CN102583309B - Method for preparing mesoporous carbon/graphite sheet composite material by expanded graphite intercalation - Google Patents
Method for preparing mesoporous carbon/graphite sheet composite material by expanded graphite intercalation Download PDFInfo
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- CN102583309B CN102583309B CN201210015943.2A CN201210015943A CN102583309B CN 102583309 B CN102583309 B CN 102583309B CN 201210015943 A CN201210015943 A CN 201210015943A CN 102583309 B CN102583309 B CN 102583309B
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Abstract
The invention provides a method for preparing a mesoporous carbon/graphite sheet composite material by expanded graphite intercalation, belongs to the field of preparation of a mesoporous carbon and graphite sheet composite material, and aims at solving the technical problems that the mesoporous carbon based composite material is high in production cost, a device required by reaction is complex, the reaction condition is rigorous, the productivity is low, industrialized production is difficult and the like. The method provided by the invention comprises the following steps of: conducting thermal expansion treatment on expanded graphite and then modifying via a surface active agent; preparing a mesoporous carbon precursor; preparing a mesoporous carbon/graphite sheet composite material precursor; and carbonizing. The mesoporous carbon and graphite sheet composite material prepared by the method provided by the invention has the characteristics that electric-conduction is good, the thickness and the size of a hole are controllable, the specific surface area is large and the like, and the prepared mesoporous carbon/graphite sheet composite material has important application value in the fields such as fuel cells, lithium-ion batteries and super capacitors. According to the invention, the cheap expanded graphite is taken as the raw material, so that the method has the characteristics of low cost, simpleness, easiness in industrial production and the like.
Description
Technical field
The invention belongs to the preparation field of mesoporous carbon back carbon material.Be specifically related to the preparation method of mesoporous carbon/graphite flake matrix material.
Background technology
Meso-porous carbon material has the advantages such as stable physicochemical property, higher specific surface area and pore size be adjustable, is therefore widely used in the fields such as fuel cell, lithium ion battery and ultracapacitor.Because the electroconductibility of mesoporous carbon itself is very low, this can affect the performance of its performance thus limit its application in some fields.In order to improve the electroconductibility of mesoporous carbon sill, therefore the carbon material of itself and high conductivity is necessary to carry out compound, at present conventional is by itself and carbon nanotube and Graphene compound, prepares the C-base composte material of mesoporous carbon/carbon nanotube and mesoporous carbon/Graphene.Although this can improve the performance of mesoporous carbon sill, expensive due to carbon nanotube and Graphene, thus limit commercially producing of these matrix materials.
Expanded graphite is obtained through simple acid treatment by natural graphite, there is the advantage such as low price, good conductivity, with it as raw material, under the condition of vacuum aided, adopt mesoporous carbon precursor graft process, mesoporous carbon/graphite flake matrix material can be prepared.The mesoporous carbon back carbon material of the method preparation synthesis has low cost.Be easy to advantages such as commercially producing.
Summary of the invention
The present invention will solve that existing mesoporous carbon back carbon composite production cost is high, reaction required equipment complexity, severe reaction conditions, yield poorly, be difficult to the technical problems such as suitability for industrialized production; And provide the method for preparing mesoporous carbon/graphite sheet composite material by expanded graphite intercalation.
The present invention prepares the productive rate of mesoporous carbon/graphite flake matrix material more than 99.9%.Adopt different oxy-compound, structure that aldehyde compound controls product, adopt different tensio-active agents can adjustment hole size, by the electroconductibility regulating consumption to regulate and control prepared matrix material, thus preparation has the mesoporous carbon/graphite flake matrix material of different structure character and is applied to different field.Mesoporous carbon prepared by the present invention and graphene composite material have the features such as good conductivity, thickness is controlled, hole dimension is controlled, specific surface area is larger, and its intermediate pore size size is 2 ~ 20nm, and thickness is 10 ~ 100nm, and specific surface area is 400 ~ 1000m
2/ g, mesoporous carbon/graphite flake matrix material prepared by the method has important using value in fields such as fuel cell, lithium ion battery and ultracapacitors.The present invention adopts cheap expanded graphite as raw material, and adopts the mature technologies such as ultrasonic, hydro-thermal, carbonization, and required equipment is simple, reaction conditions is gentle, has that cost is low, method simple, be easy to the features such as suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the porous nano graphite flake that test one is synthesized.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: in present embodiment, the method for preparing mesoporous carbon/graphite sheet composite material by expanded graphite intercalation is carried out as follows:
Step one, thermal expansion process is carried out to expanded graphite, then be (10 ~ 1) in the mass ratio of expanded graphite and tensio-active agent: the ratio of 10 adds in the solution containing surfactant A, re-use ultrasonic method or heated and stirred method carries out finishing, wherein containing a kind of or wherein several mixing that the solvent C in the solution of surfactant A is in water, ethanol, propyl alcohol and ethylene glycol, be 1: 10 ~ 500 containing the mass ratio of surfactant A and solvent C in the solution of surfactant A;
Step 2, surfactant B is dissolved in solvent D, add oxy-compound and aldehyde compound again, the mass ratio of oxy-compound and aldehyde compound is 1: 3 ~ 6, then 50 DEG C ~ 75 DEG C, stirring velocity reacts 30min ~ 20h under being 200r/min ~ 400r/min condition, obtain mesoporous carbon precursor solution, wherein said solvent D is the mixing in a kind of in water, ethanol or two, the mass ratio of surfactant B and solvent D is 1: 20 ~ 1: 50, and the total mass of oxy-compound and aldehyde compound and the mass ratio of solvent D are 1: 8 ~ 20;
Step 3, expanded graphite after processing through step one is placed in vacuum filtration bottle, under the condition vacuumized, be 1 in the mass ratio of expanded graphite and mesoporous carbon precursor solution after processing through step one: the mesoporous carbon precursor solution that step 2 obtains is added drop-wise in vacuum filtration bottle by the ratio of (50 ~ 300), after being added dropwise to complete (time for adding is ten minutes), continue to vacuumize 5min ~ 2h (object is exactly interlayer mesoporous carbon precursor being intercalation into expanded graphite), then hydrothermal method or microwave method is adopted to process, obtain matrix material precursor,
Step 4, under inert gas atmosphere condition, 600 DEG C ~ 1000 DEG C are risen to by room temperature with the heat-up rate of 2 DEG C/min ~ 20 DEG C/min, carry out carbonization to matrix material precursor under constant temperature, carbonization time is 1h ~ 6h, and wherein said inert gas atmosphere flow is 120mL/min ~ 400mL/min; Namely mesoporous carbon/graphite flake matrix material is obtained.
Present embodiment prepares the productive rate of mesoporous carbon/graphite flake matrix material more than 99.9%.Adopt different oxy-compound, structure that aldehyde compound controls product, adopt different tensio-active agents can adjustment hole size, by the electroconductibility regulating consumption to regulate and control prepared matrix material, thus preparation has the mesoporous carbon/graphite flake matrix material of different structure character and is applied to different field.Mesoporous carbon prepared by the present invention and graphene composite material have the features such as good conductivity, thickness is controlled, hole dimension is controlled, specific surface area is larger, and its intermediate pore size size is 2 ~ 20nm, and thickness is 10 ~ 100nm, and specific surface area is 400 ~ 1000m
2/ g, mesoporous carbon/graphite flake matrix material prepared by the method has important using value in fields such as fuel cell, lithium ion battery and ultracapacitors.
Embodiment two: present embodiment and embodiment one unlike: the method that described in step one, thermal expansion process adopts is microwave heating method or high-temperature heating method; During described microwave heating expanded graphite, microwave power is 3.0 ~ 5.0kW, and heat-up time is 10s ~ 2min; It is in a nitrogen atmosphere that described heat prepares thermal expansion process, and gas flow is 100 ~ 300mL/min, and Heating temperature is 800 ~ 2000 DEG C, and heat-up time is 10s ~ 2min.Other step is identical with embodiment one with parameter.
Embodiment three: present embodiment and embodiment one or two unlike: the ultrasonic method described in step one be ultrasonic frequency be 3 ~ 30KHz, under ultrasonic power is 200 ~ 700W condition, ultrasonic time is 5min ~ 2h; Heated and stirred method described in step one be temperature be 30 ~ 60 DEG C, under stirring velocity is 150 ~ 300r/min condition, churning time is 5min ~ 2h.Other step is identical with embodiment one or two with parameter.
Embodiment four: one of present embodiment and embodiment one to three unlike: the surfactant A described in step one is the one in cationic surfactant, aniorfic surfactant, nonionogenic tenside and amphoterics; Described cationic surfactant is cetyl trimethylammonium bromide, cetyl dimethyl benzyl ammonium bromide, hexadecanol polyoxyethylene ether dimethyl-octa alkyl ammomium chloride, Dodecyl Polyoxyethylene Ether base dimethyl ammonium methyl chloride; Described aniorfic surfactant is sodium lauryl sulphate, sodium laurylsulfonate, cetyl benzenesulfonic acid sodium, sodium stearyl sulfate; Described nonionic surface active agent is Polyvinylpyrolidone (PVP), propanediol polyoxypropylene Soxylat A 25-7, structure alcohol polyoxyethylene poly-oxygen propylene aether, polyurethane polyureas oxypropylene polyethenoxy ether; Described amphoterics is EO
20PO
70eO
20(P123), EO
106pO
70eO
106(F127), dimethyl dodecyl amine oxide, dodecyl dihydroxy ethyl amine oxide, tetradecyl dihydroxy ethyl amine oxide, hexadecyl dihydroxy ethyl amine oxide.Other step is identical with one of embodiment one to three with parameter.
Embodiment five: one of present embodiment and embodiment one to four unlike: the surfactant B described in step 2 is the one in cationic surfactant, aniorfic surfactant, nonionogenic tenside and amphoterics; Described cationic surfactant is cetyl trimethylammonium bromide, cetyl dimethyl benzyl ammonium bromide, hexadecanol polyoxyethylene ether dimethyl-octa alkyl ammomium chloride, Dodecyl Polyoxyethylene Ether base dimethyl ammonium methyl chloride; Described aniorfic surfactant is sodium lauryl sulphate, sodium laurylsulfonate, cetyl benzenesulfonic acid sodium, sodium stearyl sulfate; Described nonionic surface active agent is Polyvinylpyrolidone (PVP), propanediol polyoxypropylene Soxylat A 25-7, structure alcohol polyoxyethylene poly-oxygen propylene aether, polyurethane polyureas oxypropylene polyethenoxy ether; Described amphoterics is EO
20pO
70eO
20(P123), EO
106pO
70eO
106(F127), dimethyl dodecyl amine oxide, dodecyl dihydroxy ethyl amine oxide, tetradecyl dihydroxy ethyl amine oxide, hexadecyl dihydroxy ethyl amine oxide.Other step is identical with one of embodiment one to four with parameter.
Embodiment six: one of present embodiment and embodiment one to five unlike: the oxy-compound described in step 2 is furfuryl alcohol, phenol, phenyl methylcarbamate, pyrocatechol, Resorcinol, Resorcinol, benzenetriol, naphthols or anthrol.Other step is identical with one of embodiment one to five with parameter.
Embodiment seven: one of present embodiment and embodiment one to six unlike: the aldehyde compound described in step 2 is furfural, the undecyl aldehyde, phenyl aldehyde, formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, enanthaldehyde, octanal, aldehyde C-9 or capraldehyde.Other step is identical with one of embodiment one to six with parameter.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: the hydrothermal method described in step 3 is under 110 ~ 180 DEG C of conditions, and the hydro-thermal time is 8 ~ 30h.Other step is identical with one of embodiment one to seven with parameter.
Embodiment nine: one of present embodiment and embodiment one to eight are react 2 ~ 10min under microwave intensity is the condition of 1 ~ 10kW unlike: the microwave method described in step 3.Other step is identical with one of embodiment one to eight with parameter.
Embodiment ten: present embodiment and one of embodiment one to nine are a kind of in nitrogen, argon gas, helium unlike: the rare gas element described in step 4 or wherein severally mix.Other step is identical with one of embodiment one to nine with parameter.
Solvent described in present embodiment is mixture, is mixed by any ratio between each solvent.
Adopt following verification experimental verification invention effect:
Test one: preparing mesoporous carbon/graphite sheet composite material by expanded graphite intercalation is completed by following step: one, in a nitrogen atmosphere, gas flow is 200mL/min, Heating temperature is 1100 DEG C, and heat-up time is that 30s heating expanded graphite obtains thermal expansion graphite.Take 0.1g thermal expansion graphite, add 1.6g cetyl benzenesulfonic acid sodium after adding 20mL water again, ultrasonic 30min, prepare surfactant modified expanded graphite; Two, 0.3g Polyvinylpyrolidone (PVP) is dissolved in 30g water, adds phenol and 1.5g formaldehyde between 0.6g respectively, then 50 ~ 60 DEG C, stirring velocity reacts 4h under being 300r/min condition, obtains mesoporous carbon precursor solution; Three, be placed in vacuum filtration bottle by surfactant modified expanded graphite obtained in step one, under the condition vacuumized, the mesoporous carbon precursor solution that step 2 obtains is added drop-wise in expanded graphite, after being added dropwise to complete, continues to vacuumize 40min; Four, product step 3 prepared is hydro-thermal 10h at 160 DEG C of temperature, obtained mesoporous carbon/graphite precursor; Five, mesoporous carbon step 4 obtained/graphite flake precursor is under argon gas condition, and gas flow is 180mL/min, rises to 850 DEG C with the heat-up rate of 3 DEG C/min by room temperature, and constant temperature 4h, namely obtain mesoporous carbon/graphite flake matrix material.
As shown in Figure 1, as can be seen from the figure, its microscopic appearance is two-dimensional sheet structure to the projection electron microscope photo of mesoporous carbon/graphite flake matrix material prepared by present embodiment, and hole dimension is 8 ~ 15nm, demonstrates the generation of porous nano graphite flake.
Test two: this test with test one unlike: the method preparing thermal expansion graphite described in step one is microwave heating method, and microwave power is 4.0kW, and heat-up time is 30s.Other step and parameter identical with test one.
Mesoporous carbon/graphite flake matrix material microscopic appearance that this test obtains is two-dimensional sheet structure, and hole dimension size is 3nm, and thickness is 5nm, and specific surface area is 561m
2/ g.
Test three: this test with test one unlike: the method preparing thermal expansion graphite described in step one is high-temperature heating method, and in a nitrogen atmosphere, gas flow is 150mL/min, and Heating temperature is 1000 DEG C, and heat-up time is 15s.Other step and parameter identical with test one.
Mesoporous carbon/graphite flake matrix material microscopic appearance that this test obtains is two-dimensional sheet structure, and hole dimension size is 5nm, and thickness is 10nm, and specific surface area is 457m
2/ g.
Test four: this test with test one unlike: the tensio-active agent described in step one is sodium lauryl sulphate.Other step and parameter identical with test one.
Mesoporous carbon/graphite flake matrix material microscopic appearance that this test obtains is two-dimensional sheet structure, and hole dimension size is 3nm, and thickness is 5nm, and specific surface area is 624m
2/ g.
Test five: this test with test one unlike: the tensio-active agent described in step one is EO
20pO
70eO
20(P123).Other step and parameter identical with test one.
Mesoporous carbon/graphite flake matrix material microscopic appearance that this test obtains is two-dimensional sheet structure, and hole dimension size is 8nm, and thickness is 15nm, and specific surface area is 786m
2/ g.
Test six: this test with test one unlike: the tensio-active agent described in step one is Polyvinylpyrolidone (PVP).Other step and parameter identical with test one.
Mesoporous carbon/graphite flake matrix material microscopic appearance that this test obtains is two-dimensional sheet structure, and hole dimension size is 10nm, and thickness is 72nm, and specific surface area is 534m
2/ g.
Test seven: this test with test one unlike: the oxy-compound described in step 2 is phenyl methylcarbamate, and aldehyde compound is phenyl aldehyde.Other step and parameter identical with test one.
Mesoporous carbon/graphite flake matrix material microscopic appearance that this test obtains is two-dimensional sheet structure, and hole dimension size is 5nm, and thickness is 75nm, and specific surface area is 408m
2/ g.
Test eight: this test with test one unlike: the tensio-active agent described in step 2 is cetyl benzenesulfonic acid sodium.Other step and parameter identical with test one.
Mesoporous carbon/graphite flake matrix material microscopic appearance that this test obtains is two-dimensional sheet structure, and hole dimension size is 6nm, and thickness is 54nm, and specific surface area is 514m
2/ g.
Test nine: this test with test one unlike: the ultrasonic method described in step one be ultrasonic frequency be 40KHz, under ultrasonic power is 300W condition, ultrasonic time is 20min.Other step and parameter identical with test one.
Mesoporous carbon/graphite flake matrix material microscopic appearance that this test obtains is two-dimensional sheet structure, and hole dimension size is 3nm, and thickness is 45nm, and specific surface area is 417m
2/ g.
Claims (1)
1. the method for preparing mesoporous carbon/graphite sheet composite material by expanded graphite intercalation, it is characterized in that preparing mesoporous carbon/graphite sheet composite material by expanded graphite intercalation is completed by following step: one, in a nitrogen atmosphere, gas flow is 200mL/min, Heating temperature is 1100 DEG C, and heat-up time is that 30s heating expanded graphite obtains thermal expansion graphite; Take 0.1g thermal expansion graphite, after adding 20mL water, add 1.6g EO again
20pO
70eO
20(P123), ultrasonic 30min, prepares surfactant modified expanded graphite; Two, 0.3g Polyvinylpyrolidone (PVP) is dissolved in 30g water, adds phenol and 1.5g formaldehyde between 0.6g respectively, then 50 ~ 60 DEG C, stirring velocity reacts 4h under being 300r/min condition, obtains mesoporous carbon precursor solution; Three, be placed in vacuum filtration bottle by surfactant modified expanded graphite obtained in step one, under the condition vacuumized, the mesoporous carbon precursor solution that step 2 obtains is added drop-wise in expanded graphite, after being added dropwise to complete, continues to vacuumize 40min; Four, product step 3 prepared is hydro-thermal 10h at 160 DEG C of temperature, obtained mesoporous carbon/graphite precursor; Five, mesoporous carbon step 4 obtained/graphite flake precursor is under argon gas condition, and gas flow is 180mL/min, rises to 850 DEG C with the heat-up rate of 3 DEG C/min by room temperature, and constant temperature 4h, namely obtain mesoporous carbon/graphite flake matrix material.
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| CN103072974B (en) * | 2012-11-09 | 2014-11-05 | 中国海洋石油总公司 | Method for coating artificial graphitic carbon anode material surface |
| CN103259018B (en) * | 2013-04-27 | 2015-06-10 | 黑龙江大学 | Preparation method of porous graphite flake applied to super-electric negative pole of lithium battery |
| CN104289256B (en) * | 2013-07-18 | 2016-08-17 | 中国科学院大连化学物理研究所 | A kind of preparation method of electrocatalyst for fuel cell carrier |
| CN107402247A (en) * | 2017-07-21 | 2017-11-28 | 张娟 | A kind of preparation method of electrochemical sensor nano-graphene/chitosan complex film modified electrode |
| CN108084583B (en) * | 2017-11-29 | 2021-01-01 | 吉林云亭石墨烯技术股份有限公司 | Preparation method of graphene and preparation of sound insulation graphene EPS |
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| CN1719645A (en) * | 2004-07-06 | 2006-01-11 | 中国科学院大连化学物理研究所 | A kind of bipolar board for new proton exchange film fuel battery preparation technology |
| CN102167308A (en) * | 2011-01-30 | 2011-08-31 | 黑龙江大学 | Method for preparing mesoporous carbon and graphene composite material |
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| CN1719645A (en) * | 2004-07-06 | 2006-01-11 | 中国科学院大连化学物理研究所 | A kind of bipolar board for new proton exchange film fuel battery preparation technology |
| CN102167308A (en) * | 2011-01-30 | 2011-08-31 | 黑龙江大学 | Method for preparing mesoporous carbon and graphene composite material |
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