CN110078058A - A kind of three-dimensional porous graphene-polymer presoma conversion ceramic composite and preparation method thereof - Google Patents
A kind of three-dimensional porous graphene-polymer presoma conversion ceramic composite and preparation method thereof Download PDFInfo
- Publication number
- CN110078058A CN110078058A CN201910274621.1A CN201910274621A CN110078058A CN 110078058 A CN110078058 A CN 110078058A CN 201910274621 A CN201910274621 A CN 201910274621A CN 110078058 A CN110078058 A CN 110078058A
- Authority
- CN
- China
- Prior art keywords
- graphene
- dimensional
- polymer
- dimensional porous
- ceramic composite
- 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.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 239000000919 ceramic Substances 0.000 title claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 77
- 239000002243 precursor Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000006193 liquid solution Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000005336 cracking Methods 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000004108 freeze drying Methods 0.000 claims description 16
- 239000000017 hydrogel Substances 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910010293 ceramic material Inorganic materials 0.000 claims description 4
- 229960003638 dopamine Drugs 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229920001709 polysilazane Polymers 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 150000003233 pyrroles Chemical group 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 229920003257 polycarbosilane Polymers 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims 1
- 238000001338 self-assembly Methods 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- -1 Graphite Alkene Chemical class 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 239000004964 aerogel Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000002906 microbiologic effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of three-dimensional porous graphene-polymer presoma conversion ceramic composites and preparation method thereof.It using three-dimensional porous graphene network structure as skeleton, is impregnated, is freeze-dried by polybenzazole precursor liquid solution, crosslinking, cracking process obtains three-dimensional porous graphene-polymer presoma conversion ceramic composite.This method can overcome graphene to reunite and disperse non-uniform disadvantage in polybenzazole precursor liquid solution.Three-dimensional grapheme network skeleton not only can effectively improve conductivity of composite material energy, while can be improved the active site of composite material.In metal ion battery, pyrostat and electromagnetic shielding material field have broad application prospects.
Description
Technical field
The present invention relates to a kind of three-dimensional porous graphene-polymer presoma conversion ceramic composite and its preparation sides
Method belongs to technical field of composite preparation.
Background technique
Polymer precursor converts ceramic material (Polymer-derived ceramics, PDCs) due to good
High-temperature behavior and adjustable electric property are widely used in metal ion battery, microbiological fuel cell, pyrostat,
MEMS and electromagnetic shielding field.However since the content of the Nano grade carbon cluster (free carbon) in PDC is lower, very great Cheng
It is limited on degree in electricity and the potential application of electrochemical field.Accordingly, with respect to the method quilt for how improving PDC electric conductivity
It developed in succession, including change cracking temperature, conductive materials are introduced using rich carbon matrix precursor and in ceramic matrix.Graphite
Alkene and its derivative, the material very excellent as a kind of electric conductivity have been introduced in PDC to change its physical property.
Researcher generallys use the method for traditional " from top to bottom " such as mechanical mixture or chemical crosslinking for graphene or oxygen at present
Graphite alkene is mixed with polymer precursor, crosslinking, and cracking obtains graphene/polymer precursor conversion ceramic composite.
However the high-specific surface area characteristic of graphene causes it to be easy random stacking and reunite, so that there are many microcosmic scarce for composite material
It falls into；Low graphene carrying capacity, graphene disorder distribution in the base and disconnected conductive network structure make composite wood simultaneously
Expect that the raising space of electric conductivity is limited.It therefore will be before being scattered in of graphene uniform by the method for traditional " from top to bottom "
There are still many bottlenecks in drive liquid solution.
Summary of the invention
Technology of the invention solves the problems, such as: in order to solve graphene film bad dispersibility in polybenzazole precursor liquid solution,
The shortcomings that carrying capacity is low and disorder distribution provides a kind of three-dimensional porous graphene-polymer presoma conversion ceramic composite,
It is a further object of the present invention to provide the preparation methods of above-mentioned material；In order to solve graphene in polybenzazole precursor liquid solution
The problem of bad dispersibility, prepares porous graphene-polymer precursor conversion ceramics the present invention provides a kind of " from bottom to top "
The method of material.
The technical solution of the present invention is as follows: a kind of three-dimensional porous graphene-polymer presoma converts ceramic composite,
Before being characterized in that three-dimensional grapheme network structure filled polymer presoma converts ceramic material, and polymer is presented in network internal
It drives body conversion ceramics-graphene-polymer presoma and converts ceramic " sandwich " structure；It is total that the quality of graphene accounts for composite material
The 1~50% of quality.
It is preferred that the polymer precursor conversion ceramics are one or more of SiOC, SiOCN or SiCN.
The density of three-dimensional porous graphene-polymer presoma conversion ceramic composite of the present invention is 11.5~
1500mg/cm3, conductivity is 1.2~165S/m.
Above-mentioned three-dimensional porous graphene-polymer presoma conversion Ceramic Composite material is prepared the present invention also provides a kind of
The method of material, the specific steps of which are as follows:
(1) graphene oxide water solution and reducing agent are measured respectively, the mass ratio of graphene oxide and reducing agent is 1:(1
~5)；By magnetic agitation, mixed solution is obtained after ultrasonic disperse；
(2) mixed solution prepared by step (1) is transferred in vial, sealing is placed into 50-90 DEG C of baking oven certainly
Assembling 6~for 24 hours after, obtain three-dimensional redox graphene hydrogel；
(3) the three-dimensional redox graphene hydrogel that step (2) is prepared is put into aging in the aqueous solution of ethyl alcohol
Afterwards, freezing 12 under conditions of being put into -20~-80 DEG C~for 24 hours, taking-up are put into freeze drying equipment dry, obtain three-dimensional reduction
Graphite oxide aerogel；
(4) aeroge that step (3) is prepared is placed in tube furnace, and in Ar atmosphere, temperature rises to 800~1000
DEG C, 1~3h is kept the temperature, Temperature fall obtains three-dimensional nitrogen-doped graphene aeroge；
(5) polymer precursor and organic solvent are measured in container, is stirred；Wherein polymer precursor and
The mass volume ratio of organic solvent is 5~200mg/ml；
(6) the obtained three-dimensional nitrogen-doped graphene aeroge of step (4) is put into the solution that step (5) is configured
In, it sufficiently submerges, and be transferred into vacuum oven and impregnate；
(7) material after dipping in step (6) is taken out, 6~12h is freezed under conditions of putting it into -20~-80 DEG C,
Drying in freeze drying equipment is put it into again, obtains the three-dimensional graphene composite material of polybenzazole precursor liquid solution package；
(8) three-dimensional graphene composite material for wrapping up polybenzazole precursor liquid solution obtained in step (7) places pipe
In formula furnace, calcining obtains three-dimensional porous graphene-polymer presoma conversion ceramic composite.
Reducing agent is any one in pyrroles, aniline, dopamine or ethylenediamine in preferred steps (1).
Ageing time in preferred steps (3) is 24~72h；Drying time is 12~72h in freeze drying equipment.
Polybenzazole precursor liquid solution in preferred steps (5) be in polysiloxanes, Polycarbosilane or polysilazane etc. extremely
Few one kind；Organic solvent is any one in the tert-butyl alcohol, amphene or the tert-butyl alcohol-amphene.
The vacuum degree of vacuum oven is 100-300mbar in preferred steps (6)；Temperature is 30-60 DEG C；Dip time is
1~3h.
In preferred steps (7) in freeze drying equipment drying time be 12~for 24 hours.
Calcining described in preferred steps (8) are as follows: in Ar atmosphere, rise to 200 according to the heating rate of 1~5 DEG C/min
~300 DEG C of 1~3h of heat preservation crosslinkings rise to 900~1100 DEG C according still further to the heating rate of 1~5 DEG C/min, and 1~3h of heat preservation is cracked,
Then Temperature fall finally obtains three-dimensional porous graphene-polymer presoma conversion ceramic composite.
The utility model has the advantages that
The present invention is freezed using three-dimensional porous graphene aerogel as three-dimensional network skeleton using the solvent impregnated combination of high-melting-point
Seasoning is successfully prepared a kind of three-dimensional porous graphene-polymer presoma conversion ceramic composite, avoids graphene
Aeroge solves graphene film bad dispersibility, carrying capacity in polybenzazole precursor liquid solution in the contraction and collapsing of dipping process
The problem of low and disorder distribution.Polymer precursor conversion is presented inside the network unit of prepared three-dimensional porous composite material
Ceramics-graphene-polymer presoma converts ceramic " sandwich " structure, the cause of the light porous material and conventional method preparation
Close graphene-polymer presoma conversion ceramic material is compared, and electric conductivity is excellent, density low several orders of magnitude the case where
Under, conductivity can reach the even high several orders of magnitude of the same order of magnitude.
Detailed description of the invention
Fig. 1 is the pictorial diagram of 1 different phase material prepared of example；
Fig. 2 is three-dimensional porous nitrogen-doped graphene aeroge micro-structure diagram in example 1；
Fig. 3 is three-dimensional porous graphene in example 1/polymer precursor conversion ceramic composite SEM picture；
Fig. 4 is three-dimensional porous graphene in example 1/polymer precursor conversion ceramic composite TEM picture；
Fig. 5 is three-dimensional porous graphene in example 2/polymer precursor conversion ceramic composite SEM picture；
Fig. 6 is three-dimensional porous graphene in example 3/polymer precursor conversion ceramic composite SEM picture；
Fig. 7 is three-dimensional porous graphene in example 4/polymer precursor conversion ceramic composite SEM picture；
Fig. 8 is that three-dimensional porous and reported closely knit graphene/polymer precursor prepared by example 1,2,3 and 4 turns
Change the density and conductivity relational graph of ceramic composite.
Specific embodiment
Example 1.
(1) a certain amount of graphene oxide water solution (5mg/ml) and pyrroles three-dimensional porous grapheme material preparation: are measured
The mass ratio of monomer, graphene oxide and pyrrole monomer is 1:5.Then pyrroles is added dropwise while stirring in graphene oxide water solution
In, by magnetic agitation, ultrasonic disperse in cold water obtains mixed solution.Mixed solution is transferred in vial and is sealed, is put into
In 60 DEG C of baking ovens, takes out later obtain redox graphene hydrogel for 24 hours.Hydrogel is put into ethanol/water mixed solution
After aging for 24 hours, 12h is freezed under conditions of being put into -80 DEG C, taking-up is put into drying in freeze drying equipment and for 24 hours, obtains three-dimensional reduction
Graphite oxide aerogel (GA).Then by GA at 900 DEG C, 2h is heat-treated in argon atmosphere, Temperature fall obtains three-dimensional nitrogen and mixes
Miscellaneous graphene aerogel (NGA).
(2) three-dimensional porous graphene/polymer precursor conversion ceramic composite preparation: first by polymer precursor
Polysiloxanes and the tert-butyl alcohol are mixed evenly, and proportion is 50mg/ml.Then NGA is put into mixed solution, so that mixing
Solution sufficiently submerges NGA, and is transferred into vacuum oven, impregnates 2h, vacuum degree 200mabr, and temperature is 30 DEG C.
12h is freezed under conditions of putting it into -80 DEG C after taking-up, then is put it into drying in freeze drying equipment and for 24 hours, obtained polymer
The three-dimensional graphene composite material (NGA-P) of precursor solution package, finally obtains three-dimensional graphite by Pintsch process for NGA-P
Alkene/polymer precursor conversion ceramic composite (NGA-PDC), cracking condition are as follows: in Ar atmosphere, be warming up to 1 DEG C/min
250 DEG C, 2h is kept the temperature, is warming up to 1100 DEG C immediately with 1 DEG C/min, keeps the temperature Temperature fall after 3h.Fig. 1 is NGA-PDC preparation process
Middle different phase pictorial diagram, including graphene aerogel (GA), nitrogen-doped graphene aeroge (NGA), nitrogen-doped graphene gas
Gel/polybenzazole precursor composite material (NGA-P) and graphene/polymer precursor convert ceramic composite (NGA-
PDC).Fig. 2 and Fig. 3 is respectively NGA and NGA-PDC micro-structure diagram.As it can be seen that nitrogen-doped graphene aeroge (NGA) shows
Three-dimensional porous network structure is to form the good three-dimensional framework of composite material.After introducing PDC, composite material is still presented
Three-dimensional porous network structure out, and polymer precursor conversion ceramics/graphene/polymer precursor conversion is presented in network internal
Ceramic " sandwich " structure (Fig. 4) has been effectively relieved graphene as conductive filler and has been unevenly distributed and reunites existing in PDC
As.NGA-PDC is NGA-SiOC composite material, density 78.2mg/cm under this condition3, conductivity 8.4S/m, wherein graphite
Alkene content accounts for the 12.5% of gross mass.
The three-dimensional porous grapheme material preparation of example 2. (1): a certain amount of graphene oxide water solution (3mg/ml) is measured
And ethylenediamine, the mass ratio of graphene oxide and ethylenediamine are 1:1.Then ethylenediamine is added dropwise while stirring in graphene oxide water
In solution, by magnetic agitation, ultrasonic disperse in cold water obtains mixed solution.Mixed solution is transferred in vial and is sealed,
It is put into 90 DEG C of baking ovens, is taken out after 6h and obtain redox graphene hydrogel.Hydrogel is put into ethanol/water mixed solution
It after middle aging 72h, is freezed under conditions of being put into -50 DEG C for 24 hours, taking-up is put into freeze drying equipment dry 12h, obtains three-dimensional go back
Former graphite oxide aerogel (GA).Then by GA at 800 DEG C, 1h is heat-treated in argon atmosphere, Temperature fall obtains three-dimensional nitrogen
Doped graphene aeroge (NGA).
(2) three-dimensional porous graphene/polymer precursor conversion ceramic composite preparation: first by polymer precursor
Polysiloxanes and amphene are mixed evenly, and proportion is 5mg/ml.Then NGA is put into mixed solution, so that mixing is molten
Liquid sufficiently submerges NGA, and is transferred into vacuum oven, impregnates 1h, vacuum degree 100mabr, and temperature is 60 DEG C.It takes
6h is freezed under conditions of putting it into -20 DEG C after out, then puts it into dry 12h in freeze drying equipment, before obtaining polymer
The three-dimensional graphene composite material (NGA-P) for driving liquid solution package, finally obtains three-dimensional graphite by Pintsch process for NGA-P
Alkene/polymer precursor conversion ceramic composite (NGA-PDC), cracking condition are as follows: in Ar atmosphere, be warming up to 5 DEG C/min
200 DEG C, 1h is kept the temperature, is warming up to 900 DEG C immediately with 5 DEG C/min, keeps the temperature Temperature fall after 1h.NGA-PDC is three-dimensional under this condition
Porous NGA-SiOC composite material (Fig. 5), density 11.5mg/cm3, conductivity 1.2S/m.Wherein graphene content is total
The 48.4% of quality.
Example 3.
(1) a certain amount of graphene oxide water solution (5mg/ml) and DOPA three-dimensional porous grapheme material preparation: are measured
The mass ratio of amine, graphene oxide and dopamine is 1:2.Then dopamine is added dropwise while stirring in graphene oxide water solution
In, by magnetic agitation, ultrasonic disperse in cold water obtains mixed solution.Mixed solution is transferred in vial and is sealed, is put into
In 90 DEG C of baking ovens, is taken out after 6h and obtain redox graphene hydrogel.Hydrogel is put into ethanol/water mixed solution always
It after changing 48h, is freezed under conditions of being put into -20 DEG C for 24 hours, taking-up is put into freeze drying equipment dry 72h, obtains three-dimensional oxygen reduction
Graphite alkene aeroge (GA).Then by GA at 1000 DEG C, 2h is heat-treated in argon atmosphere, Temperature fall obtains three-dimensional nitrogen and mixes
Miscellaneous graphene aerogel (NGA).
(2) three-dimensional porous graphene/polymer precursor conversion ceramic composite preparation: first by polymer precursor
Polysilazane, polysiloxanes and the tert-butyl alcohol-amphene are mixed evenly, and proportion is 100mg/ml.Then NGA is put into mixing
It in solution, so that mixed solution sufficiently submerges NGA, and is transferred into vacuum oven, impregnates 2h, vacuum degree is
100mabr, temperature are 50 DEG C.6h is freezed under conditions of putting it into -20 DEG C after taking-up, then is put it into freeze drying equipment
Dry 12h, obtains the three-dimensional graphene composite material (NGA-P) of polybenzazole precursor liquid solution package, NGA-P is finally passed through height
Anneal crack solution obtains three-dimensional grapheme/polymer precursor conversion ceramic composite (NGA-PDC), cracking condition are as follows: Ar atmosphere
In, 300 DEG C are warming up to 3 DEG C/min, keeps the temperature 3h, is warming up to 1000 DEG C immediately with 3 DEG C/min, keeps the temperature Temperature fall after 2h.It should
Under the conditions of NGA-PDC be three-dimensional porous NGA-SiOCN composite material (Fig. 6), density 144mg/cm3, conductivity 85.5S/
M, wherein graphene content is the 7.4% of gross mass.
Example 4.
(1) three-dimensional porous grapheme material preparation: measuring a certain amount of graphene oxide water solution (5mg/ml) and aniline,
The mass ratio of graphene oxide and aniline is 1:3.Then aniline is added dropwise while stirring in graphene oxide water solution, by magnetic
Power stirs, and ultrasonic disperse in cold water obtains mixed solution.Mixed solution is transferred in vial and is sealed, 80 DEG C of baking ovens are put into
In, it is taken out after 12h and obtains redox graphene hydrogel.Hydrogel is put into aging 48h in ethanol/water mixed solution
Afterwards, it is freezed under conditions of being put into -20 DEG C for 24 hours, taking-up is put into freeze drying equipment dry 72h, obtains three-dimensional oxygen reduction fossil
Black alkene aeroge (GA).Then by GA at 1000 DEG C, 2h is heat-treated in argon atmosphere, Temperature fall obtains three-dimensional N doping stone
Black alkene aeroge (NGA).
(2) three-dimensional porous graphene/polymer precursor conversion ceramic composite preparation: first by polymer precursor
Polysilazane and amphene are mixed evenly, and proportion is 200mg/ml.Then NGA is put into mixed solution, so that mixing
Solution sufficiently submerges NGA, and is transferred into vacuum oven, impregnates 2h, vacuum degree 300mabr, and temperature is 60 DEG C.
6h is freezed under conditions of putting it into -20 DEG C after taking-up, then puts it into dry 12h in freeze drying equipment, obtains polymer
The three-dimensional graphene composite material (NGA-P) of precursor solution package, finally obtains three-dimensional graphite by Pintsch process for NGA-P
Alkene/polymer precursor conversion ceramic composite (NGA-PDC), cracking condition are as follows: in Ar atmosphere, be warming up to 3 DEG C/min
250 DEG C, 3h is kept the temperature, is warming up to 1000 DEG C immediately with 3 DEG C/min, keeps the temperature Temperature fall after 2h.NGA-PDC is three-dimensional under this condition
Porous NGA-SiCN composite material (Fig. 7), density 1.5g/cm3, conductivity 165S/m, the wherein total matter of graphene content Zhan
The 1.2% of amount.
Three-dimensional porous and reported closely knit graphene prepared by above example 1,2,3 and 4/polymer precursor conversion
The density and conductivity relational graph of ceramic composite are as shown in Figure 8.It can be seen that the low-density composite of this patent preparation
Conductivity can reach the same order of magnitude with densified composite.This three-dimensional porous graphene/polymer precursor turns
Change ceramic composite in metal ion battery, electromagnetic shielding, the fields such as microbiological fuel cell have broad application prospects.
Claims (10)
1. a kind of three-dimensional porous graphene-polymer presoma converts ceramic composite, it is characterised in that three-dimensional grapheme net
Network structure filling polymer precursor converts ceramic material, and network internal is presented polymer precursor and converts ceramics-graphene-
Polymer precursor converts ceramic " sandwich " structure；The quality of graphene accounts for the 1~50% of composite material gross mass.
2. three-dimensional porous graphene-polymer presoma according to claim 1 converts ceramic composite, feature exists
Ceramic in the polymer precursor conversion is one or more of SiOC, SiOCN or SiCN.
3. three-dimensional porous graphene-polymer presoma according to claim 1 converts ceramic composite, feature exists
In: density is 11.5~1500mg/cm3, conductivity is 1.2~165 S/m.
4. a kind of three-dimensional porous graphene-polymer presoma as described in claim 1 for preparing converts ceramic composite
Method, the specific steps of which are as follows:
(1) graphene oxide water solution and reducing agent are measured respectively, the mass ratio of graphene oxide and reducing agent is 1:(1~5)；
By magnetic agitation, mixed solution is obtained after ultrasonic disperse；
(2) mixed solution prepared by step (1) is transferred in vial, sealing is placed into self assembly 6 in 50-90 DEG C of baking oven
~for 24 hours after, obtain three-dimensional redox graphene hydrogel；
(3) the three-dimensional redox graphene hydrogel that step (2) is prepared is put into the aqueous solution of ethyl alcohol after aging, is put
Freezing 12 under conditions of entering -20~-80 DEG C~for 24 hours, taking-up are put into freeze drying equipment dry, obtain three-dimensional oxygen reduction fossil
Black alkene aeroge；
(4) aeroge that step (3) is prepared is placed in tube furnace, and in Ar atmosphere, temperature rises to 800~1000 DEG C, is protected
1~3h of temperature, Temperature fall obtain three-dimensional nitrogen-doped graphene aeroge；
(5) polymer precursor and organic solvent are measured in container, is stirred；Wherein polymer precursor and organic
The mass volume ratio of solvent is 5~200mg/ml；
(6) the obtained three-dimensional nitrogen-doped graphene aeroge of step (4) is put into the solution that step (5) is configured, is filled
Sub-dip does not have, and is transferred into vacuum oven and impregnates；
(7) material after dipping in step (6) is taken out, 6~12h is freezed under conditions of putting it into -20~-80 DEG C, then will
It is put into drying in freeze drying equipment, obtains the three-dimensional graphene composite material of polybenzazole precursor liquid solution package；
(8) three-dimensional graphene composite material for wrapping up polybenzazole precursor liquid solution obtained in step (7) places tube furnace
In, calcining obtains three-dimensional porous graphene-polymer presoma conversion ceramic composite.
5. according to the method described in claim 4, it is characterized in that reducing agent is pyrroles, aniline, dopamine or second in step (1)
Any one in diamines.
6. according to the method described in claim 4, it is characterized in that the ageing time in step (3) is 24~72h；Freeze-drying
Drying time is 12~72h in equipment.
7. according to the method described in claim 4, it is characterized in that the polybenzazole precursor liquid solution in step (5) is poly- silicon oxygen
At least one of alkane, Polycarbosilane or polysilazane etc.；Organic solvent is appointing in the tert-butyl alcohol, amphene or the tert-butyl alcohol-amphene
It anticipates one kind.
8. according to the method described in claim 4, it is characterized in that the vacuum degree of vacuum oven is 100- in step (6)
300mbar；Temperature is 30-60 DEG C；Dip time is 1~3h.
9. according to the method described in claim 4, it is characterized in that in step (7) in freeze drying equipment drying time be 12~
24h。
10. according to the method described in claim 4, it is characterized in that calcining described in step (8) are as follows: in Ar atmosphere, press
200~300 DEG C of 1~3h of heat preservation crosslinkings are risen to according to the heating rate of 1~5 DEG C/min, according still further to the heating rate of 1~5 DEG C/min
900~1100 DEG C are risen to, heat preservation 1~3h cracking, then Temperature fall, finally obtains three-dimensional porous graphene-polymer forerunner
Body converts ceramic composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910274621.1A CN110078058A (en) | 2019-04-08 | 2019-04-08 | A kind of three-dimensional porous graphene-polymer presoma conversion ceramic composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910274621.1A CN110078058A (en) | 2019-04-08 | 2019-04-08 | A kind of three-dimensional porous graphene-polymer presoma conversion ceramic composite and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110078058A true CN110078058A (en) | 2019-08-02 |
Family
ID=67414418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910274621.1A Pending CN110078058A (en) | 2019-04-08 | 2019-04-08 | A kind of three-dimensional porous graphene-polymer presoma conversion ceramic composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110078058A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110726754A (en) * | 2019-10-22 | 2020-01-24 | 南京信息工程大学 | Preparation method and gas-sensitive application of graphene aerogel assembled on surface of device in situ |
| CN110808359A (en) * | 2019-08-15 | 2020-02-18 | 浙江工业大学 | MnO (MnO)2Preparation method of/rGO/PANI aerogel and application of aerogel in water-based zinc ion battery |
| CN110922191A (en) * | 2019-12-20 | 2020-03-27 | 厦门大学 | Silicon carbide polymer precursor ceramic defect healing method |
| CN111704467A (en) * | 2020-05-20 | 2020-09-25 | 深圳市科思飞科技有限公司 | Organic ceramic precursor and ceramic product |
| CN111943705A (en) * | 2020-08-28 | 2020-11-17 | 陕西科技大学 | Graphene/pyrolytic carbon/silicon carbide electromagnetic shielding composite material and preparation method thereof |
| CN112047690A (en) * | 2020-09-08 | 2020-12-08 | 邹发明 | Porous concrete composite material for wall |
| CN112735840A (en) * | 2021-01-04 | 2021-04-30 | 云南大学 | Triphenylphosphino porous organic polymer and graphene aerogel composite, preparation method thereof and application of supercapacitor |
| CN113201195A (en) * | 2021-06-15 | 2021-08-03 | 西北工业大学 | Barium strontium titanate porous ceramic/polyvinylidene fluoride composite material and preparation method thereof |
| JPWO2021225092A1 (en) * | 2020-05-07 | 2021-11-11 | ||
| CN114436269A (en) * | 2021-12-16 | 2022-05-06 | 南京信息工程大学 | Graphene-silicon-based aerogel and preparation method thereof |
| CN115385715A (en) * | 2022-09-15 | 2022-11-25 | 南京信息工程大学 | Porous carbon-rich silicon carbon nitrogen ceramic wave-absorbing heat-conducting material and preparation method thereof |
| CN116768648A (en) * | 2023-04-25 | 2023-09-19 | 天津中德应用技术大学 | Three-dimensional network micro-nano structure silicon-based precursor ultrahigh temperature elastic ceramic, preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105645403A (en) * | 2016-03-28 | 2016-06-08 | 南京邮电大学 | Preparation method of high-performance nitrogen-doped three-dimensional graphene |
| CN106946581A (en) * | 2017-04-20 | 2017-07-14 | 哈尔滨工业大学 | A kind of method that use 3D printing technique prepares conductive graphene/inorganic polymer composite material |
| CN108250728A (en) * | 2018-03-09 | 2018-07-06 | 四川大学 | A kind of polymer/graphene aeroge composite foam material and preparation method thereof |
| CN109243670A (en) * | 2018-09-14 | 2019-01-18 | 昆明理工大学 | A method of enhancing three-dimensional graphene framework structure prepares three-dimensional grapheme/polymer composite material |
-
2019
- 2019-04-08 CN CN201910274621.1A patent/CN110078058A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105645403A (en) * | 2016-03-28 | 2016-06-08 | 南京邮电大学 | Preparation method of high-performance nitrogen-doped three-dimensional graphene |
| CN106946581A (en) * | 2017-04-20 | 2017-07-14 | 哈尔滨工业大学 | A kind of method that use 3D printing technique prepares conductive graphene/inorganic polymer composite material |
| CN108250728A (en) * | 2018-03-09 | 2018-07-06 | 四川大学 | A kind of polymer/graphene aeroge composite foam material and preparation method thereof |
| CN109243670A (en) * | 2018-09-14 | 2019-01-18 | 昆明理工大学 | A method of enhancing three-dimensional graphene framework structure prepares three-dimensional grapheme/polymer composite material |
Non-Patent Citations (1)
| Title |
|---|
| CHEN SHEN等: "Anisotropic electrical conductivity in polymer derived ceramics induced by graphene aerogels", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110808359A (en) * | 2019-08-15 | 2020-02-18 | 浙江工业大学 | MnO (MnO)2Preparation method of/rGO/PANI aerogel and application of aerogel in water-based zinc ion battery |
| CN110726754A (en) * | 2019-10-22 | 2020-01-24 | 南京信息工程大学 | Preparation method and gas-sensitive application of graphene aerogel assembled on surface of device in situ |
| CN110726754B (en) * | 2019-10-22 | 2021-11-02 | 南京信息工程大学 | Preparation method and gas-sensitive application of graphene aerogel assembled on surface of device in situ |
| CN110922191A (en) * | 2019-12-20 | 2020-03-27 | 厦门大学 | Silicon carbide polymer precursor ceramic defect healing method |
| JPWO2021225092A1 (en) * | 2020-05-07 | 2021-11-11 | ||
| JP7260061B2 (en) | 2020-05-07 | 2023-04-18 | Dic株式会社 | Porous silicon oxycarbide composite material and method for producing porous silicon oxycarbide composite material |
| WO2021225092A1 (en) * | 2020-05-07 | 2021-11-11 | Dic株式会社 | Porous silicon oxycarbide composite material and method for manufacturing same |
| CN111704467A (en) * | 2020-05-20 | 2020-09-25 | 深圳市科思飞科技有限公司 | Organic ceramic precursor and ceramic product |
| CN111704467B (en) * | 2020-05-20 | 2022-04-29 | 深圳市科思飞科技有限公司 | Organic ceramic precursor and ceramic product |
| CN111943705A (en) * | 2020-08-28 | 2020-11-17 | 陕西科技大学 | Graphene/pyrolytic carbon/silicon carbide electromagnetic shielding composite material and preparation method thereof |
| CN112047690B (en) * | 2020-09-08 | 2022-08-19 | 邹发明 | Porous concrete composite material for wall |
| CN112047690A (en) * | 2020-09-08 | 2020-12-08 | 邹发明 | Porous concrete composite material for wall |
| CN112735840A (en) * | 2021-01-04 | 2021-04-30 | 云南大学 | Triphenylphosphino porous organic polymer and graphene aerogel composite, preparation method thereof and application of supercapacitor |
| CN113201195A (en) * | 2021-06-15 | 2021-08-03 | 西北工业大学 | Barium strontium titanate porous ceramic/polyvinylidene fluoride composite material and preparation method thereof |
| CN114436269A (en) * | 2021-12-16 | 2022-05-06 | 南京信息工程大学 | Graphene-silicon-based aerogel and preparation method thereof |
| CN115385715A (en) * | 2022-09-15 | 2022-11-25 | 南京信息工程大学 | Porous carbon-rich silicon carbon nitrogen ceramic wave-absorbing heat-conducting material and preparation method thereof |
| CN115385715B (en) * | 2022-09-15 | 2023-09-19 | 南京信息工程大学 | Porous carbon-rich silicon-carbon-nitrogen ceramic heat absorption waveguide material and preparation method thereof |
| CN116768648A (en) * | 2023-04-25 | 2023-09-19 | 天津中德应用技术大学 | Three-dimensional network micro-nano structure silicon-based precursor ultrahigh temperature elastic ceramic, preparation method and application |
| CN116768648B (en) * | 2023-04-25 | 2024-04-09 | 天津中德应用技术大学 | Three-dimensional network micro-nano structure silicon-based precursor ultrahigh temperature elastic ceramic, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110078058A (en) | A kind of three-dimensional porous graphene-polymer presoma conversion ceramic composite and preparation method thereof | |
| Wang et al. | N-doped honeycomb-like porous carbon towards high-performance supercapacitor | |
| CN106783197B (en) | A kind of ZIF-8 pyrolysis porous carbon-graphene composite material and its preparation method and application | |
| CN106601490B (en) | A kind of preparation method of biomass-based nitrogenous porous carbon and porous carbon and application thereof | |
| CN106517136B (en) | A kind of preparation method of iron/nitrogen co-doped ordered mesoporous carbon material | |
| CN102730680B (en) | High-density high-rigidity graphene porous carbon material as well as preparation method and applications thereof | |
| CN109385254B (en) | Graphene elastic polymer phase-change composite material and preparation method thereof | |
| CN112094625A (en) | Boron nitride nanotube aerogel/phase change heat conduction composite material and preparation method thereof | |
| CN106115652B (en) | A kind of B and/or P, N codope perilla leaf porous carbon and preparation method thereof | |
| CN108516548A (en) | A kind of preparation method of high mesoporous rate activated carbon and its activated carbon of acquisition | |
| CN110684510A (en) | Heat-conduction-enhanced heat-energy-storage shape-stabilized phase-change composite material and preparation method thereof | |
| CN107591250B (en) | A kind of porous carbon composite and its preparation method and application of CoO- N doping | |
| CN109461915A (en) | A kind of preparation method of the positive electrode of lithium-sulfur cell | |
| CN105742600A (en) | Preparation method for silicon dioxide/carbon nano composite aerogel negative electrode material of lithium ion battery | |
| CN107017091A (en) | Nitrogenous multistage porous carbon/graphene composite material and its preparation method and application | |
| CN102887711B (en) | Drying process of gelcasting large-sized and complex-shaped silicon carbide ceramic biscuit | |
| CN108831757B (en) | A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge | |
| CN105742655B (en) | A kind of classifying porous carbon material of fuel cell and its preparation and application | |
| Ma et al. | ZIF-derived mesoporous carbon materials prepared by activation via Na2SiO3 for supercapacitor | |
| CN108314003A (en) | Preparation method of nitrogen-doped porous carbon particles | |
| CN107963620A (en) | A kind of preparation method of high nitrogen doped Carbon Materials | |
| CN108039283B (en) | A kind of rich N doping multi-stage porous carbon material and the preparation method and application thereof based on in-situ polymerization | |
| CN109461594A (en) | A kind of three-dimensional porous graphene/active carbon electrode material of the doping of high voltage and preparation method thereof | |
| CN104167298A (en) | Graphene-protein derived carbon supercapcaitor material and preparation method thereof | |
| CN106115697A (en) | A kind of preparation method of the rich surface activated carbon containing petal-shaped Graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190802 |
|
| WD01 | Invention patent application deemed withdrawn after publication |