CN114835115A - Preparation method and application of active mesophase carbon microspheres - Google Patents

Preparation method and application of active mesophase carbon microspheres Download PDF

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CN114835115A
CN114835115A CN202210524213.9A CN202210524213A CN114835115A CN 114835115 A CN114835115 A CN 114835115A CN 202210524213 A CN202210524213 A CN 202210524213A CN 114835115 A CN114835115 A CN 114835115A
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mesocarbon microbeads
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mesocarbon
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CN114835115B (en
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杨志涛
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Beijing Technology R & D Center Of Baotailong New Materials Co ltd
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • 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
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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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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    • 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 preparation method of an active mesocarbon microbead, which comprises the steps of pretreating the mesocarbon microbead, including intercalation and dilatation, introducing more activating agents into the mesocarbon microbead, removing volatile components in the mesocarbon microbead through heat treatment, and reducing the using amount of the activating agents; secondly, in the activation stage, besides using an alkaline substance as an activator, a catalyst containing transition metal ions is added, so that the activation efficiency and the activation effect are improved; and finally, in the activation stage, programmed heating and segmented reaction are adopted, hydroxide ions and carbon are reacted to form a-C-OH structure in the first heating period, and-OH gradually leaves in the second heating period along with continuous heating to form a porous structure. The process can improve the reaction efficiency and achieve the purpose of high efficiency and energy saving. Compared with the traditional porous carbon material, the activated mesocarbon microbeads have better volume density and are widely applicable to the fields of energy storage, catalysis, adsorption materials and the like.

Description

Preparation method and application of active mesophase carbon microspheres
Technical Field
The invention relates to the technical field of capacitor electrode materials, in particular to a preparation method of an active mesocarbon microbead and application of the mesocarbon microbead in different fields.
Background
Along with the continuous acceleration of the global industrialization process, the world population is continuously increased, and the traditional fossil energy is irreversibly consumed, so that the problem of serious environmental pollution is caused. Global temperature warming, rising sea level and other problems are more serious than one year, and alternative renewable energy sources are urgently needed to be searched. The emergence of environmentally friendly energy sources such as wind energy, solar energy, nuclear energy, and biological energy has brought a boon to global energy problems, but the supply of energy is limited to natural environments, and therefore it is important to develop clean renewable energy sources and portable energy storage devices to solve the current energy problems.
The super capacitor has the advantages of high power density, high charging/discharging speed, long cycle life, wide working temperature range and the like, and is widely applied to the fields of electronic communication, electric power traffic systems, aerospace and the like. The super capacitor can be divided into a double electric layer super capacitor and a Faraday pseudocapacitor according to an energy storage mechanism, the double electric layer super capacitor mainly stores energy through physical electrostatic absorption/desorption of electrolyte ions, most of electrode materials are carbon materials, and the electrode materials play a decisive role in the electrochemical performance of the capacitor, so that the material selection and the performance improvement are hot spots for scientific research all the time.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of active mesocarbon microbeads, and the obtained mesocarbon microbeads have the characteristics of high mesoporosity, high strength coefficient and low expansion coefficient.
The second purpose of the invention is to provide the application of the active mesophase carbon microspheres prepared by the method in the fields of energy storage, catalysis, adsorption materials and the like.
In order to realize the purpose, the technical scheme of the invention is as follows:
the invention relates to a preparation method of an active mesocarbon microbead, which comprises the following steps:
(1) pretreating the mesocarbon microbeads;
preferably, the mesophase carbon microspheres are micron-sized spherical carbon materials formed by separating mesophase spherules from an asphalt matrix through a thermal polycondensation reaction to generate anisotropic mesophase spherules when the heat treatment is carried out on the pitch compounds. The mesocarbon microbeads are novel carbon materials and are mainly used as high-end lithium battery negative electrode materials. The mesocarbon microbeads used in the invention have the following physicochemical parameters: the particle size D50 is 15-35 μm, the volatile component is less than 10%, the ash content is 0.1-0.4%, the toluene insoluble substance is greater than 95%, and the quinoline insoluble substance is 95-98%.
Preferably, the pre-treatment comprises: sequentially carrying out oxidation intercalation, crushing and heating on the mesocarbon microbeads;
preferably, the oxidation intercalation comprises the steps of dipping the mesocarbon microbeads in concentrated sulfuric acid and then adding hydrogen peroxide. The process aims at solving the problems that based on the stable structure of the spherical mesocarbon microbeads, an activating agent and a catalyst are difficult to enter the interior of a material, so that the traditional alkali activation process needs to adopt excessive activating agent and longer reaction time; the pretreatment process opens the spherical mesocarbon microbeads to form an oxidation intercalation layer, so that the mesocarbon microbeads form a channel capable of accommodating an activating agent.
Preferably, after the oxidation intercalation is finished, the oxidation intercalation material is cleaned and then crushed to 50-400 meshes, and then heated for 1-8 hours at 100-400 ℃. The crushing aims at improving the contact area of the material, the activator and the catalyst so that the activator permeates into the material crystal lattice; the heating aims to remove the volatile components in the mesocarbon microbeads, reduce the dosage of the activating agent and improve the activating efficiency.
Preferably, the concentration of concentrated sulfuric acid in the oxidation intercalation process is 2-18 mol/L, and the mass of the concentrated sulfuric acid is 10-1000 times of that of the mesocarbon microbeads; the concentration of hydrogen peroxide is 0.10-9.79 mol/L, and the mass of the hydrogen peroxide is 0.1-2 times of that of the mesocarbon microbeads; the immersion time was 2 h.
Preferably, the grinding is carried out by adopting a sand grinding or ball milling process, the rotation speed of the sand grinding or ball milling is 50-500 rpm, and the time is 0.5-20 h.
(2) Adding an alkaline substance into the pretreated mesocarbon microbeads, and activating under a heating condition;
preferably, the alkaline substance is used as an activator and is selected from one or more of potassium carbonate, potassium hydroxide, potassium bicarbonate, sodium carbonate, sodium hydroxide and sodium bicarbonate.
Preferably, the mass ratio of the mesocarbon microbeads to the alkaline substances is 5: 1-1: 5.
Preferably, the pretreated mesocarbon microbeads are mixed with alkaline substances and then ground for 0.5-2 hours, and then activated.
Preferably, a catalyst is added during the activation process, the catalyst being a carbonate, nitrate or chloride of a transition metal, in particular cobalt or nickel, such as cobalt carbonate, cobalt nitrate, cobalt chloride, nickel carbonate, nickel nitrate, nickel chloride. Preferably, the mass ratio of the catalyst to the pretreated mesocarbon microbeads is (0.01-0.1): 1. The catalyst has the function of enabling transition metal ions to enter gaps of the graphite layer at high temperature, and improving the size of crystal lattices so as to facilitate the infiltration of an activating agent for activation reaction, thereby improving the activation efficiency and the activation effect.
Preferably, the heating adopts a segmented temperature programming process. Wherein the first stage of temperature rise: the temperature rise rate is 1-5 ℃/min at 0-200 ℃, and the second stage of temperature rise: the temperature rise rate is 3-20 ℃/min at 200-600 ℃, and the temperature rise in the third stage is as follows: the heating rate is 1-20 ℃/min at 600-1000 ℃, and the activation is carried out for 3-6 h after the temperature is raised to 600-1000 ℃. The process is programmed heating and sectional reaction, and the programmed heating aims at controlling the reaction rate; in the segmented reaction process, the temperature is raised in the first segment, the activating agent further permeates into the mesocarbon microbead crystal lattice, and the crystal lattice size is continuously increased in the process that the catalyst enters the mesocarbon microbead crystal lattice, so that the pre-reaction of the activating agent and the mesocarbon microbead is promoted; and in the second stage of temperature rise, hydroxyl ions in the activator react with carbon to form a-C-OH structure, and along with the continuous temperature rise, the-OH gradually leaves during the third stage of temperature rise to form a porous structure. The process can improve the reaction efficiency and achieve the purpose of high efficiency and energy saving.
(3) Cleaning and drying the activated mesocarbon microbeads;
preferably, the cleaning comprises: and cleaning the activated mesocarbon microbeads for 5-6 times by using deionized water, cleaning for 2-4 times by using hydrochloric acid with the concentration of 0.1-2 mol/L, and cleaning for 5-6 times by using deionized water.
Preferably, the drying comprises: and (3) placing the cleaned mesocarbon microbeads in a drying box, wherein the drying temperature is 50-150 ℃, and the drying time is 0.5-5 h.
The invention also relates to the application of the mesocarbon microbeads in the fields of energy storage, catalysis and adsorption materials.
The invention has the beneficial effects that:
the invention provides a preparation method of active mesocarbon microbeads, which comprises the steps of firstly pretreating the mesocarbon microbeads, including intercalation and dilatation, introducing more activating agents into the mesocarbon microbeads, and then removing volatile components in the mesocarbon microbeads through heat treatment to reduce the using amount of the activating agents;
secondly, in the activation stage, besides the alkaline substance as an activator, a catalyst containing transition metal ions is added, so that the activator can easily permeate into the mesocarbon microbeads to carry out activation reaction, thereby improving the activation efficiency and the activation effect;
and finally, in the activation stage, programmed heating and segmented reaction are adopted, hydroxide ions and carbon are reacted to form a-C-OH structure in the first heating period, and-OH gradually leaves in the second heating period along with continuous heating to form a porous structure. The process can improve the reaction efficiency and achieve the purpose of high efficiency and energy saving.
The specific surface area of the mesocarbon microbeads obtained by the method can reach 3371.3m 2 In terms of a/g and a relative activityThe carbon material has the characteristics of high mesoporous rate, high strength coefficient and low expansion coefficient. The specific capacitance can reach 840F/g, compared with the traditional porous carbon material, the activated mesophase carbon microsphere has better volume density, and is widely applicable to the fields of energy storage, catalysis, adsorption materials and the like.
Drawings
FIG. 1 is a scanning electron micrograph of the unactivated mesophase carbon microspheres of comparative example 1.
FIG. 2 is a scanning electron micrograph of the mesocarbon microbeads of example 1 after activation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
A preparation method of active mesophase carbon microspheres comprises the following steps:
(1) pretreating the mesocarbon microbeads: adding 20g of mesocarbon microbeads into 500ml of sulfuric acid with the concentration of 18.3mol/L, mixing and stirring for 2 hours, dropwise adding 100ml of hydrogen peroxide with the concentration of 2mol/L, and reacting for 2 hours after dropwise adding. And (3) cleaning the solid phase substance after the reaction is finished, wherein the solid phase substance is cleaned by adopting excessive distilled water until the pH value is more than 3, and the cleaned sample is dried for later use.
After cleaning and drying, a ball milling process is adopted to crush the mesocarbon microbeads to 200 meshes, and then the mesocarbon microbeads are heated in a drying oven at 180 ℃ for 6 hours. The mesocarbon microbeads used in the embodiment of the invention are produced by Baotailong New Material Co., Ltd.
(2) Activating mesocarbon microbeads: mixing the dried potassium hydroxide powder with the pretreated mesocarbon microbeads according to the mass ratio of 3:1, grinding for 2 hours, and gradually adding cobalt nitrate in the grinding process, wherein the mass ratio of the cobalt nitrate to the mesocarbon microbeads is 0.02: 1. And (2) placing the ground sample in a high-temperature furnace, performing activation treatment by adopting a programmed heating mode, wherein the heating rate is 5 ℃/min at 0-200 ℃, the heating rate is 10 ℃/min at 200-600 ℃, the heating rate is 2 ℃/min at 600-1000 ℃, activating for 4 hours after the temperature is raised to 1000 ℃, and cooling the product to room temperature after the reaction is finished.
(3) Cleaning the activated mesocarbon microbead material: and cleaning and drying the activated mesocarbon microbeads. The cleaning comprises the following steps: and washing with deionized water for 6 times, then washing with 0.5mol/L hydrochloric acid for 4 times, and then washing with deionized water for 6 times.
The drying comprises the following steps: and (3) putting the cleaned mesocarbon microbeads in a drying box, heating to 120 ℃, and drying for 4 hours to obtain the active mesocarbon microbeads.
The following performance tests were performed on the activated mesocarbon microbeads prepared as described above:
the specific surface area of the solid substance is determined according to the national standard GB/T19587-2004 gas adsorption BET principle. The specific surface area of the material is determined to be 3371.3m by adopting a BELSORP MAX II specific surface area tester 2 /g。
According to the national standard GB/T37386-2019 activated carbon for the super capacitor, a Hiden Analytical/IGA 001 weight analyzer is adopted to determine that the total pore volume of the material is 1.41m 3 Per g, average pore volume of 2.39m 3 The mesopore ratio was 86.67%.
Determining the specific capacitance of the material by cyclic voltammetry, comprising: preparing an electrode slice from the activated mesocarbon microbeads and Polytetrafluoroethylene (PTFE) according to the mass ratio of 9:1, forming three electrodes with a platinum electrode and a Hg/HgO electrode, and testing in a 3M KOH solution. The specific capacitance was 839.7F/g at a current density of 1A/g and 679.2F/g at a current density of 10A/g.
Example 2
A preparation method of active mesophase carbon microspheres comprises the following steps:
(1) pretreating the mesocarbon microbeads: adding 20g of mesocarbon microbeads into 500ml of sulfuric acid with the concentration of 15mol/L, mixing and stirring for 2 hours, dropwise adding 150ml of hydrogen peroxide with the concentration of 1mol/L, and reacting for 2 hours after dropwise adding. And (3) cleaning the solid phase substance after the reaction is finished, wherein the solid phase substance is cleaned by adopting excessive distilled water until the pH value is more than 3, and the cleaned sample is dried for later use.
The intermediate phase carbon microspheres are crushed to 100 meshes by adopting a ball milling process and then heated in a drying oven at 200 ℃ for 4 hours.
(2) Mixing the dried sodium hydroxide powder with the pretreated mesocarbon microbeads in a mass ratio of 5:1, grinding for 2 hours, and gradually adding nickel chloride in the grinding process, wherein the mass ratio of the nickel chloride to the mesocarbon microbeads is 0.05: 1. And (3) placing the ground sample in a high-temperature furnace, activating by adopting a programmed heating mode, heating at 0-200 ℃ at a heating rate of 3 ℃/min, heating at 200-600 ℃ at a heating rate of 5 ℃/min, heating at 600-1000 ℃ at a heating rate of 1 ℃/min, heating to 800 ℃, activating for 5 hours, and cooling the product to room temperature after the reaction is finished.
(3) And cleaning and drying the activated mesocarbon microbeads. The cleaning comprises the following steps: and (3) washing with deionized water for 5 times, then washing with 1mol/L hydrochloric acid for 3 times, and then washing with deionized water for 6 times. The drying comprises the following steps: and (3) placing the washed mesocarbon microbeads in a drying box, heating to 100 ℃, and drying for 5 hours to obtain the active mesocarbon microbeads.
Example 3
A preparation method of active mesophase carbon microspheres comprises the following steps:
(1) pretreating the mesocarbon microbeads: adding 20g of mesocarbon microbeads into 500ml of 17mol/L sulfuric acid, mixing and stirring for 2 hours, dropwise adding 300ml of 0.5mol/L hydrogen peroxide, and reacting for 2 hours after dropwise addition. And (3) cleaning the solid phase substance after the reaction is finished, wherein the solid phase substance is cleaned by adopting excessive distilled water until the pH value is more than 3, and the cleaned sample is dried for later use.
The intermediate phase carbon microspheres are crushed to 150 meshes by adopting a ball milling process and then heated in a drying oven at 150 ℃ for 5 hours.
(2) Mixing the dried sodium carbonate powder with the pretreated mesocarbon microbeads in a mass ratio of 1:3, grinding for 2 hours, and gradually adding cobalt carbonate in the grinding process, wherein the mass ratio of the cobalt carbonate to the mesocarbon microbeads is 0.01: 1. And (3) placing the ground sample in a high-temperature furnace, activating by adopting a programmed heating mode, wherein the heating rate is 5 ℃/min at 0-200 ℃, 10 ℃/min at 200-600 ℃, 2 ℃/min at 600-1000 ℃, activating for 4 hours after heating to 1000 ℃, and cooling the product to room temperature after the reaction is finished.
(3) And cleaning and drying the activated mesocarbon microbeads. The washing and drying process was the same as in example 1.
Comparative example 1
Step (1) is not subjected to oxidation intercalation treatment, namely: pretreatment the preferable intermediate phase carbon microspheres are ground into 200 meshes by adopting a ball milling process, and then heated in a drying oven at 180 ℃ for 6 hours. The other preparation process is the same as that of example 1.
Comparative example 2
Step (2) no potassium hydroxide powder is added, namely: grinding the pretreated mesocarbon microbeads for 2 hours, gradually adding cobalt nitrate in the grinding process, wherein the mass ratio of the cobalt nitrate to the mesocarbon microbeads is 0.02:1, and then carrying out activation treatment. The other preparation process is the same as example 1.
Comparative example 3
The step (2) does not add cobalt nitrate, namely: mixing the dried potassium hydroxide powder with the pretreated mesocarbon microbeads according to the mass ratio of 3:1, grinding for 2 hours, and then carrying out activation treatment. The other preparation process is the same as that of example 1.
Comparative example 4
The intermediate phase carbon microsphere is not activated.
The active mesocarbon microbeads obtained in the above examples and comparative examples were subjected to cyclic voltammetry using the same method as in example 1, and the specific capacitances obtained at a current density of 1A/g and a current density of 10A/g were shown in Table 1.
TABLE 1
Figure BDA0003643399630000081
As can be seen from the test data of the examples and the comparative examples, the comparative examples 1 to 3 change the preparation process, and the specific surface area and the specific capacitance are reduced compared with the examples. Comparative example 4 is an unactivated mesocarbon microbead with a very low specific surface area and no porous structure.
FIG. 1 is an electron micrograph of mesophase carbon microbeads before activation, corresponding to comparative example 4; FIG. 2 is an electron micrograph of the activated carbon, which corresponds to example 1. It can be seen that the surface morphology of the activated mesocarbon microbeads is greatly changed, the surface is rough and the surface of the microbeads is clustered. The performance characterization result of the material is comprehensively considered, the specific surface area of the activated mesocarbon microbeads is greatly increased, and the material is proved to become a porous material after being treated by the activation process.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (10)

1. A preparation method of active mesocarbon microbeads is characterized by comprising the following steps:
(1) pretreating the mesocarbon microbeads, wherein the pretreatment comprises oxidizing intercalation, crushing and heating of the mesocarbon microbeads in sequence;
(2) adding an alkaline substance into the pretreated mesocarbon microbeads, and activating under a heating condition;
(3) and cleaning and drying the activated mesocarbon microbeads to obtain the activated mesocarbon microbeads.
2. The method according to claim 1, wherein in the step (1), the mesocarbon microbeads have the following physicochemical parameters: the particle size D50 is 15-35 μm, the volatile component is less than 10%, the ash content is 0.1-0.4%, the toluene insoluble substance is greater than 95%, and the quinoline insoluble substance is 95-98%.
3. The method of claim 1, wherein in the step (1), the step of oxidizing and intercalating comprises immersing the mesocarbon microbeads in concentrated sulfuric acid, and then adding hydrogen peroxide.
4. The method according to claim 1, wherein in the step (1), after the oxidation intercalation is finished, the obtained oxidation intercalation material is cleaned and crushed to 50-400 meshes, and then heated at 100-400 ℃ for 1-8 hours.
5. The method according to claim 1, wherein in the step (2), the alkaline substance is selected from one or more of potassium carbonate, potassium hydroxide, potassium bicarbonate, sodium carbonate, sodium hydroxide and sodium bicarbonate;
and/or the mass ratio of the mesocarbon microbeads to the alkaline substances is 5: 1-1: 5.
6. The method according to claim 1, wherein in the step (2), the pretreated mesocarbon microbeads are mixed with alkaline substances, ground for 0.5-2 hours, and then activated.
7. The method according to claim 1, wherein in the step (2), a catalyst is added in the activation process, and the catalyst is selected from one or more of cobalt carbonate, cobalt nitrate, cobalt chloride, nickel carbonate, nickel nitrate and nickel chloride;
and/or the mass ratio of the catalyst to the pretreated mesocarbon microbeads is (0.01-0.1): 1.
8. The method of claim 1, wherein in step (2), the heating is performed by a step-programmed temperature raising process, wherein the first step of temperature raising comprises: the temperature rise rate is 1-5 ℃/min at 0-200 ℃, and the second stage of temperature rise: the temperature rise rate is 3-20 ℃/min at 200-600 ℃, and the temperature rise in the third stage is as follows: the heating rate is 1-20 ℃/min at 600-1000 ℃, and the activation is carried out for 3-6 h after the temperature is raised to 600-1000 ℃.
9. The method of claim 1, wherein in step (3), the cleaning comprises: washing the activated mesocarbon microbeads for 5-6 times by using deionized water, then washing for 2-4 times by using hydrochloric acid with the concentration of 0.1-2 mol/L, and then washing for 5-6 times by using deionized water;
and/or, the drying comprises: and (3) placing the cleaned mesocarbon microbeads in a drying box, wherein the drying temperature is 50-150 ℃, and the drying time is 0.5-5 h.
10. The application of the mesocarbon microbeads prepared by the method of any one of claims 1 to 9 in the fields of energy storage, catalysis and adsorption materials.
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CN102631915A (en) * 2011-12-07 2012-08-15 天津市贝特瑞新能源材料有限责任公司 Fuel-cell catalyst with intermediate-phase carbon microspheres load Pt (platinum) and preparation method and application of fuel-cell catalyst
CN104045080A (en) * 2014-06-27 2014-09-17 福州大学 Activated graphene sheet and preparation method thereof
CN104098078A (en) * 2013-04-07 2014-10-15 中国科学院长春应用化学研究所 Activated mesocarbon microbeads, preparation method thereof and supercapacitor

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101393800A (en) * 2008-10-11 2009-03-25 广西师范大学 Electrode material for super capacitor and preparing method thereof
CN102631915A (en) * 2011-12-07 2012-08-15 天津市贝特瑞新能源材料有限责任公司 Fuel-cell catalyst with intermediate-phase carbon microspheres load Pt (platinum) and preparation method and application of fuel-cell catalyst
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