CN112331482A - Porous carbon composite material and preparation method and application thereof - Google Patents
Porous carbon composite material and preparation method and application thereof Download PDFInfo
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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
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
Abstract
The invention discloses a porous carbon composite material and a preparation method and application thereof. The obtained material has rich pore structure, excellent conductivity and excellent specific capacity stability. The obtained product can be widely applied to electrode materials of electrochemical energy storage elements. The method has the advantages of low price of raw materials and simple production steps, can directly synthesize the tubular carbon-porous carbon composite material by calcination, and is suitable for industrial mass production.
Description
Technical Field
The invention belongs to the technical field of preparation of composite carbon materials, and particularly relates to a porous carbon composite material and a preparation method thereof, and also relates to an application of the porous carbon composite material.
Background
The development and application of new energy in China are increasingly urgent due to the proposal of an energy strategy system, and especially the large-scale production of new energy automobiles puts higher requirements on the performance of energy storage devices. The electrode material as a core material is the most important factor limiting the application and development thereof. The porous carbon material becomes an indispensable electrode material in a super capacitor and a lithium ion capacitor due to the abundant pore structure and good chemical stability. At present, the porous carbon material used for the capacitor electrode material in China mainly comprises biomass activated carbon, and has the advantages of higher specific surface area, wide raw material source and low manufacturing cost. However, most of the activated carbon obtained by the activation method is amorphous carbon, which has poor conductivity, and a certain conductive agent needs to be added when the activated carbon is used as an electrode.
To improve the conductivity of carbonaceous materials, there are two main approaches. One is to improve the conductivity of the porous carbon by chemically modifying the carbon, such as by chemical (e.g., S, N heteroelement) doping, to change the electronic and lattice structure of the carbon material. The porous carbon is chemically doped, and usually, a heteroatom precursor is mixed into a carbon precursor, for example, ammonia gas, urea, melamine or imidazole ionic liquid and the like are introduced as a nitrogen precursor, or thiophene, thiourea, sodium sulfite, unsaturated organic sulfonate and the like are used as sulfur precursors, and then the sulfur-nitrogen doped porous carbon is prepared by high-temperature carbonization. A plurality of research works show that the conductivity and the pseudo capacitance of the carbon material after nitrogen doping are improved, so that the carbon material shows excellent performance when being applied as a capacitor.
In addition, some researchers have constructed a conductive network by compounding carbon nanotubes into activated carbon or porous carbon to improve the conductivity of the material, such as chinese patents CN103500820A and CN 105776181A. The main principle is that soluble carbon precursors (such as phenol, formaldehyde and micromolecular polymers) are coated on the surface of the uniformly dispersed carbon nano tube, and then the carbon-coated carbon nano tube is obtained through drying and high-temperature carbonization. In addition, researchers work to prepare the carbon nanotube composite porous carbon by the method, the obtained composite material shows excellent capacitance performance, and particularly after the carbon nanotube is compounded, the multiplying power performance of the composite material is obviously improved due to the improvement of the conductivity.
The doping of the heteroatom to the porous carbon material is beneficial to improving the capacity and the conductivity of the porous carbon material to a certain extent in the electrochemical energy storage application, however, the capacity improvement of the heteroatom is shown by the pseudocapacitance, the pseudocapacitance generated by the redox reaction is difficult to support a long-time cycle, and the capacity attenuation is easily caused in the practical application.
The method for preparing the composite material by coating carbon on the carbon nano tube has complex steps, the coated carbon pore structure is not rich and controllable, and KOH or CO is required to be subsequently used2The requirement of electrochemical energy storage application can be met only by carrying out activation pore-forming.
The present invention is different from the above two paths, and avoids improving the conductivity by doping, but utilizes tubular or fibrous carbon material with large length-diameter ratio to construct a conductive network to improve the conductivity of the porous carbon.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a preparation method of a porous carbon composite material, which aims to solve the problems in the prior art.
The invention content is as follows: a preparation method of a porous carbon composite material comprises the following steps:
(1) dispersing a porous template agent in water to form a suspension;
(2) preparing an aqueous solution by using a catalyst precursor, and slowly dripping the aqueous solution of the catalyst precursor into the suspension obtained in the step (1) under stirring to obtain a mixed solution;
(3) carrying out ultrasonic treatment on the mixed solution obtained in the step (2), carrying out suction filtration and drying, and crushing the dried filter cake into powder;
(4) calcining the powder obtained in the step (3) to obtain a porous template agent with the function of catalytically growing tubular carbon;
(5) directly and uniformly mixing the porous template agent with the function of catalyzing the growth of tubular carbon obtained in the step (4) and a carbon precursor according to a stoichiometric ratio or uniformly mixing the porous template agent and the carbon precursor in a medium, and drying to obtain a mixture;
(6) calcining the mixture obtained in the step (5) under the protection of inert atmosphere, cooling to room temperature and taking out;
(7) and (4) carrying out acid washing or alkali washing on the substance obtained in the step (6) to remove the corresponding template agent, so as to obtain the tubular carbon-porous carbon composite material.
Preferably, the porous template comprises one or more of metal oxide, molecular sieve, natural ore, diatomite and peat soil. More preferably, the porous template is porous magnesium oxide. Preferably, the catalyst precursor is soluble salt of one or more elements of iron, cobalt, nickel, copper and zinc. More preferably, the catalyst precursor is a nitrate or sulfate of iron or nickel, such as nickel nitrate hexahydrate, nickel sulfate hexahydrate, or iron nitrate nonahydrate.
In a preferred embodiment, in the step (2), the molar concentration of the catalyst precursor in the mixed solution obtained is 1 to 1000 mmol/L. Most preferably 3-35 mmol/L.
As a preferable mode, the temperature of the calcination in the step (4) is 350-700 ℃, and the calcination time is 50-75 min. Most preferably at 550 ℃ for 60 min.
Preferably, the carbon precursor is one or more of starch, sucrose, coal tar, pitch and thermoplastic phenolic resin. More preferably, the carbon precursor is one of sucrose, coal tar and pitch.
Preferably, in the step (5), the stoichiometric ratio of the porous template agent with the function of catalytically growing tubular carbon to the carbon precursor is as follows according to the mass ratio: 1, (0.5-100); more preferably, the ratio of 1: (0.5-10).
Preferably, in the step (6), the calcining temperature is 500-; more preferably, the temperature of the calcination is 700-950 ℃. Most preferably, the calcination is carried out at 800-850 ℃ for 40 min.
Preferably, in the step (2), the dropping rate is 10 to 20min/10ml of water.
The invention also aims to provide the porous carbon composite material prepared by the preparation method of the porous carbon composite material.
The invention also aims to provide an electrode of a capacitor, which comprises the porous carbon composite material prepared by the preparation method of the porous carbon composite material.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a method for directly preparing a tubular carbon-porous carbon composite material with enhanced conductivity, which solves the problems of complicated steps and uncontrollable structure of a two-step method for preparing the carbon nanotube-porous carbon composite material. The material obtained by the method has rich pore structures, excellent conductivity and excellent specific capacity stability. The obtained product can be widely applied to electrode materials of electrochemical energy storage elements. The method has the advantages of low raw material price, simple production steps, wide application range of process conditions, good stability and repeatability, can directly synthesize the tubular carbon-porous carbon composite material by calcination, and is suitable for industrial mass production. And makes a certain contribution to the application development of the carbonaceous composite material in various application fields.
Drawings
Fig. 1 is a transmission electron micrograph of a tubular carbon-porous carbon composite prepared by taking example 1 as an example.
FIG. 2 is a graph showing the rate capability of the tubular carbon-porous carbon composite material obtained in example 1 at 1.5-4.2V.
FIG. 3 is a graph of the cycle performance at 2A/g of the tubular carbon-porous carbon composite obtained in example 1.
FIG. 4 is a CV plot of 100mV/s for a tubular carbon-porous carbon composite assembled symmetrical capacitor made in accordance with example 2.
Fig. 5 is a graph showing specific capacitance curves of the tubular carbon-porous carbon composite material prepared in example 2 and the material prepared in the comparative example at different current densities.
Detailed Description
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following will briefly describe the embodiments.
Example 1
(1) Dispersing 10g of porous magnesium oxide in 100ml of water to form suspension;
(2) dissolving 0.25g of nickel sulfate hexahydrate in 10ml of water to prepare an aqueous solution, slowly dripping the aqueous solution into the magnesium oxide suspension obtained in the step (1) under stirring to obtain a mixed solution, wherein the dripping time is controlled to be 10-20 min;
(3) carrying out ultrasonic treatment on the mixed solution obtained in the step (2) for 30min, carrying out suction filtration and drying, and crushing the dried filter cake into powder;
(4) calcining the powder obtained in the step (3) at 550 ℃ for 30min to obtain a porous template agent with the function of catalytically growing tubular carbon;
(5) taking 5g of the porous template agent with the function of catalyzing the growth of tubular carbon obtained in the step (4), uniformly stirring and mixing the porous template agent with 5g of asphalt in ethanol, drying and crushing to obtain a mixture;
(6) placing the mixture obtained in the step (5) in a porcelain boat, calcining for 40min at 800 ℃ in a high-temperature furnace under the protection of nitrogen, cooling to room temperature, and taking out;
(7) and (3) boiling the black powdery substance obtained in the step (6) in 10% diluted hydrochloric acid for 30min to remove the template agent magnesium oxide, carrying out suction filtration and water washing for multiple times until the substance is neutral, and drying a filter cake to obtain the tubular carbon-porous carbon composite material.
The transmission electron micrograph of the tubular carbon-porous carbon composite material prepared by the method is shown in figure 1, and it can be seen that tubular carbon fibers are uniformly inserted in the middle of the carbon layer to form a conductive network structure and can provide a certain supporting effect for the carbon layer. The rate capability of the lithium ion capacitor anode is shown in figure 2, and the lithium ion capacitor anode has a specific capacity close to 110mAh/g under the current density of 0.5A/g when the voltage is 1.5-4.2V. The cycling performance at 2A/g is shown in FIG. 3, and it can be seen that there is no decay in specific capacity after 5000 cycles at 2A/g.
Example 2
(1) 20g of porous magnesium oxide is dispersed in 100ml of water to form suspension;
(2) dissolving 0.25g of nickel sulfate hexahydrate in 10ml of water to prepare an aqueous solution, slowly dripping the aqueous solution into the magnesium oxide suspension obtained in the step (1) under stirring to obtain a mixed solution, wherein the dripping time is controlled to be 10-20 min;
(3) carrying out ultrasonic treatment on the mixed solution obtained in the step (2) for 30min, carrying out suction filtration and drying, and crushing the dried filter cake into powder;
(4) calcining the powder obtained in the step (3) at 550 ℃ for 30min to obtain a porous template agent with the function of catalytically growing tubular carbon;
(5) taking 10g of the porous template agent with the function of catalyzing the growth of tubular carbon obtained in the step (4), uniformly stirring and mixing the porous template agent with 10g of asphalt in ethanol, drying and crushing to obtain a mixture;
(6) placing the mixture obtained in the step (5) in a porcelain boat, calcining for 40min at 800 ℃ in a high-temperature furnace under the protection of nitrogen, cooling to room temperature, and taking out;
(7) and (3) boiling the black powdery substance obtained in the step (6) in 10% diluted hydrochloric acid for 30min to remove the template agent magnesium oxide, carrying out suction filtration and water washing for multiple times until the substance is neutral, and drying a filter cake to obtain the tubular carbon-porous carbon composite material.
The transmission electron micrograph of the prepared tubular carbon-porous carbon composite was similar to that of example 1.
At 1mol/L of Na2SO4The resulting composite was assembled into a symmetrical capacitor for electrolyte, which exhibited a nearly rectangular CV curve at a sweep rate of 100mV/s, as seen in FIG. 4, and exhibited excellent electric double layer capacitance energy storage characteristics. The specific capacitance at a current density of 1A/g was 96.42F/g.
Example 3
(1) Dispersing 10g of porous magnesium oxide in 100ml of water to form suspension;
(2) dissolving 1g of nickel nitrate hexahydrate in 10ml of water to prepare an aqueous solution, slowly dripping the aqueous solution into the magnesium oxide suspension obtained in the step (1) under stirring to obtain a mixed solution, wherein the dripping time is controlled to be 10-20 min;
(3) carrying out ultrasonic treatment on the mixed solution obtained in the step (2) for 30min, carrying out suction filtration and drying, and crushing the dried filter cake into powder;
(4) calcining the powder obtained in the step (3) at 550 ℃ for 30min to obtain a porous template agent with the function of catalytically growing tubular carbon;
(5) taking 7.5g of the porous template agent with the function of catalyzing the growth of tubular carbon obtained in the step (4), and directly grinding and uniformly mixing with 5g of asphalt to obtain a mixture;
(6) placing the mixture obtained in the step (5) in a porcelain boat, calcining for 40min at 850 ℃ in a high-temperature furnace under the protection of nitrogen, cooling to room temperature, and taking out;
(7) and (3) boiling the black powdery substance obtained in the step (6) in 10% diluted hydrochloric acid for 30min to remove the template agent magnesium oxide, carrying out suction filtration and water washing for multiple times until the substance is neutral, and drying a filter cake to obtain the tubular carbon-porous carbon composite material.
The transmission electron micrograph of the prepared tubular carbon-porous carbon composite was similar to that of example 1.
Example 4
(1) 20g of porous magnesium oxide is dispersed in 200ml of water to form suspension;
(2) dissolving 0.3g of ferric nitrate nonahydrate in 10ml of water to prepare an aqueous solution, slowly dripping the aqueous solution into the magnesium oxide suspension obtained in the step (1) under stirring to obtain a mixed solution, wherein the dripping time is controlled to be 10-20 min;
(3) carrying out ultrasonic treatment on the mixed solution obtained in the step (2) for 30min, carrying out suction filtration and drying, and crushing the dried filter cake into powder;
(4) calcining the powder obtained in the step (3) at 550 ℃ for 30min to obtain a porous template agent with the function of catalytically growing tubular carbon;
(5) directly grinding and uniformly mixing 5g of the porous template agent with the tubular carbon catalytic growth function obtained in the step (4) with 5g of asphalt to obtain a mixture;
(6) placing the mixture obtained in the step (5) in a porcelain boat, calcining for 40min at 850 ℃ in a high-temperature furnace under the protection of nitrogen, cooling to room temperature, and taking out;
(7) and (3) boiling the black powdery substance obtained in the step (6) in 10% diluted hydrochloric acid for 30min to remove the template agent magnesium oxide, carrying out suction filtration and water washing for multiple times until the substance is neutral, and drying a filter cake to obtain the tubular carbon-porous carbon composite material.
The transmission electron micrograph of the prepared tubular carbon-porous carbon composite was similar to that of example 1.
Example 5
(1) Dispersing 10g of porous magnesium oxide in 100ml of water to form suspension;
(2) dissolving 1g of nickel nitrate hexahydrate in 10ml of water to prepare an aqueous solution, slowly dripping the aqueous solution into the magnesium oxide suspension obtained in the step (1) under stirring to obtain a mixed solution, wherein the dripping time is controlled to be 10-20 min;
(3) carrying out ultrasonic treatment on the mixed solution obtained in the step (2) for 30min, carrying out suction filtration and drying, and crushing the dried filter cake into powder;
(4) calcining the powder obtained in the step (3) at 550 ℃ for 30min to obtain a porous template agent with the function of catalytically growing tubular carbon;
(5) taking 7.5g of the porous template agent with the function of catalyzing the growth of tubular carbon obtained in the step (4), and directly stirring and uniformly mixing with 20g of coal tar to obtain a mixture;
(6) placing the mixture obtained in the step (5) in a porcelain boat, calcining for 40min at 850 ℃ in a high-temperature furnace under the protection of nitrogen, cooling to room temperature, and taking out;
(7) and (3) boiling the black powdery substance obtained in the step (6) in 10% diluted hydrochloric acid for 30min to remove the template agent magnesium oxide, carrying out suction filtration and water washing for multiple times until the substance is neutral, and drying a filter cake to obtain the tubular carbon-porous carbon composite material.
The transmission electron micrograph of the prepared tubular carbon-porous carbon composite was similar to that of example 1.
Example 6
(1) Dispersing 10g of porous magnesium oxide in 100ml of water to form suspension;
(2) dissolving 1g of nickel nitrate hexahydrate in 10ml of water to prepare an aqueous solution, slowly dripping the aqueous solution into the magnesium oxide suspension obtained in the step (1) under stirring to obtain a mixed solution, wherein the dripping time is controlled to be 10-20 min;
(3) carrying out ultrasonic treatment on the mixed solution obtained in the step (2) for 30min, carrying out suction filtration and drying, and crushing the dried filter cake into powder;
(4) calcining the powder obtained in the step (3) at 550 ℃ for 30min to obtain a porous template agent with the function of catalytically growing tubular carbon;
(5) mixing 10g of the porous template agent with the function of catalyzing the growth of tubular carbon obtained in the step (4) with an aqueous solution containing 20g of cane sugar, stirring for 30min, drying or evaporating to remove the solvent, drying, and crushing into powder to obtain a mixture;
(6) placing the mixture obtained in the step (5) in a porcelain boat, calcining for 40min at 850 ℃ in a high-temperature furnace under the protection of nitrogen, cooling to room temperature, and taking out;
(7) and (3) boiling the black powdery substance obtained in the step (6) in 10% diluted hydrochloric acid for 30min to remove the template agent magnesium oxide, carrying out suction filtration and water washing for multiple times until the substance is neutral, and drying a filter cake to obtain the tubular carbon-porous carbon composite material.
The transmission electron micrograph of the prepared tubular carbon-porous carbon composite was similar to that of example 1.
The tubular carbon in the tubular carbon-porous carbon composite material of the product of the embodiment of the invention refers to carbon nano tubes, carbon fibers or other simple substance carbon materials with larger length-diameter ratio.
Comparative example
Directly grinding 7.5g of porous magnesium oxide and 5g of asphalt, uniformly mixing, placing in a porcelain boat, and calcining at 850 ℃ for 40min under the protection of nitrogen in a high-temperature furnace. Cooling to room temperature and taking out. And placing the obtained black powder in 10% dilute hydrochloric acid, boiling for half an hour to remove the template agent, performing suction filtration and water washing for many times until the black powder is neutral, and drying a filter cake to obtain the porous carbon material.
The transmission electron micrograph of the tubular carbon-porous carbon composite material prepared in example 1 is shown in fig. 1, and the positive electrode rate performance graph at 1.5-4.2V and the cycle performance graph at 2A/g are shown in fig. 2 and fig. 3. Fig. 1 shows that the tubular carbon fibers are uniformly inserted between the carbon layers to provide a certain supporting effect for the carbon layers, and the transmission electron microscope photos of the embodiments 2 to 6 are similar to the carbon layers, and the anode multiplying power and the cycle performance under the same test conditions are also similar, namely, when the voltage range is 1.5 to 4.2V, the specific volume is close to 110mAh/g under the current density of 0.5A/g; after 5000 cycles at 2A/g, the specific capacity had hardly any decay.
It can be seen that the product obtained in the examples is not only excellent in morphology and electrical properties, but also can obtain a tubular carbon-porous carbon composite material with good morphology and consistency, excellent electrical properties and stability under the conditions of more or less catalyst content, wider proportion of the template agent to the carbon source and different mixing modes due to different system conditions of each example. The process of the scheme has the advantages of wide application range of process conditions, good stability and good repeatability.
FIG. 4 is a CV plot of 100mV/s for a tubular carbon-porous carbon composite assembled symmetrical capacitor made in accordance with example 2. At 1mol/L of Na2SO4The resulting composite was assembled into a symmetrical capacitor for electrolyte, which exhibited a nearly rectangular CV curve at a sweep rate of 100mV/s, as seen in FIG. 4, and exhibited excellent electric double layer capacitance energy storage characteristics. Of course, the electric double layer capacitor energy storage characteristics exhibited by the electrolyte solutions using other electrolytes as solutes under the test conditions (e.g., 6mol/L KOH at the same sweep rate) were also excellent. The CV diagrams under the same conditions for the other examples are also similar to example 2.
Fig. 5 is a graph showing specific capacitance curves of the tubular carbon-porous carbon composite material prepared in example 2 and the material prepared in the comparative example at different current densities. The specific capacitance at the current density of 1A/g is 96.42F/g, which is obviously improved compared with the porous carbon without tubular carbon in the comparative example (the specific capacitance at the current density of 1A/g is 84.71F/g), and the decay rate is greatly improved compared with the material of the comparative example along with the increase of the current. The specific capacitance curves for the other examples at different current densities were similar to those of example 2, and were above the curves for the comparative examples at different current densities.
As can be seen from the above, the tubular carbon-porous carbon composite materials prepared by the methods of examples 1 to 6 of the present embodiment have nearly rectangular CV curves in the same electrolyte and at the same sweeping speed, and show excellent energy storage characteristics of the electric double layer capacitor. The specific capacitance under a certain current density is obviously improved compared with the porous carbon without tubular carbon in the comparative example, and the attenuation rate is greatly improved compared with that of the comparative example material along with the increase of the current. The product obtained by the scheme can be widely applied to electrode materials of capacitors of electrochemical energy storage elements, and contributes to the application and development of carbon composite materials in the field of electrical energy storage.
The above embodiments are only intended to illustrate the preferred embodiments of the present invention, and it should be noted that, for those skilled in the art, various modifications and equivalent substitutions can be made without departing from the principle of the present invention, and the scope of the present invention is still covered by the claims.
Claims (10)
1. The preparation method of the porous carbon composite material is characterized by comprising the following steps:
(1) dispersing a porous template agent in water to form a suspension;
(2) preparing an aqueous solution by using a catalyst precursor, and slowly dripping the aqueous solution of the catalyst precursor into the suspension obtained in the step (1) under stirring to obtain a mixed solution;
(3) carrying out ultrasonic treatment on the mixed solution obtained in the step (2), carrying out suction filtration and drying, and crushing the dried filter cake into powder;
(4) calcining the powder obtained in the step (3) to obtain a porous template agent with the function of catalytically growing tubular carbon;
(5) directly and uniformly mixing the porous template agent with the function of catalyzing the growth of tubular carbon obtained in the step (4) and a carbon precursor according to a stoichiometric ratio or uniformly mixing the porous template agent and the carbon precursor in a medium, and drying to obtain a mixture;
(6) calcining the mixture obtained in the step (5) under the protection of inert atmosphere, cooling to room temperature and taking out;
(7) and (4) carrying out acid washing or alkali washing on the substance obtained in the step (6) to remove the corresponding template agent, so as to obtain the tubular carbon-porous carbon composite material.
2. The method for preparing the porous carbon composite material according to claim 1, wherein the porous template comprises one or more of metal oxides, molecular sieves, natural ores, diatomite and peat soil.
3. The method for preparing the porous carbon composite material according to claim 1 or the above, wherein the catalyst precursor is a soluble salt of one or more elements selected from iron, cobalt, nickel, copper and zinc.
4. The method for preparing the porous carbon composite material according to claim 1, wherein the molar concentration of the catalyst precursor in the obtained mixed solution is 1-1000mmol/L in the step (2).
5. The method as claimed in claim 1, wherein the calcination temperature in step (4) is 350-700 ℃.
6. The method for preparing the porous carbon composite material according to claim 1, wherein the carbon precursor is one or more of starch, sucrose, coal tar, pitch and thermoplastic phenolic resin.
7. The preparation method of the porous carbon composite material according to claim 1, wherein in the step (5), the stoichiometric ratio of the porous template agent with the function of catalytically growing tubular carbon to the carbon precursor is as follows according to the mass ratio: 1:(0.5-100).
8. The method as claimed in claim 1, wherein the calcination temperature in step (6) is 500-1200 ℃.
9. The porous carbon composite material prepared by the method for preparing the porous carbon composite material according to any one of claims 1 to 8.
10. An electrode for a capacitor, comprising the porous carbon composite material prepared by the method for preparing a porous carbon composite material according to any one of claims 1 to 8.
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| CN102427130A (en) * | 2011-03-23 | 2012-04-25 | 上海中兴派能能源科技有限公司 | Lithium iron phosphate-carbon nanotube composite material, preparation method, and application thereof |
| CN105776181A (en) * | 2016-04-29 | 2016-07-20 | 大连理工大学 | Preparation method of flaky nanoholes carbon and carbon nanotube composite |
| CN110518213A (en) * | 2019-08-30 | 2019-11-29 | 深圳市德方纳米科技股份有限公司 | A kind of porous silicon-carbon nano tube compound material and its preparation method and application |
| CN110562959A (en) * | 2019-07-16 | 2019-12-13 | 盐城工学院 | Preparation method of carbon nanotube-porous carbon composite material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102427130A (en) * | 2011-03-23 | 2012-04-25 | 上海中兴派能能源科技有限公司 | Lithium iron phosphate-carbon nanotube composite material, preparation method, and application thereof |
| CN105776181A (en) * | 2016-04-29 | 2016-07-20 | 大连理工大学 | Preparation method of flaky nanoholes carbon and carbon nanotube composite |
| CN110562959A (en) * | 2019-07-16 | 2019-12-13 | 盐城工学院 | Preparation method of carbon nanotube-porous carbon composite material |
| CN110518213A (en) * | 2019-08-30 | 2019-11-29 | 深圳市德方纳米科技股份有限公司 | A kind of porous silicon-carbon nano tube compound material and its preparation method and application |
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