CN103318871B - 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
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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
Due to the active demand of human society to new function material, carbon material more and more receives people's concern.The carbon material relatively at present with 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.Carbon material has been widely used in the fields such as the energy, environment, machinery, electronics at present.
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, cheap, produce simple and easy.Microcrystalline carbon irregular alignment in 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 current absorbent charcoal material, the irregular alignment of its carbon crystalline substance makes it 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; Aperture is less 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 from greying and the surface tissue improvement of material, start with.Graphite crystal stratiform ordered structure has more good physics, chemical property, as good electrochemical stability and good electroconductibility.It by gac greying, is the feasible way that strengthens its electroconductibility.Realizing at present the preparation of greying gac is mainly greying in presoma carbonization process, as solid-phase pyrolysis, and chemical Vapor deposition process etc.Another feasible method is that moulding carbon material is carried out to graphitization processing, comprises arc discharge method, high-temperature activation method etc.
Many researchers adopts chemical Vapor deposition process or high-temperature activation legal system for graphitized carbon material in recent years.The general pattern of chemical meteorology deposition method products obtained therefrom, size be homogeneous comparatively, can effectively control 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.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 to the orderly conversion to crystal structure of graphite by turbostratic.But this kind of method is comparatively harsh for the selection of raw material, mostly is the chemical product that mineralizes that cost is higher, and recyclability is poor, and exploitation and extractive process are unfavorable for environmental protection, while complex process, equipment requirements is high, and productive rate is low, poor stability.In sum, explore and for expanding graphitization nano carbon material industryization, apply significant to the regulation and control of graphitization nano carbon material degree of graphitization, the comprehensive improved effective ways of surface tissue.Existing absorbent charcoal material electroconductibility is poor, 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 poor, aperture is less, complicated process of preparation, synthesis temperature are higher, the technical problem that is not suitable for scale operation, thereby a kind of preparation method of gac as raw material synthetic graphite porous carbon materials of take is provided.
Of the present inventionly a kind ofly take the preparation method that gac is raw material synthetic graphite porous carbon materials and carry out according to the following steps:
One, the dispersion of gac: gac is evenly mixed with solvent, then under the condition that is 100r/min～350r/min at rotating speed, stir 3h～9h and obtain homogeneous reaction liquid, in homogeneous reaction liquid, add surfactant soln, continue to stir under the condition be 100r/min～350r/min at rotating speed 1h～3h liquid that is uniformly mixed; The quality of described gac and the volume ratio of solvent are (0.1g～10g): 100mL; Described gac and the mass ratio of the solute in surfactant soln are (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: in the even mixed solution obtaining to step 1, add metal catalyst, then the rotating speed with 100r/min～350r/min stirs 4h～8h, finally by crossing sonic oscillation 30min～120min, obtains title complex; The mass ratio of the gac described in the metal catalyst described in step 2 and step 1 is 1: (1～10);
Three, solidifying of title complex: the title complex that step 2 is obtained is vacuum-drying 2h～24h under the condition of 20 ℃～100 ℃, then naturally cools to room temperature and obtains curing title complex;
Four, thermal treatment: be warming up to 500 ℃～1000 ℃ from room temperature with the temperature rise rate of 5 ℃/min～30 ℃/min under the protection of the rare gas element that the curing title complex that step 3 is obtained is 30mL/min～200mL/min in airshed, then be to be incubated 1h～6h under the condition of 500 ℃～1000 ℃ to obtain carbon material in temperature;
Five, acid treatment: the carbon material obtaining 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 in temperature, be vacuum-drying 5h～10h under 60 ℃～80 ℃ conditions, obtain graphitized stephanoporate material with carbon element.
The present invention has the following advantages:
One, the present invention be take gac as raw material synthetic graphite porous carbon materials, and preparation technology is simple, and chemical property has improved 20%～40%.
Two, compare the thermal treatment temp of 2000 ℃～4000 ℃ with traditional industry method, the present invention synthesizes under the lower thermal treatment temp of 500 ℃～1000 ℃, and the reduction of energy consumption reaches 60%～85%, has improved security, is applicable to scale operation;
Three, the present invention realizes the regulation and control to gac degree of graphitization by changing consumption and the thermal treatment temp of graphitization catalyst;
Four, the synthetic graphitized stephanoporate material with carbon element of the present invention is by making microcrystalline carbon be transformed to graphite laminate ordered structure by irregular alignment, and surface has meso-hole structure, electronics, ion transport ability have been strengthened, physics, chemical stability are good, make material can be widely used in multiple electrochemical energy devices.
Accompanying drawing explanation
Fig. 1 is XRD figure spectrum, the XRD figure spectrum that in figure, a is the prepared graphitized stephanoporate material with carbon element of test one, the XRD figure spectrum that in figure, b is the prepared graphitized stephanoporate material with carbon element of test two, the XRD figure spectrum that in figure, c is the prepared graphitized stephanoporate material with carbon element of test three, the XRD figure spectrum that in figure, d is the prepared graphitized stephanoporate material with carbon element of test four, the XRD figure spectrum that in figure, e is the prepared graphitized stephanoporate material with carbon element of test five, the XRD figure spectrum that in figure, f is the prepared graphitized stephanoporate material with carbon element of test six, in figure ▲ 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 present embodiment take the preparation method that gac is raw material synthetic graphite porous carbon materials and carry out according to the following steps:
One, the dispersion of gac: gac is evenly mixed with solvent, then under the condition that is 100r/min～350r/min at rotating speed, stir 3h～9h and obtain homogeneous reaction liquid, in homogeneous reaction liquid, add surfactant soln, continue to stir under the condition be 100r/min～350r/min at rotating speed 1h～3h liquid that is uniformly mixed; The quality of described gac and the volume ratio of solvent are (0.1g～10g): 100mL; Described gac and the mass ratio of the solute in surfactant soln are (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: in the even mixed solution obtaining to step 1, add metal catalyst, then the rotating speed with 100r/min～350r/min stirs 4h～8h, finally by crossing sonic oscillation 30min～120min, obtains title complex; The mass ratio of the gac described in the metal catalyst described in step 2 and step 1 is 1: (1～10);
Three, solidifying of title complex: the title complex that step 2 is obtained is vacuum-drying 2h～24h under the condition of 20 ℃～100 ℃, then naturally cools to room temperature and obtains curing title complex;
Four, thermal treatment: be warming up to 500 ℃～1000 ℃ from room temperature with the temperature rise rate of 5 ℃/min～30 ℃/min under the protection of the rare gas element that the curing title complex that step 3 is obtained is 30mL/min～200mL/min in airshed, then be to be incubated 1h～6h under the condition of 500 ℃～1000 ℃ to obtain carbon material in temperature;
Five, acid treatment: the carbon material obtaining 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 in temperature, be vacuum-drying 5h～10h under 60 ℃～80 ℃ conditions, obtain graphitized stephanoporate material with carbon element.
Present embodiment has the following advantages:
One, the present invention be take gac as raw material synthetic graphite porous carbon materials, and preparation technology is simple, and chemical property has improved 20%～40%.
Two, compare the thermal treatment temp of 2000 ℃～4000 ℃ with traditional industry method, the present invention synthesizes under the lower thermal treatment temp of 500 ℃～1000 ℃, and the reduction of energy consumption reaches 60%～85%, has improved security, is applicable to scale operation;
Three, the present invention realizes the regulation and control to gac degree of graphitization by changing consumption and the thermal treatment temp of graphitization catalyst;
Four, the synthetic graphitized stephanoporate material with carbon element of the present invention is by making microcrystalline carbon be transformed to graphite laminate ordered structure by irregular alignment, and surface has meso-hole structure, electronics, ion transport ability have been strengthened, physics, chemical stability are good, make material can be widely used in multiple electrochemical energy devices.
Embodiment two: present embodiment is different from embodiment one: the solvent described in step 1 is a kind of in distilled water, ethanol, ethylene glycol and Virahol or several mixture wherein; Gac described in step 1 is a kind of in cocoanut active charcoal, active fruit shell carbon, wood activated charcoal and coal mass active carbon or several mixture wherein; The solute of the surfactant soln described in step 1 is a kind of in polyvinylpyrrolidone, sodium lauryl sulphate and Sodium dodecylbenzene sulfonate or several mixture wherein, and the solvent of surfactant soln is deionized water.Other is identical with embodiment one.
Embodiment three: present embodiment is different from one of embodiment one or two: in step 1, gac is evenly mixed with solvent, then under the condition that is 200r/min～300r/min at rotating speed, stir 5h～7h and obtain homogeneous reaction liquid, then in homogeneous reaction liquid, add surfactant soln, continue to stir under the condition be 200r/min～300r/min at rotating speed 1h～3h liquid that is uniformly mixed.Other is identical with one of embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: the quality of the gac described in step 1 and the volume ratio of solvent are (3g～7g): 100mL; The mass ratio of the solute in the gac described in step 1 and surfactant soln is (30～70): 1; The volumetric molar concentration of the surfactant soln described in step 1 is 0.005mol/L～0.01mol/L.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: the metal catalyst described in 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 nickel acetate or several mixture wherein.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five: the mass ratio of the gac described in the metal catalyst described in step 2 and step 1 is 1: (4～6).Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six: be warming up to 700 ℃～900 ℃ from room temperature with the temperature rise rate of 10 ℃/min～20 ℃/min under the protection of the rare gas element that the curing title complex in step 4, step 3 being obtained is 80mL/min～150mL/min in airshed, then be to be incubated 3h～5h under the condition of 700 ℃～900 ℃ to obtain carbon material in temperature.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven: the rare gas element described in step 4 is a kind of in nitrogen, argon gas and carbonic acid gas or the mixed gas of two kinds wherein.Other is identical with one of embodiment one to seven.
When the rare gas element described in present embodiment is the mixed gas of two kinds, pass into mode as follows: 1, when rare gas element is the mixed gas of nitrogen and argon gas, the airshed of nitrogen of take passes into nitrogen and argon gas as 80mL/min～150mL/min as 80mL/min～150mL/min and the airshed of argon gas of take simultaneously.2,, when rare gas element is the mixed gas of nitrogen and carbonic acid gas, the airshed of nitrogen of take passes into nitrogen and carbonic acid gas as 80mL/min～150mL/min as 80mL/min～150mL/min and the airshed of carbonic acid gas of take simultaneously.3,, when rare gas element is the mixed gas of argon gas and carbonic acid gas, the airshed of argon gas of take passes into argon gas and carbonic acid gas as 80mL/min～150mL/min as 80mL/min～150mL/min and the airshed of carbonic acid gas of take simultaneously.
Embodiment nine: present embodiment is different from one of embodiment one to eight: the carbon material obtaining with sour circumfluence method treatment step four in step 5, obtain washing lotion, again with distilled water wash washing lotion to the pH of washing lotion be 6.8～7.2, then in temperature, be vacuum-drying 7h～9h under 60 ℃～80 ℃ conditions, obtain graphitized stephanoporate material with carbon element.Other is identical with one of embodiment one to eight.
Embodiment ten: present embodiment is different from one of embodiment one to nine: the sour circumfluence method described in step 5 is carried out according to the following steps:
The carbon material that step 4 is obtained is dissolved in acid solution, in temperature, is then cooling for reflux 1h～12h under 50 ℃～90 ℃ and the stirring velocity condition that is 100r/min～350r/min, 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 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: it is to realize by the following method that this test a kind of be take the method that gac is raw material synthetic graphite porous carbon materials:
One, the dispersion of gac: business active fruit shell carbon is scattered in ethanol, then under the condition that is 350r/min at rotating speed, stir 3h and obtain homogeneous reaction liquid, then in homogeneous reaction liquid, add PVP solution, continue to stir under the condition be 350r/min at rotating speed the 3h liquid that is uniformly mixed; The described quality of business active fruit shell carbon and the volume ratio of ethanol are 1g: 100mL; The weight ratio of the solute in business active fruit shell carbon and 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: in the even mixed solution obtaining to step 1, add iron nitrate, then the rotating speed with 350r/min stirs 8h, finally by crossing sonic oscillation 30min, obtains title complex; The mass ratio of the iron nitrate described in the business active fruit shell carbon described in step 1 and step 2 is 5: 1;
Three, solidifying of title complex: the title complex that step 2 is obtained is vacuum-drying 24h under the condition of 100 ℃, then naturally cools to room temperature and obtains curing title complex;
Four, thermal treatment: be warming up to 500 ℃ from room temperature with the temperature rise rate of 30 ℃/min under the protection of the argon gas that the curing title complex that step 3 is obtained is 30mL/min in airshed, then be incubated 1h obtain carbon material under the condition of 500 ℃;
Five, acid treatment: thus the presoma of carbon material with the carbon material that sour circumfluence method treatment step four obtains, obtained, with 3 pH to the presoma of carbon material of presoma of distilled water centrifuge washing carbon material, be 7.0 again, then vacuum-drying 8h under 80 ℃ of conditions, obtains graphitized stephanoporate material with carbon element.
Wherein, the acid-treated method in step 5 is that the carbon material that step 4 is obtained is dissolved in salpeter solution, in temperature, is then cooling for reflux 12h under 90 ℃ and the stirring velocity condition that is 350r/min, 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: it is to realize by the following method that this test a kind of be take the method that gac is raw material synthetic graphite porous carbon materials:
One, the dispersion of gac: business active fruit shell carbon is scattered in ethanol, then under the condition that is 350r/min at rotating speed, stir 3h and obtain homogeneous reaction liquid, then in homogeneous reaction liquid, add PVP solution, continue to stir under the condition be 350r/min at rotating speed the 3h liquid that is uniformly mixed; The described quality of business active fruit shell carbon and the volume ratio of ethanol are 1g: 100mL; The weight ratio of the solute in business active fruit shell carbon and 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: in the even mixed solution obtaining to step 1, add iron nitrate, then the rotating speed with 350r/min stirs 8h, finally by crossing sonic oscillation 30min, obtains title complex; The mass ratio of the iron nitrate described in the business active fruit shell carbon described in step 1 and step 2 is 5: 1;
Three, solidifying of title complex: the title complex that step 2 is obtained is vacuum-drying 24h under the condition of 100 ℃, then naturally cools to room temperature and obtains curing title complex;
Four, thermal treatment: be warming up to 600 ℃ from room temperature with the temperature rise rate of 30 ℃/min under the protection of the argon gas that the curing title complex that step 3 is obtained is 30mL/min in airshed, then be incubated 1h obtain carbon material under the condition of 600 ℃;
Five, acid treatment: thus the presoma of carbon material with the carbon material that sour circumfluence method treatment step four obtains, obtained, 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, obtains graphitized stephanoporate material with carbon element.
Wherein, the acid-treated method in step 5 is that the carbon material that step 4 is obtained is dissolved in salpeter solution, in temperature, is then cooling for reflux 12h under 90 ℃ and the stirring velocity condition that is 350r/min, 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: it is to realize by the following method that this test a kind of be take the method that gac is raw material synthetic graphite porous carbon materials:
One, the dispersion of gac: business active fruit shell carbon is scattered in ethanol, then under the condition that is 350r/min at rotating speed, stir 3h and obtain homogeneous reaction liquid, then in homogeneous reaction liquid, add PVP solution, continue to stir under the condition be 350r/min at rotating speed the 3h liquid that is uniformly mixed; The described quality of business active fruit shell carbon and the volume ratio of ethanol are 1g: 100mL; The weight ratio of the solute in business active fruit shell carbon and 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: in the even mixed solution obtaining to step 1, add iron nitrate, then the rotating speed with 350r/min stirs 8h, finally by crossing sonic oscillation 30min, obtains title complex; The mass ratio of the iron nitrate described in the business active fruit shell carbon described in step 1 and step 2 is 5: 1;
Three, solidifying of title complex: the title complex that step 2 is obtained is vacuum-drying 24h under the condition of 100 ℃, then naturally cools to room temperature and obtains curing title complex;
Four, thermal treatment: be warming up to 700 ℃ from room temperature with the temperature rise rate of 30 ℃/min under the protection of the argon gas that the curing title complex that step 3 is obtained is 30mL/min in airshed, then be incubated 1h obtain carbon material under the condition of 700 ℃;
Five, acid treatment: thus the presoma of carbon material with the carbon material that sour circumfluence method treatment step four obtains, obtained, 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, obtains graphitized stephanoporate material with carbon element.
Wherein, the acid-treated method in step 5 is that the carbon material that step 4 is obtained is dissolved in salpeter solution, in temperature, is then cooling for reflux 12h under 90 ℃ and the stirring velocity condition that is 350r/min, 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: it is to realize by the following method that this test a kind of be take the method that gac is raw material synthetic graphite porous carbon materials:
One, the dispersion of gac: business active fruit shell carbon is scattered in ethanol, then under the condition that is 350r/min at rotating speed, stir 3h and obtain homogeneous reaction liquid, then in homogeneous reaction liquid, add PVP solution, continue to stir under the condition be 350r/min at rotating speed the 3h liquid that is uniformly mixed; The described quality of business active fruit shell carbon and the volume ratio of ethanol are 1g: 100mL; The weight ratio of the solute in business active fruit shell carbon and 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: in the even mixed solution obtaining to step 1, add iron nitrate, then the rotating speed with 350r/min stirs 8h, finally by crossing sonic oscillation 30min, obtains title complex; The mass ratio of the iron nitrate described in the business active fruit shell carbon described in step 1 and step 2 is 5: 1;
Three, solidifying of title complex: the title complex that step 2 is obtained is vacuum-drying 24h under the condition of 100 ℃, then naturally cools to room temperature and obtains curing title complex;
Four, thermal treatment: be warming up to 800 ℃ from room temperature with the temperature rise rate of 30 ℃/min under the protection of the argon gas that the curing title complex that step 3 is obtained is 30mL/min in airshed, then be incubated 1h obtain carbon material under the condition of 800 ℃;
Five, acid treatment: thus the presoma of carbon material with the carbon material that sour circumfluence method treatment step four obtains, obtained, 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, obtains graphitized stephanoporate material with carbon element.
Wherein, the acid-treated method in step 5 is that the carbon material that step 4 is obtained is dissolved in salpeter solution, in temperature, is then cooling for reflux 12h under 90 ℃ and the stirring velocity condition that is 350r/min, 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; This is tested prepared graphitized stephanoporate material with carbon element and 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, product microscopic appearance is 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 clearly be seen that the diffraction fringe of 002 crystal face of graphite and its have micropore and meso-hole structure by Fig. 4.The generation of graphitized stephanoporate material with carbon element in this test can be described by Fig. 3 and Fig. 4, and the raising of material degree of graphitization is representing that the carbon atom in material is transformed to stratiform ordered structure by unformed shape, can improve the specific conductivity of material significantly; 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: it is to realize by the following method that this test a kind of be take the method that gac is raw material synthetic graphite porous carbon materials:
One, the dispersion of gac: business active fruit shell carbon is scattered in ethanol, then under the condition that is 350r/min at rotating speed, stir 3h and obtain homogeneous reaction liquid, then in homogeneous reaction liquid, add PVP solution, continue to stir under the condition be 350r/min at rotating speed the 3h liquid that is uniformly mixed; The described quality of business active fruit shell carbon and the volume ratio of ethanol are 1g: 100mL; The weight ratio of the solute in business active fruit shell carbon and 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: in the even mixed solution obtaining to step 1, add iron nitrate, then the rotating speed with 350r/min stirs 8h, finally by crossing sonic oscillation 30min, obtains title complex; The mass ratio of the iron nitrate described in the business active fruit shell carbon described in step 1 and step 2 is 5: 1;
Three, solidifying of title complex: the title complex that step 2 is obtained is vacuum-drying 24h under the condition of 100 ℃, then naturally cools to room temperature and obtains curing title complex;
Four, thermal treatment: be warming up to 900 ℃ from room temperature with the temperature rise rate of 30 ℃/min under the protection of the argon gas that the curing title complex that step 3 is obtained is 30mL/min in airshed, then be incubated 1h obtain carbon material under the condition of 900 ℃;
Five, acid treatment: thus the presoma of carbon material with the carbon material that sour circumfluence method treatment step four obtains, obtained, 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, obtains graphitized stephanoporate material with carbon element.
Wherein, the acid-treated method in step 5 is that the carbon material that step 4 is obtained is dissolved in salpeter solution, in temperature, is then cooling for reflux 12h under 90 ℃ and the stirring velocity condition that is 350r/min, 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: it is to realize by the following method that this test a kind of be take the method that gac is raw material synthetic graphite porous carbon materials:
One, the dispersion of gac: business active fruit shell carbon is scattered in ethanol, then under the condition that is 350r/min at rotating speed, stir 3h and obtain homogeneous reaction liquid, then in homogeneous reaction liquid, add PVP solution, continue to stir under the condition be 350r/min at rotating speed the 3h liquid that is uniformly mixed; The described quality of business active fruit shell carbon and the volume ratio of ethanol are 1g: 100mL; The weight ratio of the solute in business active fruit shell carbon and 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: in the even mixed solution obtaining to step 1, add iron nitrate, then the rotating speed with 350r/min stirs 8h, finally by crossing sonic oscillation 30min, obtains title complex; The mass ratio of the iron nitrate described in the business active fruit shell carbon described in step 1 and step 2 is 5: 1;
Three, solidifying of title complex: the title complex that step 2 is obtained is vacuum-drying 24h under the condition of 100 ℃, then naturally cools to room temperature and obtains curing title complex;
Four, thermal treatment: be warming up to 1000 ℃ from room temperature with the temperature rise rate of 30 ℃/min under the protection of the argon gas that the curing title complex that step 3 is obtained is 30mL/min in airshed, then be incubated 1h obtain carbon material under the condition of 1000 ℃;
Five, acid treatment: thus the presoma of carbon material with the carbon material that sour circumfluence method treatment step four obtains, obtained, 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, obtains graphitized stephanoporate material with carbon element.
Wherein, the acid-treated method in step 5 is that the carbon material that step 4 is obtained is dissolved in salpeter solution, in temperature, is then cooling for reflux 12h under 90 ℃ and the stirring velocity condition that is 350r/min, 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 XRD figure spectrum, the XRD figure spectrum that in figure, a is the prepared graphitized stephanoporate material with carbon element of test one, the XRD figure spectrum that in figure, b is the prepared graphitized stephanoporate material with carbon element of test two, the XRD figure spectrum that in figure, c is the prepared graphitized stephanoporate material with carbon element of test three, the XRD figure spectrum that in figure, d is the prepared graphitized stephanoporate material with carbon element of test four, the XRD figure spectrum that in figure, e is the prepared graphitized stephanoporate material with carbon element of test five, the XRD figure spectrum that in figure, f is the prepared graphitized stephanoporate material with carbon element of test six, wherein, ▲ be graphite 002 crystal face of graphitized stephanoporate material with carbon element.There is the characteristic diffraction peak of graphite 002 crystal face in the graphitized stephanoporate material with carbon element of this test preparation as shown in Figure 1, there is degree of graphitization preferably, and degree of graphitization raises and strengthens with thermal treatment temp, thereby can illustrate that the degree of graphitization of graphitized stephanoporate material with carbon element can regulate by the change to thermal treatment temp.
Test seven: it is to realize by the following method that this test a kind of be take the method that gac is raw material synthetic graphite porous carbon materials:
One, the dispersion of gac: business cocoanut active charcoal is scattered in distilled water, then under the condition that is 150r/min at rotating speed, stir 9h and obtain homogeneous reaction liquid, then in homogeneous reaction liquid, add SDS solution, continue to stir under the condition be 150r/min at rotating speed the 1h liquid that is uniformly mixed; The described quality of business cocoanut active charcoal and the volume ratio of distilled water are 5g: 100mL; The weight ratio of the solute in business cocoanut active charcoal and 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: in the even mixed solution obtaining to step 1, add rose vitriol, then the rotating speed with 150r/min stirs 4h, finally by crossing sonic oscillation 120min, obtains title complex; The mass ratio of the rose vitriol described in the business cocoanut active charcoal described in step 1 and step 2 is 10: 1;
Three, solidifying of title complex: the title complex that step 2 is obtained is vacuum-drying 4h under the condition of 80 ℃, then naturally cools to room temperature and obtains curing title complex;
Four, thermal treatment: be warming up to 1000 ℃ from room temperature with the temperature rise rate of 15 ℃/min under the protection of the carbon dioxide that the curing title complex that step 3 is obtained is 200mL/min in airshed, then be incubated 6h obtain carbon material under the condition of 1000 ℃;
Five, acid treatment: thus the presoma of carbon material with the carbon material that sour circumfluence method treatment step four obtains, obtained, 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, obtains graphitized stephanoporate material with carbon element.
Wherein, acid-treated method in step 5 is in the carbon material vitriolization and mixed in hydrochloric acid acid solution that step 4 is obtained, then in temperature, be cooling for reflux 6h under 80 ℃ and the stirring velocity condition that is 250r/min, 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, product microscopic appearance is 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 raising of material degree of graphitization is representing that the carbon atom in material is transformed to stratiform ordered structure by unformed shape, can improve the specific conductivity of material significantly.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: it is to realize by the following method that this test a kind of be take the method that gac is raw material synthetic graphite porous carbon materials:
One, the dispersion of gac: business active fruit shell carbon is scattered in ethanol, then under the condition that is 250r/min at rotating speed, stir 6h and obtain homogeneous reaction liquid, then in homogeneous reaction liquid, add SDBS solution, continue to stir under the condition be 250r/min at rotating speed the 2h liquid that is uniformly mixed; The described quality of business active fruit shell carbon and the volume ratio of ethanol are 2g: 100mL; The weight ratio of the solute in business active fruit shell carbon and 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: in the even mixed solution obtaining to step 1, add single nickel salt, then the rotating speed with 250r/min stirs 6h, finally by crossing sonic oscillation 90min, obtains title complex; The mass ratio of the single nickel salt described in the business active fruit shell carbon described in step 1 and step 2 is 3: 1;
Three, solidifying of title complex: the title complex that step 2 is obtained is vacuum-drying 12h under the condition of 90 ℃, then naturally cools to room temperature and obtains curing title complex;
Four, thermal treatment: be warming up to 900 ℃ from room temperature with the temperature rise rate of 20 ℃/min under the protection of the argon gas that the curing title complex that step 3 is obtained is 50mL/min in airshed, then be incubated 4h obtain carbon material under the condition of 900 ℃;
Five, acid treatment: thus the presoma of carbon material with the carbon material that sour circumfluence method treatment step four obtains, obtained, 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, obtains graphitized stephanoporate material with carbon element.
Wherein, the acid-treated method in step 5 is that the carbon material that step 4 is obtained is dissolved in salpeter solution, in temperature, is then cooling for reflux 10h under 70 ℃ and the stirring velocity condition that is 150r/min, 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, product microscopic appearance is 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 raising of material degree of graphitization is representing that the carbon atom in material is transformed to stratiform ordered structure by unformed shape, can improve the specific conductivity of material significantly.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 (9)
1. the preparation method that the gac of take is raw material synthetic graphite porous carbon materials, is characterized in that a kind ofly take the preparation method that gac is raw material synthetic graphite porous carbon materials and carrying out according to the following steps:
One, the dispersion of gac: gac is evenly mixed with solvent, then under the condition that is 100r/min～350r/min at rotating speed, stir 3h～9h and obtain homogeneous reaction liquid, in homogeneous reaction liquid, add surfactant soln, continue to stir under the condition be 100r/min～350r/min at rotating speed 1h～3h liquid that is uniformly mixed; Described gac is one or both the mixture in cocoanut active charcoal and coal mass active carbon; Described solvent is a kind of in distilled water, ethanol, ethylene glycol and Virahol or several mixture wherein; The quality of described gac and the volume ratio of solvent are (0.1g～10g): 100mL; The solute of described surfactant soln is a kind of in polyvinylpyrrolidone, sodium lauryl sulphate and Sodium dodecylbenzene sulfonate or several mixture wherein, and the solvent of surfactant soln is deionized water; Described gac and the mass ratio of the solute in surfactant soln are (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: in the even mixed solution obtaining to step 1, add metal catalyst, then the rotating speed with 100r/min～350r/min stirs 4h～8h, finally by crossing sonic oscillation 30min～120min, obtains title complex; The mass ratio of the gac described in the metal catalyst described in step 2 and step 1 is 1:(1～10);
Three, solidifying of title complex: the title complex that step 2 is obtained is vacuum-drying 2h～24h under the condition of 20 ℃～100 ℃, then naturally cools to room temperature and obtains curing title complex;
Four, thermal treatment: be warming up to 500 ℃～1000 ℃ from room temperature with the temperature rise rate of 5 ℃/min～30 ℃/min under the protection of the rare gas element that the curing title complex that step 3 is obtained is 30mL/min～200mL/min in airshed, then be to be incubated 1h～6h under the condition of 500 ℃～1000 ℃ to obtain carbon material in temperature;
Five, acid treatment: the carbon material obtaining 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 in temperature, be vacuum-drying 5h～10h under 60 ℃～80 ℃ conditions, obtain graphitized stephanoporate material with carbon element.
2. a kind of preparation method of gac as raw material synthetic graphite porous carbon materials of take according to claim 1, it is characterized in that in step 1, gac evenly being mixed with solvent, then under the condition that is 200r/min～300r/min at rotating speed, stir 5h～7h and obtain homogeneous reaction liquid, then in homogeneous reaction liquid, add surfactant soln, continue to stir under the condition be 200r/min～300r/min at rotating speed 1h～3h liquid that is uniformly mixed.
3. a kind of preparation method that gac is raw material synthetic graphite porous carbon materials of take according to claim 1, is characterized in that the quality of the gac described in step 1 and the volume ratio of solvent are for (3g～7g): 100mL; The mass ratio of the solute in the gac described in step 1 and surfactant soln is (30～70): 1; The volumetric molar concentration of the surfactant soln described in step 1 is 0.005mol/L～0.01mol/L.
4. a kind of preparation method that gac is raw material synthetic graphite porous carbon materials of take according to claim 1, is characterized in that the metal catalyst described in 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 nickel acetate or several mixture wherein.
5. a kind of preparation method that gac is raw material synthetic graphite porous carbon materials of take according to claim 1, the mass ratio that it is characterized in that the gac described in the metal catalyst described in step 2 and step 1 is 1:(4～6).
6. a kind of preparation method of gac as raw material synthetic graphite porous carbon materials of take according to claim 1; under the protection of the rare gas element that the curing title complex that it is characterized in that in step 4, step 3 being obtained is 80mL/min～150mL/min in airshed, from room temperature, with the temperature rise rate of 10 ℃/min～20 ℃/min, be warming up to 700 ℃～900 ℃, then in temperature, be under the condition of 700 ℃～900 ℃, to be incubated 3h～5h to obtain carbon material.
7. a kind of preparation method that gac is raw material synthetic graphite porous carbon materials of take according to claim 1, is characterized in that the rare gas element described in step 4 is a kind of in nitrogen, argon gas and carbonic acid gas or the mixed gas of two kinds wherein.
8. a kind of preparation method of gac as raw material synthetic graphite porous carbon materials of take according to claim 1, it is characterized in that the carbon material obtaining with sour circumfluence method treatment step four in step 5, obtain washing lotion, again with distilled water wash washing lotion to the pH of washing lotion be 6.8～7.2, then in temperature, be vacuum-drying 7h～9h under 60 ℃～80 ℃ conditions, obtain graphitized stephanoporate material with carbon element.
9. a kind of preparation method that gac is raw material synthetic graphite porous carbon materials of take according to claim 1, is characterized in that the sour circumfluence method described in step 5 carries out according to the following steps:
The carbon material that step 4 is obtained is dissolved in acid solution, in temperature, is then cooling for reflux 1h～12h under 50 ℃～90 ℃ and the stirring velocity condition that is 100r/min～350r/min, 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 phosphoric acid solution or several mixed acid solution wherein.
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| 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 |
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| CN107814385B (en) * | 2017-11-16 | 2020-07-31 | 华中科技大学 | Method for treating industrial wastewater and preparing graphite type porous carbon material by using biomass coke |
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