CN103318871A - Preparation method for synthesizing graphite porous carbon material with activated carbon serving as raw material - Google Patents
Preparation method for synthesizing graphite porous carbon material with activated carbon serving as raw material Download PDFInfo
- Publication number
- CN103318871A CN103318871A CN2013102769057A CN201310276905A CN103318871A CN 103318871 A CN103318871 A CN 103318871A CN 2013102769057 A CN2013102769057 A CN 2013102769057A CN 201310276905 A CN201310276905 A CN 201310276905A CN 103318871 A CN103318871 A CN 103318871A
- Authority
- CN
- China
- Prior art keywords
- gac
- carbon
- obtains
- preparation
- under
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention provides a preparation method for synthesizing a graphite porous carbon material with activated carbon serving as a raw material, relates to a preparation method for synthesizing the graphite porous carbon material, and aims at solving the technical problems of the conventional activated carbon materials that the electrical conductivity is relatively low, the aperture is relatively small, the preparation process is complex, the temperature in synthesis is relatively high, and the massive production cannot be realized. The preparation method comprises the following steps of: 1, diffusing activated carbon; 2, performing coordinate bond to the activated carbon and a catalyst; 3, curing a coordination compound; 4, thermally processing; 5, performing acid treatment. The preparation method is mainly applied to the preparation of the graphite porous carbon material.
Description
Technical field
The present invention relates to a kind of preparation method of synthetic graphite porous carbon materials.
Background technology
Because human society is to the active demand of new function material, carbon material more and more receives people's concern.The carbon material that relatively has at present using value comprises gac, carbon fiber, Graphenes etc., these carbon materials can embody unique advantageous properties such as high strength, thermotolerance, rub resistance, resistance to chemical attack, conduction, heat conduction, radioprotective, damping value are low, noise reduction, damping.In recent years, in order further to develop its function and to improve its performance, people have carried out large quantity research to aspects such as the degree of crystallinity of carbon material, grand microtexture and surface property.The carbon current material has been widely used in the fields such as the energy, environment, machinery, electronics.
Gac is that a kind of pore texture is flourishing, and specific surface area is very large, the carbon material that adsorptive power is very strong, and by shell, coconut husk, timber, the raw materials such as coal are through carbonization, and the steps such as activation are prepared from, and are cheap, produce simple and easy.Microcrystalline carbon irregular alignment in the gac forms a large amount of pores, and tap density is lower, and specific surface area is larger.It is widely used in energy resource system, purification of water quality, the Application Areass such as Gas Phase Adsorption and lithium cell.But in present absorbent charcoal material, the irregular alignment of its carbon crystalline substance makes it relatively poor with respect to other carbon material electroconductibility, and it is block that microtexture is more, surface apertures is generally less, these drawbacks limit the application prospect of gac at lithium cell, gac is during as cathode of lithium battery, and the bad meeting of electroconductibility causes the decline of charge-discharge velocity and the loss of cell container; The aperture is less then can be affected lithium ion and electrolyte ion in the embedding of negative pole and deviate from speed, and then affects capacity and discharge and recharge the time of response.Therefore, how promoting and improve material electroconductibility and aperture structure is the key that improves its application performance.
Improve the performance of gac, mainly start with from greying and the surface tissue improvement of material.Graphite crystal stratiform ordered structure has more good physics, chemical property, such as preferably electrochemical stability and good electroconductibility.The feasible way that strengthens its electroconductibility with the gac greying.Realize that at present the preparation of greying gac mainly is greying in the presoma carbonization process, such as solid-phase pyrolysis, chemical Vapor deposition process etc.Another feasible method is that the moulding carbon material is carried out graphitization processing, comprises arc discharge method, high-temperature activation method etc.
Many researchers adopts chemical Vapor deposition process or the standby graphitized carbon material of high-temperature activation legal system in recent years.The general pattern of chemical meteorology deposition method products obtained therefrom, size be homogeneous comparatively, can effectively control the product pattern, is suitable for producing in batches.But its products obtained therefrom specific surface area is generally very low, and performance is difficult to further raising.The high-temperature activation method can make material be converted into greying crystalline state carbon by decolorizing carbon, and its cardinal principle is to utilize thermal activation that the carbon atom of thermodynamic instability is realized by the orderly conversion of turbostratic to crystal structure of graphite.But this kind method is comparatively harsh for the selection of raw material, mostly is the higher chemical product that mineralizes of cost, and recyclability is poor, and exploitation and extractive process are unfavorable for environmental protection, the while complex process, and equipment requirements is high, and productive rate is low, poor stability.In sum, explore graphitization nano carbon material degree of graphitization regulation and control, the comprehensive improved effective ways of surface tissue significant for expanding graphitization nano carbon material industry application.Existing absorbent charcoal material electroconductibility is relatively poor, the aperture is less, complicated process of preparation, synthesis temperature are higher, be not suitable for scale operation.
Summary of the invention
The present invention be to solve that existing absorbent charcoal material electroconductibility is relatively poor, the aperture is less, complicated process of preparation, synthesis temperature are higher, the technical problem that is not suitable for scale operation, thereby provide a kind of take the preparation method of gac as raw material synthetic graphite porous carbon materials.
A kind of preparation method take gac as raw material synthetic graphite porous carbon materials of the present invention carries out according to the following steps:
One, the dispersion of gac: gac is evenly mixed with solvent, then under rotating speed is the condition of 100r/min～350r/min, stir 3h～9h and obtain homogeneous reaction liquid, in homogeneous reaction liquid, add surfactant soln, continue under rotating speed is the condition of 100r/min～350r/min, to stir 1h～3h liquid that is uniformly mixed; The quality of described gac and the volume ratio of solvent are (0.1g～10g): 100mL; The mass ratio of the solute in described gac and the surfactant soln is (10～100): 1; The volumetric molar concentration of described surfactant soln is 0.0005mol/L～0.05mol/L;
Two, gac is combined with the coordination of catalyzer: add metal catalyst in the even mixed solution that obtains to step 1, then the rotating speed with 100r/min～350r/min stirs 4h～8h, obtains title complex finally by crossing sonic oscillation 30min～120min; The mass ratio of the gac described in the metal catalyst described in the step 2 and the step 1 is 1: (1～10);
Three, the curing of title complex: then the title complex vacuum-drying 2h～24h under 20 ℃～100 ℃ condition with step 2 obtains naturally cools to the title complex that room temperature obtains solidifying;
Four, thermal treatment: the title complex of the curing that step 3 is obtained is to be warming up to 500 ℃～1000 ℃ from room temperature with the temperature rise rate of 5 ℃/min～30 ℃/min under the protection of rare gas element of 30mL/min～200mL/min in airshed, is incubated 1h～6h again under temperature is 500 ℃～1000 ℃ condition and obtains carbon material;
Five, acid treatment: the carbon material that obtains with sour circumfluence method treatment step four, obtain the presoma of carbon material, again with the presoma of 2～4 carbon materials of distilled water centrifuge washing to the pH of the presoma of carbon material be 6.8～7.2, then be vacuum-drying 5h～10h under 60 ℃～80 ℃ conditions in temperature, namely obtain graphitized stephanoporate material with carbon element.
The present invention has the following advantages:
One, the present invention is take gac as raw material synthetic graphite porous carbon materials, and preparation technology is simple, and chemical property has improved 20%～40%.
Two, compare 2000 ℃～4000 ℃ thermal treatment temp with the traditional industry method, the present invention synthesizes under 500 ℃～1000 ℃ lower thermal treatment temp, and the reduction of energy consumption reaches 60%～85%, has improved security, is applicable to scale operation;
Three, consumption and the thermal treatment temp of the present invention by changing graphitization catalyst realizes regulation and control to the gac degree of graphitization;
Four, the graphitized stephanoporate material with carbon element that synthesizes of the present invention is by making microcrystalline carbon be transformed to the graphite laminate ordered structure by irregular alignment, and the surface has meso-hole structure, electronics, ion transport ability have been strengthened, physics, chemical stability are good, so that material can be widely used in multiple electrochemical energy devices.
Description of drawings
Fig. 1 is the XRD figure spectrum, a is the XRD figure spectrum of test one prepared graphitized stephanoporate material with carbon element among the figure, b is the XRD figure spectrum of test two prepared graphitized stephanoporate material with carbon element among the figure, c is the XRD figure spectrum of test three prepared graphitized stephanoporate material with carbon element among the figure, d is the XRD figure spectrum of test four prepared graphitized stephanoporate material with carbon element among the figure, e is the XRD figure spectrum of test five prepared graphitized stephanoporate material with carbon element among the figure, f is the XRD figure spectrum of test six prepared graphitized stephanoporate material with carbon element among the figure, among the figure ▲ and be graphite 002 crystal face of graphitized stephanoporate material with carbon element;
Fig. 2 is the nitrogen adsorption desorption curve of test four gained graphitized stephanoporate material with carbon element;
Fig. 3 is 25000 times of transmission electron microscope pictures of test four gained graphitized stephanoporate material with carbon element;
Fig. 4 is 400000 times of transmission electron microscope pictures of test four gained graphitized stephanoporate material with carbon element;
Fig. 5 is 300000 times of transmission electron microscope pictures of test seven gained graphitized stephanoporate material with carbon element;
Fig. 6 is 400000 times of transmission electron microscope pictures of test eight gained graphitized stephanoporate material with carbon element.
Embodiment
Embodiment one: a kind ofly in the present embodiment carry out according to the following steps take the preparation method of gac as raw material synthetic graphite porous carbon materials:
One, the dispersion of gac: gac is evenly mixed with solvent, then under rotating speed is the condition of 100r/min～350r/min, stir 3h～9h and obtain homogeneous reaction liquid, in homogeneous reaction liquid, add surfactant soln, continue under rotating speed is the condition of 100r/min～350r/min, to stir 1h～3h liquid that is uniformly mixed; The quality of described gac and the volume ratio of solvent are (0.1g～10g): 100mL; The mass ratio of the solute in described gac and the surfactant soln is (10～100): 1; The volumetric molar concentration of described surfactant soln is 0.0005mol/L～0.05mol/L;
Two, gac is combined with the coordination of catalyzer: add metal catalyst in the even mixed solution that obtains to step 1, then the rotating speed with 100r/min～350r/min stirs 4h～8h, obtains title complex finally by crossing sonic oscillation 30min～120min; The mass ratio of the gac described in the metal catalyst described in the step 2 and the step 1 is 1: (1～10);
Three, the curing of title complex: then the title complex vacuum-drying 2h～24h under 20 ℃～100 ℃ condition with step 2 obtains naturally cools to the title complex that room temperature obtains solidifying;
Four, thermal treatment: the title complex of the curing that step 3 is obtained is to be warming up to 500 ℃～1000 ℃ from room temperature with the temperature rise rate of 5 ℃/min～30 ℃/min under the protection of rare gas element of 30mL/min～200mL/min in airshed, is incubated 1h～6h again under temperature is 500 ℃～1000 ℃ condition and obtains carbon material;
Five, acid treatment: the carbon material that obtains with sour circumfluence method treatment step four, obtain the presoma of carbon material, again with the presoma of 2～4 carbon materials of distilled water centrifuge washing to the pH of the presoma of carbon material be 6.8～7.2, then be vacuum-drying 5h～10h under 60 ℃～80 ℃ conditions in temperature, namely obtain graphitized stephanoporate material with carbon element.
Present embodiment has the following advantages:
One, the present invention is take gac as raw material synthetic graphite porous carbon materials, and preparation technology is simple, and chemical property has improved 20%～40%.
Two, compare 2000 ℃～4000 ℃ thermal treatment temp with the traditional industry method, the present invention synthesizes under 500 ℃～1000 ℃ lower thermal treatment temp, and the reduction of energy consumption reaches 60%～85%, has improved security, is applicable to scale operation;
Three, consumption and the thermal treatment temp of the present invention by changing graphitization catalyst realizes regulation and control to the gac degree of graphitization;
Four, the graphitized stephanoporate material with carbon element that synthesizes of the present invention is by making microcrystalline carbon be transformed to the graphite laminate ordered structure by irregular alignment, and the surface has meso-hole structure, electronics, ion transport ability have been strengthened, physics, chemical stability are good, so that material can be widely used in multiple electrochemical energy devices.
Embodiment two: what present embodiment and embodiment one were different is: the solvent described in the step 1 is a kind of in distilled water, ethanol, ethylene glycol and the Virahol or several mixture wherein; Gac described in the step 1 is a kind of in cocoanut active charcoal, active fruit shell carbon, wood activated charcoal and the coal mass active carbon or several mixture wherein; The solute of the surfactant soln described in the step 1 is a kind of in polyvinylpyrrolidone, sodium lauryl sulphate and the Sodium dodecylbenzene sulfonate or several mixture wherein, and the solvent of surfactant soln is deionized water.Other is identical with embodiment one.
Embodiment three: what present embodiment was different from one of embodiment one or two is: in the step 1 gac is evenly mixed with solvent, then under rotating speed is the condition of 200r/min～300r/min, stir 5h～7h and obtain homogeneous reaction liquid, then in homogeneous reaction liquid, add surfactant soln, continue under rotating speed is the condition of 200r/min～300r/min, to stir 1h～3h liquid that is uniformly mixed.Other is identical with one of embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is: the quality of the gac described in the step 1 and the volume ratio of solvent are (3g～7g): 100mL; The mass ratio of the solute in the gac described in the step 1 and the surfactant soln is (30～70): 1; The volumetric molar concentration of the surfactant soln described in the step 1 is 0.005mol/L～0.01mol/L.Other is identical with one of embodiment one to three.
Embodiment five: what present embodiment was different from one of embodiment one to four is: the metal catalyst described in the step 2 is a kind of in Iron nitrate, ferrous sulfate, iron protochloride, iron nitrate, ferric sulfate, iron(ic) chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobalt chloride, Cobaltous diacetate, single nickel salt, nickelous nitrate, nickelous chloride and the nickel acetate or several mixture wherein.Other is identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is: the mass ratio of the gac described in the metal catalyst described in the step 2 and the step 1 is 1: (4～6).Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different from one of embodiment one to six is: the title complex of the curing that in the step 4 step 3 is obtained is to be warming up to 700 ℃～900 ℃ from room temperature with the temperature rise rate of 10 ℃/min～20 ℃/min under the protection of rare gas element of 80mL/min～150mL/min in airshed, is incubated 3h～5h again under temperature is 700 ℃～900 ℃ condition and obtains carbon material.Other is identical with one of embodiment one to six.
Embodiment eight: what present embodiment was different from one of embodiment one to seven is: the rare gas element described in the step 4 is a kind of in nitrogen, argon gas and the carbonic acid gas or two kinds mixed gas wherein.Other is identical with one of embodiment one to seven.
When the described rare gas element of present embodiment is two kinds mixed gas, pass into mode as follows: 1, when rare gas element is the mixed gas of nitrogen and argon gas, pass into simultaneously nitrogen and argon gas take the airshed of nitrogen as 80mL/min～150mL/min with take the airshed of argon gas as 80mL/min～150mL/min.2, when rare gas element is the mixed gas of nitrogen and carbonic acid gas, pass into simultaneously nitrogen and carbonic acid gas take the airshed of nitrogen as 80mL/min～150mL/min with take the airshed of carbonic acid gas as 80mL/min～150mL/min.3, when rare gas element is the mixed gas of argon gas and carbonic acid gas, pass into simultaneously argon gas and carbonic acid gas take the airshed of argon gas as 80mL/min～150mL/min with take the airshed of carbonic acid gas as 80mL/min～150mL/min.
Embodiment nine: what present embodiment was different from one of embodiment one to eight is: the carbon material that obtains with sour circumfluence method treatment step four in the step 5, obtain washing lotion, again with the distilled water wash washing lotion to the pH of washing lotion be 6.8～7.2, then be vacuum-drying 7h～9h under 60 ℃～80 ℃ conditions in temperature, namely obtain graphitized stephanoporate material with carbon element.Other is identical with one of embodiment one to eight.
Embodiment ten: what present embodiment was different from one of embodiment one to nine is: the sour circumfluence method described in the step 5 is carried out according to the following steps:
The carbon material that step 4 is obtained is dissolved in the acid solution, is that 50 ℃～90 ℃ and stirring velocity are cooling for reflux 1h～12h under the condition of 100r/min～350r/min in temperature then, then naturally cools to the presoma that room temperature obtains carbon material; The quality of described carbon material and the volume ratio of acid solution are (0.1g～10g): 100mL; The concentration of described acid solution is 0.1mol/L～6mol/L, and wherein said acid solution is a kind of in hydrochloric acid soln, salpeter solution, sulphuric acid soln and the phosphoric acid solution or several mixed acid solution wherein.Other is identical with one of embodiment one to nine.
By following verification experimental verification beneficial effect of the present invention:
Test one: a kind of method take gac as raw material synthetic graphite porous carbon materials of this test is to realize by the following method:
One, the dispersion of gac: commercial active fruit shell carbon is scattered in the ethanol, then be to stir 3h under the condition of 350r/min to obtain homogeneous reaction liquid at rotating speed, then add PVP solution in the homogeneous reaction liquid, continue under rotating speed is the condition of 350r/min, to stir the 3h liquid that is uniformly mixed; The quality of described commercial active fruit shell carbon and the volume ratio of ethanol are 1g: 100mL; The weight ratio of the solute in commercial active fruit shell carbon and the PVP solution is 10: 1; The volumetric molar concentration of PVP solution is 0.003mol/L;
Two, gac is combined with the coordination of catalyzer: add iron nitrate in the even mixed solution that obtains to step 1, then the rotating speed with 350r/min stirs 8h, obtains title complex finally by crossing sonic oscillation 30min; The mass ratio of the iron nitrate described in the commercial active fruit shell carbon described in the step 1 and the step 2 is 5: 1;
Three, the curing of title complex: then the title complex vacuum-drying 24h under 100 ℃ condition with step 2 obtains naturally cools to the title complex that room temperature obtains solidifying;
Four, thermal treatment: the title complex of the curing that step 3 is obtained is to be warming up to 500 ℃ from room temperature with the temperature rise rate of 30 ℃/min under the protection of argon gas of 30mL/min in airshed, and insulation 1h obtains carbon material under 500 ℃ condition again;
Five, acid treatment: thus the presoma of carbon material obtained with the carbon material that sour circumfluence method treatment step four obtains, 3 pH to the presoma of carbon material of presoma with distilled water centrifuge washing carbon material are 7.0 again, then vacuum-drying 8h under 80 ℃ of conditions namely obtains graphitized stephanoporate material with carbon element.
Wherein, the acid-treated method in the step 5 is that the carbon material that step 4 obtains is dissolved in the salpeter solution, is that 90 ℃ and stirring velocity are cooling for reflux 12h under the condition of 350r/min in temperature then, then naturally cools to the presoma that room temperature obtains carbon material; Wherein, the quality of the carbon material that step 4 obtains and the volume ratio of nitric acid are 0.1g: 100mL, and the concentration of salpeter solution is 6mol/L.
Test two: a kind of method take gac as raw material synthetic graphite porous carbon materials of this test is to realize by the following method:
One, the dispersion of gac: commercial active fruit shell carbon is scattered in the ethanol, then be to stir 3h under the condition of 350r/min to obtain homogeneous reaction liquid at rotating speed, then add PVP solution in the homogeneous reaction liquid, continue under rotating speed is the condition of 350r/min, to stir the 3h liquid that is uniformly mixed; The quality of described commercial active fruit shell carbon and the volume ratio of ethanol are 1g: 100mL; The weight ratio of the solute in commercial active fruit shell carbon and the PVP solution is 10: 1; The volumetric molar concentration of PVP solution is 0.003mol/L;
Two, gac is combined with the coordination of catalyzer: add iron nitrate in the even mixed solution that obtains to step 1, then the rotating speed with 350r/min stirs 8h, obtains title complex finally by crossing sonic oscillation 30min; The mass ratio of the iron nitrate described in the commercial active fruit shell carbon described in the step 1 and the step 2 is 5: 1;
Three, the curing of title complex: then the title complex vacuum-drying 24h under 100 ℃ condition with step 2 obtains naturally cools to the title complex that room temperature obtains solidifying;
Four, thermal treatment: the title complex of the curing that step 3 is obtained is to be warming up to 600 ℃ from room temperature with the temperature rise rate of 30 ℃/min under the protection of argon gas of 30mL/min in airshed, and insulation 1h obtains carbon material under 600 ℃ condition again;
Five, acid treatment: thus the presoma of carbon material obtained with the carbon material that sour circumfluence method treatment step four obtains, again with the presoma of 3 carbon materials of distilled water centrifuge washing to the pH of the presoma of carbon material be 7.0, then vacuum-drying 8h under 80 ℃ of conditions namely obtains graphitized stephanoporate material with carbon element.
Wherein, the acid-treated method in the step 5 is that the carbon material that step 4 obtains is dissolved in the salpeter solution, is that 90 ℃ and stirring velocity are cooling for reflux 12h under the condition of 350r/min in temperature then, then naturally cools to the presoma that room temperature obtains carbon material; Wherein, the quality of the carbon material that step 4 obtains and the volume ratio of nitric acid are 0.1g: 100mL, and the concentration of salpeter solution is 6mol/L.
Test three: a kind of method take gac as raw material synthetic graphite porous carbon materials of this test is to realize by the following method:
One, the dispersion of gac: commercial active fruit shell carbon is scattered in the ethanol, then be to stir 3h under the condition of 350r/min to obtain homogeneous reaction liquid at rotating speed, then add PVP solution in the homogeneous reaction liquid, continue under rotating speed is the condition of 350r/min, to stir the 3h liquid that is uniformly mixed; The quality of described commercial active fruit shell carbon and the volume ratio of ethanol are 1g: 100mL; The weight ratio of the solute in commercial active fruit shell carbon and the PVP solution is 10: 1; The volumetric molar concentration of PVP solution is 0.003mol/L;
Two, gac is combined with the coordination of catalyzer: add iron nitrate in the even mixed solution that obtains to step 1, then the rotating speed with 350r/min stirs 8h, obtains title complex finally by crossing sonic oscillation 30min; The mass ratio of the iron nitrate described in the commercial active fruit shell carbon described in the step 1 and the step 2 is 5: 1;
Three, the curing of title complex: then the title complex vacuum-drying 24h under 100 ℃ condition with step 2 obtains naturally cools to the title complex that room temperature obtains solidifying;
Four, thermal treatment: the title complex of the curing that step 3 is obtained is to be warming up to 700 ℃ from room temperature with the temperature rise rate of 30 ℃/min under the protection of argon gas of 30mL/min in airshed, and insulation 1h obtains carbon material under 700 ℃ condition again;
Five, acid treatment: thus the presoma of carbon material obtained with the carbon material that sour circumfluence method treatment step four obtains, again with the presoma of 3 carbon materials of distilled water centrifuge washing to the pH of the presoma of carbon material be 7.0, then vacuum-drying 8h under 80 ℃ of conditions namely obtains graphitized stephanoporate material with carbon element.
Wherein, the acid-treated method in the step 5 is that the carbon material that step 4 obtains is dissolved in the salpeter solution, is that 90 ℃ and stirring velocity are cooling for reflux 12h under the condition of 350r/min in temperature then, then naturally cools to the presoma that room temperature obtains carbon material; Wherein, the quality of the carbon material that step 4 obtains and the volume ratio of nitric acid are 0.1g: 100mL, and the concentration of salpeter solution is 6mol/L.
Test four: a kind of method take gac as raw material synthetic graphite porous carbon materials of this test is to realize by the following method:
One, the dispersion of gac: commercial active fruit shell carbon is scattered in the ethanol, then be to stir 3h under the condition of 350r/min to obtain homogeneous reaction liquid at rotating speed, then add PVP solution in the homogeneous reaction liquid, continue under rotating speed is the condition of 350r/min, to stir the 3h liquid that is uniformly mixed; The quality of described commercial active fruit shell carbon and the volume ratio of ethanol are 1g: 100mL; The weight ratio of the solute in commercial active fruit shell carbon and the PVP solution is 10: 1; The volumetric molar concentration of PVP solution is 0.003mol/L;
Two, gac is combined with the coordination of catalyzer: add iron nitrate in the even mixed solution that obtains to step 1, then the rotating speed with 350r/min stirs 8h, obtains title complex finally by crossing sonic oscillation 30min; The mass ratio of the iron nitrate described in the commercial active fruit shell carbon described in the step 1 and the step 2 is 5: 1;
Three, the curing of title complex: then the title complex vacuum-drying 24h under 100 ℃ condition with step 2 obtains naturally cools to the title complex that room temperature obtains solidifying;
Four, thermal treatment: the title complex of the curing that step 3 is obtained is to be warming up to 800 ℃ from room temperature with the temperature rise rate of 30 ℃/min under the protection of argon gas of 30mL/min in airshed, and insulation 1h obtains carbon material under 800 ℃ condition again;
Five, acid treatment: thus the presoma of carbon material obtained with the carbon material that sour circumfluence method treatment step four obtains, again with the presoma of 3 carbon materials of distilled water centrifuge washing to the pH of the presoma of carbon material be 7.0, then vacuum-drying 8h under 80 ℃ of conditions namely obtains graphitized stephanoporate material with carbon element.
Wherein, the acid-treated method in the step 5 is that the carbon material that step 4 obtains is dissolved in the salpeter solution, is that 90 ℃ and stirring velocity are cooling for reflux 12h under the condition of 350r/min in temperature then, then naturally cools to the presoma that room temperature obtains carbon material; Wherein, the quality of the carbon material that step 4 obtains and the volume ratio of nitric acid are 0.1g: 100mL, and the concentration of salpeter solution is 6mol/L.
Fig. 2 is test four gained graphitized stephanoporate material with carbon element nitrogen adsorption desorption curves, and the adsorption/desorption curve of the graphitized stephanoporate material with carbon element of this test preparation belongs to IV type thermoisopleth as seen from the figure, thereby can determine that material has meso-hole structure; The prepared graphitized stephanoporate material with carbon element of this test has larger BET specific surface area, is 1677m
2/ g.Fig. 3 is 25000 times of transmission electron microscope pictures of test four gained graphitized stephanoporate material with carbon element, and as shown in Figure 3, the product microscopic appearance is the porous thin slice, has micropore and meso-hole structure.Fig. 4 is test four gained graphitized stephanoporate material with carbon element 400000 times of transmission electron microscope pictures, can be seen clearly that by Fig. 4 the diffraction fringe of 002 crystal face of graphite and its have micropore and meso-hole structure.The generation of graphitized stephanoporate material with carbon element in this test can be described by Fig. 3 and Fig. 4, and the carbon atom that the raising of material degree of graphitization is representing in the material is transformed to the stratiform ordered structure by unformed shape, can improve significantly the specific conductivity of material; Being formed with of meso-hole structure is beneficial to ionogen at contact and the exchange interaction of material internal, thereby material electric conductivity is got a promotion.
Test five: a kind of method take gac as raw material synthetic graphite porous carbon materials of this test is to realize by the following method:
One, the dispersion of gac: commercial active fruit shell carbon is scattered in the ethanol, then be to stir 3h under the condition of 350r/min to obtain homogeneous reaction liquid at rotating speed, then add PVP solution in the homogeneous reaction liquid, continue under rotating speed is the condition of 350r/min, to stir the 3h liquid that is uniformly mixed; The quality of described commercial active fruit shell carbon and the volume ratio of ethanol are 1g: 100mL; The weight ratio of the solute in commercial active fruit shell carbon and the PVP solution is 10: 1; The volumetric molar concentration of PVP solution is 0.003mol/L;
Two, gac is combined with the coordination of catalyzer: add iron nitrate in the even mixed solution that obtains to step 1, then the rotating speed with 350r/min stirs 8h, obtains title complex finally by crossing sonic oscillation 30min; The mass ratio of the iron nitrate described in the commercial active fruit shell carbon described in the step 1 and the step 2 is 5: 1;
Three, the curing of title complex: then the title complex vacuum-drying 24h under 100 ℃ condition with step 2 obtains naturally cools to the title complex that room temperature obtains solidifying;
Four, thermal treatment: the title complex of the curing that step 3 is obtained is to be warming up to 900 ℃ from room temperature with the temperature rise rate of 30 ℃/min under the protection of argon gas of 30mL/min in airshed, and insulation 1h obtains carbon material under 900 ℃ condition again;
Five, acid treatment: thus the presoma of carbon material obtained with the carbon material that sour circumfluence method treatment step four obtains, again with the presoma of 3 carbon materials of distilled water centrifuge washing to the pH of the presoma of carbon material be 7.0, then vacuum-drying 8h under 80 ℃ of conditions namely obtains graphitized stephanoporate material with carbon element.
Wherein, the acid-treated method in the step 5 is that the carbon material that step 4 obtains is dissolved in the salpeter solution, is that 90 ℃ and stirring velocity are cooling for reflux 12h under the condition of 350r/min in temperature then, then naturally cools to the presoma that room temperature obtains carbon material; Wherein, the quality of the carbon material that step 4 obtains and the volume ratio of nitric acid are 0.1g: 100mL, and the concentration of salpeter solution is 6mol/L.
Test six: a kind of method take gac as raw material synthetic graphite porous carbon materials of this test is to realize by the following method:
One, the dispersion of gac: commercial active fruit shell carbon is scattered in the ethanol, then be to stir 3h under the condition of 350r/min to obtain homogeneous reaction liquid at rotating speed, then add PVP solution in the homogeneous reaction liquid, continue under rotating speed is the condition of 350r/min, to stir the 3h liquid that is uniformly mixed; The quality of described commercial active fruit shell carbon and the volume ratio of ethanol are 1g: 100mL; The weight ratio of the solute in commercial active fruit shell carbon and the PVP solution is 10: 1; The volumetric molar concentration of PVP solution is 0.003mol/L;
Two, gac is combined with the coordination of catalyzer: add iron nitrate in the even mixed solution that obtains to step 1, then the rotating speed with 350r/min stirs 8h, obtains title complex finally by crossing sonic oscillation 30min; The mass ratio of the iron nitrate described in the commercial active fruit shell carbon described in the step 1 and the step 2 is 5: 1;
Three, the curing of title complex: then the title complex vacuum-drying 24h under 100 ℃ condition with step 2 obtains naturally cools to the title complex that room temperature obtains solidifying;
Four, thermal treatment: the title complex of the curing that step 3 is obtained is to be warming up to 1000 ℃ from room temperature with the temperature rise rate of 30 ℃/min under the protection of argon gas of 30mL/min in airshed, and insulation 1h obtains carbon material under 1000 ℃ condition again;
Five, acid treatment: thus the presoma of carbon material obtained with the carbon material that sour circumfluence method treatment step four obtains, again with the presoma of 3 carbon materials of distilled water centrifuge washing to the pH of the presoma of carbon material be 7.0, then vacuum-drying 8h under 80 ℃ of conditions namely obtains graphitized stephanoporate material with carbon element.
Wherein, the acid-treated method in the step 5 is that the carbon material that step 4 obtains is dissolved in the salpeter solution, is that 90 ℃ and stirring velocity are cooling for reflux 12h under the condition of 350r/min in temperature then, then naturally cools to the presoma that room temperature obtains carbon material; Wherein, the quality of the carbon material that step 4 obtains and the volume ratio of nitric acid are 0.1g: 100mL, and the concentration of salpeter solution is 6mol/L.
Fig. 1 is the XRD figure spectrum, a is the XRD figure spectrum of test one prepared graphitized stephanoporate material with carbon element among the figure, b is the XRD figure spectrum of test two prepared graphitized stephanoporate material with carbon element among the figure, c is the XRD figure spectrum of test three prepared graphitized stephanoporate material with carbon element among the figure, d is the XRD figure spectrum of test four prepared graphitized stephanoporate material with carbon element among the figure, e is the XRD figure spectrum of test five prepared graphitized stephanoporate material with carbon element among the figure, f is the XRD figure spectrum of test six prepared graphitized stephanoporate material with carbon element among the figure, wherein, ▲ be graphite 002 crystal face of graphitized stephanoporate material with carbon element.The characteristic diffraction peak of graphite 002 crystal face has appearred in the graphitized stephanoporate material with carbon element of this test preparation as shown in Figure 1, has preferably degree of graphitization, and degree of graphitization raises with thermal treatment temp and strengthens, thereby the degree of graphitization that graphitized stephanoporate material with carbon element can be described can be regulated by the change to thermal treatment temp.
Test seven: a kind of method take gac as raw material synthetic graphite porous carbon materials of this test is to realize by the following method:
One, the dispersion of gac: commercial cocoanut active charcoal is scattered in the distilled water, then be to stir 9h under the condition of 150r/min to obtain homogeneous reaction liquid at rotating speed, then add SDS solution in the homogeneous reaction liquid, continue under rotating speed is the condition of 150r/min, to stir the 1h liquid that is uniformly mixed; The quality of described commercial cocoanut active charcoal and the volume ratio of distilled water are 5g: 100mL; The weight ratio of the solute in commercial cocoanut active charcoal and the SDS solution is 100: 1; The volumetric molar concentration of SDS solution is 0.005mol/L;
Two, gac is combined with the coordination of catalyzer: add rose vitriol in the even mixed solution that obtains to step 1, then the rotating speed with 150r/min stirs 4h, obtains title complex finally by crossing sonic oscillation 120min; The mass ratio of the rose vitriol described in the commercial cocoanut active charcoal described in the step 1 and the step 2 is 10: 1;
Three, the curing of title complex: then the title complex vacuum-drying 4h under 80 ℃ condition with step 2 obtains naturally cools to the title complex that room temperature obtains solidifying;
Four, thermal treatment: the title complex of the curing that step 3 is obtained is to be warming up to 1000 ℃ from room temperature with the temperature rise rate of 15 ℃/min under the protection of carbon dioxide of 200mL/min in airshed, and insulation 6h obtains carbon material under 1000 ℃ condition again;
Five, acid treatment: thus the presoma of carbon material obtained with the carbon material that sour circumfluence method treatment step four obtains, again with the presoma of 3 carbon materials of distilled water centrifuge washing to the pH of the presoma of carbon material be 7.0, then vacuum-drying 10h under 60 ℃ of conditions namely obtains graphitized stephanoporate material with carbon element.
Wherein, acid-treated method in the step 5 is in the carbon material vitriolization and mixed in hydrochloric acid acid solution that step 4 is obtained, then be that 80 ℃ and stirring velocity are cooling for reflux 6h under the condition of 250r/min in temperature, then naturally cool to the presoma that room temperature obtains carbon material; Wherein, the quality of the carbon material that step 4 obtains and the volume ratio of mixed acid solution are 0.5g: 100mL, and the concentration of sulfuric acid and mixed in hydrochloric acid acid solution is 2mol/L, and the volume ratio of sulfuric acid and hydrochloric acid is 1: 1, the massfraction of sulfuric acid is 98%, and the massfraction of hydrochloric acid is 37%.
Fig. 5 is 300000 times of transmission electron microscope pictures of test seven gained graphitized stephanoporate material with carbon element.As shown in Figure 5, the product microscopic appearance is the porous thin slice, has micropore and meso-hole structure, can clearly demonstrate the diffraction fringe of 002 crystal face of graphite.This figure illustrates the generation of graphitized stephanoporate material with carbon element in this test, and the carbon atom that the raising of material degree of graphitization is representing in the material is transformed to the stratiform ordered structure by unformed shape, can improve significantly the specific conductivity of material.Being formed with of meso-hole structure is beneficial to ionogen at contact and the exchange interaction of material internal, thereby material electric conductivity is got a promotion.
Test eight: a kind of method take gac as raw material synthetic graphite porous carbon materials of this test is to realize by the following method:
One, the dispersion of gac: commercial active fruit shell carbon is scattered in the ethanol, then be to stir 6h under the condition of 250r/min to obtain homogeneous reaction liquid at rotating speed, then add SDBS solution in the homogeneous reaction liquid, continue under rotating speed is the condition of 250r/min, to stir the 2h liquid that is uniformly mixed; The quality of described commercial active fruit shell carbon and the volume ratio of ethanol are 2g: 100mL; The weight ratio of the solute in commercial active fruit shell carbon and the SDBS solution is 50: 1; The volumetric molar concentration of SDBS solution is 0.001mol/L;
Two, gac is combined with the coordination of catalyzer: add single nickel salt in the even mixed solution that obtains to step 1, then the rotating speed with 250r/min stirs 6h, obtains title complex finally by crossing sonic oscillation 90min; The mass ratio of the single nickel salt described in the commercial active fruit shell carbon described in the step 1 and the step 2 is 3: 1;
Three, the curing of title complex: then the title complex vacuum-drying 12h under 90 ℃ condition with step 2 obtains naturally cools to the title complex that room temperature obtains solidifying;
Four, thermal treatment: the title complex of the curing that step 3 is obtained is to be warming up to 900 ℃ from room temperature with the temperature rise rate of 20 ℃/min under the protection of argon gas of 50mL/min in airshed, and insulation 4h obtains carbon material under 900 ℃ condition again;
Five, acid treatment: thus the presoma of carbon material obtained with the carbon material that sour circumfluence method treatment step four obtains, again with the presoma of 3 carbon materials of distilled water centrifuge washing to the pH of the presoma of carbon material be 7.0, then vacuum-drying 4h under 90 ℃ of conditions namely obtains graphitized stephanoporate material with carbon element.
Wherein, the acid-treated method in the step 5 is that the carbon material that step 4 obtains is dissolved in the salpeter solution, is that 70 ℃ and stirring velocity are cooling for reflux 10h under the condition of 150r/min in temperature then, then naturally cools to the presoma that room temperature obtains carbon material; Wherein, the quality of the carbon material that step 4 obtains and the volume ratio of salpeter solution are 1g: 100mL, and the concentration of salpeter solution is 4mol/L.
Fig. 6 is 400000 times of transmission electron microscope pictures of test eight gained graphitized stephanoporate material with carbon element.As shown in Figure 6, the product microscopic appearance is the porous thin slice, has micropore and meso-hole structure, can clearly demonstrate the diffraction fringe of 002 crystal face of graphite; This figure illustrates the generation of graphitized stephanoporate material with carbon element in this test, and the carbon atom that the raising of material degree of graphitization is representing in the material is transformed to the stratiform ordered structure by unformed shape, can improve significantly the specific conductivity of material.Being formed with of meso-hole structure is beneficial to ionogen at contact and the exchange interaction of material internal, thereby material electric conductivity is got a promotion.
Claims (10)
1. one kind take the preparation method of gac as raw material synthetic graphite porous carbon materials, it is characterized in that a kind ofly carrying out according to the following steps take the preparation method of gac as raw material synthetic graphite porous carbon materials:
One, the dispersion of gac: gac is evenly mixed with solvent, then under rotating speed is the condition of 100r/min～350r/min, stir 3h～9h and obtain homogeneous reaction liquid, in homogeneous reaction liquid, add surfactant soln, continue under rotating speed is the condition of 100r/min～350r/min, to stir 1h～3h liquid that is uniformly mixed; The quality of described gac and the volume ratio of solvent are (0.1g～10g): 100mL; The mass ratio of the solute in described gac and the surfactant soln is (10～100): 1; The volumetric molar concentration of described surfactant soln is 0.0005mol/L～0.05mol/L;
Two, gac is combined with the coordination of catalyzer: add metal catalyst in the even mixed solution that obtains to step 1, then the rotating speed with 100r/min～350r/min stirs 4h～8h, obtains title complex finally by crossing sonic oscillation 30min～120min; The mass ratio of the gac described in the metal catalyst described in the step 2 and the step 1 is 1: (1～10);
Three, the curing of title complex: then the title complex vacuum-drying 2h～24h under 20 ℃～100 ℃ condition with step 2 obtains naturally cools to the title complex that room temperature obtains solidifying;
Four, thermal treatment: the title complex of the curing that step 3 is obtained is to be warming up to 500 ℃～1000 ℃ from room temperature with the temperature rise rate of 5 ℃/min～30 ℃/min under the protection of rare gas element of 30mL/min～200mL/min in airshed, is incubated 1h～6h again under temperature is 500 ℃～1000 ℃ condition and obtains carbon material;
Five, acid treatment: the carbon material that obtains with sour circumfluence method treatment step four, obtain the presoma of carbon material, again with the presoma of 2～4 carbon materials of distilled water centrifuge washing to the pH of the presoma of carbon material be 6.8～7.2, then be vacuum-drying 5h～10h under 60 ℃～80 ℃ conditions in temperature, namely obtain graphitized stephanoporate material with carbon element.
2. according to claim 1 a kind of take the preparation method of gac as raw material synthetic graphite porous carbon materials, it is characterized in that the solvent described in the step 1 is a kind of in distilled water, ethanol, ethylene glycol and the Virahol or several mixture wherein; Gac described in the step 1 is a kind of in cocoanut active charcoal, active fruit shell carbon, wood activated charcoal and the coal mass active carbon or several mixture wherein; The solute of the surfactant soln described in the step 1 is a kind of in polyvinylpyrrolidone, sodium lauryl sulphate and the Sodium dodecylbenzene sulfonate or several mixture wherein, and the solvent of surfactant soln is deionized water.
3. according to claim 1 a kind of take the preparation method of gac as raw material synthetic graphite porous carbon materials, it is characterized in that in the step 1 gac evenly being mixed with solvent, then under rotating speed is the condition of 200r/min～300r/min, stir 5h～7h and obtain homogeneous reaction liquid, then in homogeneous reaction liquid, add surfactant soln, continue under rotating speed is the condition of 200r/min～300r/min, to stir 1h～3h liquid that is uniformly mixed.
4. according to claim 1 a kind of take the preparation method of gac as raw material synthetic graphite porous carbon materials, the volume ratio that it is characterized in that the quality of the gac described in the step 1 and solvent is (3g～7g): 100mL; The mass ratio of the solute in the gac described in the step 1 and the surfactant soln is (30～70): 1; The volumetric molar concentration of the surfactant soln described in the step 1 is 0.005mol/L～0.01mol/L.
5. according to claim 1 a kind of take the preparation method of gac as raw material synthetic graphite porous carbon materials, it is characterized in that the metal catalyst described in the step 2 is a kind of in Iron nitrate, ferrous sulfate, iron protochloride, iron nitrate, ferric sulfate, iron(ic) chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobalt chloride, Cobaltous diacetate, single nickel salt, nickelous nitrate, nickelous chloride and the nickel acetate or several mixture wherein.
6. according to claim 1 a kind of take the preparation method of gac as raw material synthetic graphite porous carbon materials, the mass ratio that it is characterized in that the gac described in the metal catalyst described in the step 2 and the step 1 is 1: (4～6).
7. according to claim 1 a kind of take the preparation method of gac as raw material synthetic graphite porous carbon materials; the title complex that it is characterized in that the curing that in the step 4 step 3 obtained is to be warming up to 700 ℃～900 ℃ from room temperature with the temperature rise rate of 10 ℃/min～20 ℃/min under the protection of rare gas element of 80mL/min～150mL/min in airshed, is incubated 3h～5h again under temperature is 700 ℃～900 ℃ condition and obtains carbon material.
8. according to claim 1 a kind of take the preparation method of gac as raw material synthetic graphite porous carbon materials, it is characterized in that the rare gas element described in the step 4 is a kind of in nitrogen, argon gas and the carbonic acid gas or two kinds mixed gas wherein.
9. according to claim 1 a kind of take the preparation method of gac as raw material synthetic graphite porous carbon materials, it is characterized in that the carbon material that obtains with sour circumfluence method treatment step four in the step 5, obtain washing lotion, again with the distilled water wash washing lotion to the pH of washing lotion be 6.8～7.2, then be vacuum-drying 7h～9h under 60 ℃～80 ℃ conditions in temperature, namely obtain graphitized stephanoporate material with carbon element.
10. according to claim 1 a kind of take the preparation method of gac as raw material synthetic graphite porous carbon materials, it is characterized in that the sour circumfluence method described in the step 5 carries out according to the following steps:
The carbon material that step 4 is obtained is dissolved in the acid solution, is that 50 ℃～90 ℃ and stirring velocity are cooling for reflux 1h～12h under the condition of 100r/min～350r/min in temperature then, then naturally cools to the presoma that room temperature obtains carbon material; The quality of described carbon material and the volume ratio of acid solution are (0.1g～10g): 100mL; The concentration of described acid solution is 0.1mol/L～6mol/L, and wherein said acid solution is a kind of in hydrochloric acid soln, salpeter solution, sulphuric acid soln and the phosphoric acid solution or several mixed acid solution wherein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310276905.7A CN103318871B (en) | 2013-07-03 | 2013-07-03 | Preparation method for synthesizing graphite porous carbon material with activated carbon serving as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310276905.7A CN103318871B (en) | 2013-07-03 | 2013-07-03 | Preparation method for synthesizing graphite porous carbon material with activated carbon serving as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103318871A true CN103318871A (en) | 2013-09-25 |
| CN103318871B CN103318871B (en) | 2014-12-10 |
Family
ID=49187972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310276905.7A Expired - Fee Related CN103318871B (en) | 2013-07-03 | 2013-07-03 | Preparation method for synthesizing graphite porous carbon material with activated carbon serving as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103318871B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104071786A (en) * | 2014-07-18 | 2014-10-01 | 福州大学 | Preparation method for graphitized activated carbon with high specific surface area |
| CN105280918A (en) * | 2014-10-27 | 2016-01-27 | 湖南摩根海容新材料有限责任公司 | Preparation method of isotropic graphite material |
| CN107317011A (en) * | 2017-06-28 | 2017-11-03 | 合肥工业大学 | A kind of preparation method of the ordered porous carbon coating silicon nano composite material of N doping |
| CN107739774A (en) * | 2017-06-17 | 2018-02-27 | 常州兆威不锈钢有限公司 | A kind of preparation method for making steel special carburant |
| CN107799771A (en) * | 2017-11-16 | 2018-03-13 | 湖州创亚动力电池材料有限公司 | A kind of carbon negative pole material for lithium ion battery and preparation method thereof |
| CN107814385A (en) * | 2017-11-16 | 2018-03-20 | 华中科技大学 | A kind of method for handling industrial wastewater using biomass char and preparing graphite mould porous carbon materials |
| CN108123103A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | It is graphitized activated carbon base compound additive and preparation and lead carbon battery cathode and application |
| CN109301225A (en) * | 2018-10-16 | 2019-02-01 | 周昊宸 | It is a kind of with degree of graphitization, the graphite cathode material of the double gradient-structures in aperture and its preparation and application |
| CN109467082A (en) * | 2018-12-18 | 2019-03-15 | 济南大学 | A kind of preparation method being graphitized the derivative carbon electrode material of porous corncob |
| CN109585803A (en) * | 2018-10-16 | 2019-04-05 | 湖南宸宇富基新能源科技有限公司 | A kind of artificial plumbago negative pole material and its preparation and application with gradient-structure |
| CN111732097A (en) * | 2020-06-17 | 2020-10-02 | 武汉大学 | Preparation method and application of large-specific-surface-area graphitized carbon |
| CN112250063A (en) * | 2020-10-14 | 2021-01-22 | 西安工程大学 | Method for promoting graphitization of wood biochar at low temperature |
| CN112635761A (en) * | 2019-09-24 | 2021-04-09 | 广隆光电科技股份有限公司 | Negative electrode lead paste composition of lead-acid battery, negative plate and lead-acid battery |
| CN112919466A (en) * | 2021-03-02 | 2021-06-08 | 北海艾米碳材料技术研发有限公司 | Active carbon graphene modification method for preparing super capacitor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3917806A (en) * | 1973-09-27 | 1975-11-04 | Kureha Chemical Ind Co Ltd | Method for the preparation of carbon moldings and activated carbon molding therefrom |
| CN1309620A (en) * | 1998-07-20 | 2001-08-22 | 康宁股份有限公司 | Method of making mesoporous carbon using pore formers |
| WO2012070573A1 (en) * | 2010-11-22 | 2012-05-31 | Ｊｘ日鉱日石エネルギー株式会社 | Composite container for storage of hydrogen, and hydrogen-filling method |
-
2013
- 2013-07-03 CN CN201310276905.7A patent/CN103318871B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3917806A (en) * | 1973-09-27 | 1975-11-04 | Kureha Chemical Ind Co Ltd | Method for the preparation of carbon moldings and activated carbon molding therefrom |
| CN1309620A (en) * | 1998-07-20 | 2001-08-22 | 康宁股份有限公司 | Method of making mesoporous carbon using pore formers |
| WO2012070573A1 (en) * | 2010-11-22 | 2012-05-31 | Ｊｘ日鉱日石エネルギー株式会社 | Composite container for storage of hydrogen, and hydrogen-filling method |
Non-Patent Citations (1)
| Title |
|---|
| 吴雪艳等: "多孔碳材料的制备", 《化学进展》, vol. 24, 31 March 2012 (2012-03-31), pages 262 - 274 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104071786B (en) * | 2014-07-18 | 2016-02-24 | 福州大学 | A kind of preparation method of greying gac |
| CN104071786A (en) * | 2014-07-18 | 2014-10-01 | 福州大学 | Preparation method for graphitized activated carbon with high specific surface area |
| CN105280918B (en) * | 2014-10-27 | 2018-04-10 | 湖南摩根海容新材料有限责任公司 | A kind of preparation method of isotropic graphite material |
| CN105280918A (en) * | 2014-10-27 | 2016-01-27 | 湖南摩根海容新材料有限责任公司 | Preparation method of isotropic graphite material |
| CN108123103A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | It is graphitized activated carbon base compound additive and preparation and lead carbon battery cathode and application |
| CN107739774A (en) * | 2017-06-17 | 2018-02-27 | 常州兆威不锈钢有限公司 | A kind of preparation method for making steel special carburant |
| CN107739774B (en) * | 2017-06-17 | 2019-08-09 | 江苏省镔鑫钢铁集团有限公司 | A kind of preparation method for making steel dedicated carburant |
| CN107317011A (en) * | 2017-06-28 | 2017-11-03 | 合肥工业大学 | A kind of preparation method of the ordered porous carbon coating silicon nano composite material of N doping |
| CN107814385A (en) * | 2017-11-16 | 2018-03-20 | 华中科技大学 | A kind of method for handling industrial wastewater using biomass char and preparing graphite mould porous carbon materials |
| CN107799771A (en) * | 2017-11-16 | 2018-03-13 | 湖州创亚动力电池材料有限公司 | A kind of carbon negative pole material for lithium ion battery and preparation method thereof |
| CN109301225A (en) * | 2018-10-16 | 2019-02-01 | 周昊宸 | It is a kind of with degree of graphitization, the graphite cathode material of the double gradient-structures in aperture and its preparation and application |
| CN109585803A (en) * | 2018-10-16 | 2019-04-05 | 湖南宸宇富基新能源科技有限公司 | A kind of artificial plumbago negative pole material and its preparation and application with gradient-structure |
| CN109467082A (en) * | 2018-12-18 | 2019-03-15 | 济南大学 | A kind of preparation method being graphitized the derivative carbon electrode material of porous corncob |
| CN112635761A (en) * | 2019-09-24 | 2021-04-09 | 广隆光电科技股份有限公司 | Negative electrode lead paste composition of lead-acid battery, negative plate and lead-acid battery |
| CN111732097A (en) * | 2020-06-17 | 2020-10-02 | 武汉大学 | Preparation method and application of large-specific-surface-area graphitized carbon |
| CN112250063A (en) * | 2020-10-14 | 2021-01-22 | 西安工程大学 | Method for promoting graphitization of wood biochar at low temperature |
| CN112919466A (en) * | 2021-03-02 | 2021-06-08 | 北海艾米碳材料技术研发有限公司 | Active carbon graphene modification method for preparing super capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103318871B (en) | 2014-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103318871B (en) | Preparation method for synthesizing graphite porous carbon material with activated carbon serving as raw material | |
| CN105152281B (en) | The preparation method of the classifying porous carbon material structure capacitance desalination electrode of core shell structure | |
| CN103794806B (en) | A kind of lithium air battery positive electrode Nano-iron nitride-carbon composite catalytic agent and preparation method thereof | |
| CN102130334B (en) | Graphene-based nano iron oxide composite material and preparation method thereof | |
| CN107585758B (en) | A kind of graphene aerogel and its preparation method and application | |
| CN102623693B (en) | High specific capacity spindle-shaped ferroferric oxide/carbon nano composite material for negative electrode of lithium ion battery | |
| CN106129387B (en) | A kind of iron manganese phosphate for lithium/three-dimensional carbon skeleton/carbon composite preparation method | |
| CN104098083A (en) | Method for preparing porous nano carbon materials with biomass serving as carbon source | |
| CN102757034A (en) | Method for preparing nitrogen-rich porous carbon material | |
| CN102447112A (en) | Silicon-carbon composite material, preparation method thereof and cathode material containing same as well as lithium ion battery | |
| CN103964412A (en) | Preparation method of nitrogen-doped porous-structure carbon material | |
| CN105271203A (en) | Porous co-doped graphene and preparation method thereof | |
| CN105977479B (en) | A kind of preparation method of octahedron porous silica molybdenum and its application in lithium ion battery | |
| CN102709057A (en) | Method for preparing composite of grapheme with different oxidation degrees and manganese dioxide | |
| CN109748282B (en) | Method for preparing nano silicon carbide at low temperature | |
| CN105405680B (en) | A kind of preparation method of carbon particle/manganese dioxide composite electrode material | |
| CN103400969B (en) | A kind of preparation method of high-performance lithium battery anode material of lithium iron phosphate/carbon composite powder | |
| CN106486295A (en) | The preparation method of the Graphene of high specific capacitance/high surface carbon composite | |
| CN102956359A (en) | Manganese dioxide/ferric oxide nanometer composite material as well as preparation method and application thereof | |
| CN107611380A (en) | A kind of preparation method of nickel oxide/stereochemical structure graphene composite material | |
| CN105321726B (en) | High magnification active carbon/Activated Graphite alkene combination electrode material and preparation method thereof | |
| CN106129388B (en) | A kind of LiFePO4/three-dimensional carbon skeleton/carbon composite preparation method | |
| CN106602023A (en) | Method for in-situ synthesis of graphite phase carbon nitride-copper oxide composite material | |
| CN104528712B (en) | A kind of preparation method of graphene/metal oxide three-dimensional composite material | |
| CN112017868B (en) | Mesoporous hollow carbon micron cage material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141210 Termination date: 20180703 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |