sealing machine.
Table two: pseudocapacitive electrical performance test results for samples of examples 1-10 and the material preparation provided in comparative example 1.
Volume specific capacitance F/cm3 Specific capacity retention ratio/%)
Example 1 1012 93.3% @1000 times
Example 2 1023 95.2% @1000 times
Example 3 1039 96.5% @1000 times
Example 4 960 90.5% @1000 times
Example 5 1005 96% @1000 times
Example 6 743 81% @1000 times
Example 7 824 86.1% @1000 times
Example 8 962 90.8% @1000 times
Example 9 912 91% @1000 times
Example 10 1035 96.3% @1000 times
Comparative example 1 505 45.2% @1000 times
According to the test results in the second table, the specific capacitance of the porous carbon-based composite material for the supercapacitor provided by the invention reaches 1039F/cm at most3And the specific capacitance of 96.5 percent is still kept after 1000 times of circulation, and the circulation performance of the carbon material/polymer composite material is obviously better than that of the carbon material/polymer composite material of the comparative example. As can be seen from the test results in Table two, the longer the prepolymerization time (examples 1 to 3), the higher the ultrasonic frequency (examples 3 to 5) and the longer the ultrasonic duration (examples 6 to 8), the better the cycle performance of the product. The test results of examples 3, 8 and 9 show that the larger the feed rate, the worse the volume specific capacitance and the worse the specific capacitance retention rate. The test results of example 1 and example 10 show that the addition of the silicon-based negative electrode material can obviously improve the cycle performance, and in practical application, because the silicon-based negative electrode material is expensive, the addition amount of the silicon-based negative electrode material is preferably 0.1-1% of the mass of the porous carbon material. In other embodiments, the cycle performance is deteriorated when one of the prepolymerization time, the ultrasonic frequency and the ultrasonic time feeding rate is out of the set range under the same raw material ratio. When different raw material ratios are adopted, corresponding parameters may change, but the invention concept of controlling prepolymer polymerization deposition and spray drying by using high-frequency disturbance should not be excluded from the protection scope of the application. A cliff-type decrease or deterioration in the cycle performance occurs, generally due to the breakage of the incorporated conjugated polymer; the method is based on the above, the process of growing the conductive polymer and compounding the conductive polymer with the carbon material is controlled, the stress in the conjugated polymer is released, namely the conjugated polymer is cracked, and the formed fragments can still be anchored on the carbon material without disintegration due to the fact that the conductive polymer is deposited on the surface and the pores of the porous carbon, so that the stability of the cycle performance is guaranteed.
In other embodiments, the process parameters and the reagents used are not limited to those in the above embodiments, and are not described herein again. For example, the total duration of the polymerization reaction can be substantially completed within 2-3 hours, when the ultrasonic and spray drying are completed in step 3 and the polymerization reaction is not complete, the polymerization reaction can be completely polymerized by standing, and the influence of high-frequency disturbance and spray drying on the product performance can be analyzed under the condition that certain relevant parameters are ensured.
In conclusion, the invention controls the polymerization growth size of the prepolymer through high-frequency disturbance and deposits the prepolymer in the porous material, and the mechanically soft carbon material is used as a buffer substrate to release the stress in the conjugated polymer. Even if the incorporated conjugated polymer breaks, the fragments can be anchored to the substrate without disintegrating. The method has obvious advantages in solving the problems of volume expansion and easy structure damage of the material in the overlong circulation process between the carbon material and the conductive polymer composite material, and is a new discovery.
Although the embodiments of the present invention have been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the embodiments of the present invention.

Claims (10)

1. A preparation method of a porous carbon-based composite material is characterized by comprising the following steps: the method comprises the following steps:
1) preparing porous carbon hydrogel;
2) pre-polymerization mixing: dispersing a monomer of a conductive polymer into the porous carbon hydrogel, adding a dopant solution containing an oxidative polymerization agent to perform monomer prepolymerization for 1-15 minutes to obtain a prepolymer/porous carbon composite semi-finished product;
3) high-frequency disturbance control of prepolymer polymerization deposition and spray drying: transferring the prepolymer/porous carbon composite semi-finished product into an organic solvent within 10 minutes, adding a processing aid, feeding into a spray dryer for spray drying, carrying out ultrasonic treatment with 20KHz-50KHz for 10-120 minutes during feeding, carrying out polymerization reaction while spraying, and depositing the conductive polymer on the surface and pores of the porous carbon after the size of the conductive polymer is gradually increased after the polymerization reaction is completed to obtain the porous carbon-based composite material.
2. The method of preparing a porous carbon-based composite material according to claim 1, wherein: the porous carbon hydrogel is dispersed in deionized water through a porous carbon material, and a swelling state is prepared through a hydrothermal reaction; the porous carbon material comprises one of reduced graphene oxide sheets, graphene oxide, graphite foil, etched carbon fibers, carbon nanotubes and carbon aerogel.
3. The method of preparing a porous carbon-based composite material according to claim 1, wherein: the step of dispersing the monomer of the conductive polymer into the porous carbon hydrogel is to disperse the monomer of the conductive polymer and a silicon-based negative electrode material into the porous carbon hydrogel, wherein the silicon-based negative electrode material comprises a silicon simple substance or/and silica, and the particle size of the silicon simple substance or the silica is 5nm-50 μm.
4. The method of preparing a porous carbon-based composite material according to claim 1, wherein: the monomer of the conductive polymer comprises pyrrole or/and thiophene; the oxidative polymerization agent comprises ammonium persulfate or/and ferric chloride; the dopant solution comprises sodium p-toluenesulfonate or/and hydrochloric acid.
5. The method of preparing a porous carbon-based composite material according to claim 1, wherein: the molar ratio of the monomers of the conductive polymer to the oxidative polymerization agent is 4: 1.
6. The method of preparing a porous carbon-based composite material according to claim 1, wherein: the processing aid in the step 3) comprises a sodium carboxymethylcellulose mixture, polyacrylic resin, epoxy resin, sodium alginate or polyvinyl alcohol; the organic solvent comprises at least one of ethanol, acetone, isopropanol, n-butanol and cyclohexane.
7. The method of preparing a porous carbon-based composite material according to claim 1, wherein: the inlet temperature of the spray dryer in the step 3) is controlled to be 160 ℃, the outlet temperature is controlled to be 80 ℃, and the feeding rate is set to be 100-1000 mL/h.
8. The method of preparing a porous carbon-based composite material according to claim 1, wherein: the feeding pipeline of the spray dryer is provided with an ultrasonic emitter, the sound wave regulation and control range is 20KHz-50KHz, and the working time is 10-120 minutes.
9. The method of preparing a porous carbon-based composite material according to claim 1, wherein: the porous carbon-based composite material has a median particle size of 10-100 microns.
10. A porous carbon-based composite material obtained by molding according to the production method of any one of claims 1 to 9.
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Citations (6)

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