CN106927451B - Three-dimensional structure graphene and its carbon source self-template catalytic pyrolysis preparation method - Google Patents
Three-dimensional structure graphene and its carbon source self-template catalytic pyrolysis preparation method Download PDFInfo
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Abstract
The invention discloses graphene of a kind of three-dimensional structure and preparation method thereof, includes the following steps: that (1) will be mixed by pretreated macroreticular resin with metal ion saline solution, dried after stirring, obtain adsorbing metal ions resin；(2) resin of the adsorbing metal ions is crushed, transitional mould filling agent is then added, is uniformly mixed；(3) product that step (2) obtains is added in reaming agent solution, is dried after stirring；(4) product that step (3) obtains is heat-treated in atmosphere of inert gases；(5) product obtained step (4) carry out pickling, filtering, drying to get the three-dimensional structure graphene.Above-mentioned three-dimensional grapheme material is in micropore, the open pore self supporting structure of mesoporous, macropore and micron order macroscopic pores multi-layer, it is controllable with pore structures at different levels and distribution, the number of plies is few, large specific surface area, porosity it is high with conductivity is high, density is low, is not easy the features such as stacking again, have a extensive future.
Description
Technical field
The present invention relates to technical field of graphene, more particularly to three-dimensional structure graphene and its carbon source self-template catalytic thermal
Solve preparation method.
Background technique
Graphene is as a kind of Novel Carbon Nanomaterials, because of its unique two-dimensional structure and excellent electricity, mechanics, calorifics
And optical property, it is had broad application prospects in fields such as electronic device, energy storage, catalysis, sensor and advanced composite material (ACM)s.
And low cost, macroscopic preparation of graphene and be allowed to form various three-dimensional function structures in high quality, it is to realize its large-scale application
Key.The grapheme material of existing magnanimity preparation is in two-dimensional layered structure more, and the reason of because of its fabricating technology, is made
There are a large amount of oxygen-containing group and other residues in final product, that there are resistivity is higher, is easy stack reunion again, be difficult to assemble
At three-dimensional structure, specific surface area still not big enough, low yield and it is at high cost the deficiencies of place, limit its application and mass production.
Therefore, there is the grapheme material and preparation method thereof of three-dimensional self supporting structure, become graphene research in recent years
Develop one of most active field.
Three-dimensional grapheme material preparation at present mostly uses template and self-assembly method.Template is usually with foam metal or more
Mesoporous metal etc. is template, by the methods of chemical vapor deposition, grows one or more layers graphene, etching removal in template surface
After template, three-dimensional self supporting structure graphene is obtained.
If patent of invention CN105977502A is using nickel foam as template, by the method for chemical vapor deposition in nickel foam table
One layer of graphene film of length of looking unfamiliar, obtains the graphene with three-dimensional networks structure after etching the nickel that defoams with acid solution
The grapheme material of material, this three-dimensional networks structure has biggish specific surface area and excellent electronic conduction ability,
Utilize it as the carrier of electrode material or elctro-catalyst, the contact resistance of system can be effectively reduced, in electrochemical energy storage and
Energy conversion aspect has significant advantage.But such method is limited by chemical vapor deposition method low yield and template itself cost
Higher, the template removal more factors such as difficulty, can not large-scale production and application.
If patent CN105253880A is using high molecular polymer poly furfuryl alcohol as soft template, by method that solution is hydrated by stone
Black alkene is coated in glycan alcohol soft template, then obtains three-dimensional grapheme material, the three-dimensional grapheme that this method obtains after removing removing template
The size and shape in material hole depends entirely on the partial size and shape of template, by choosing suitable template, can get various types of
The mesoporous or macropore three-dimensional grapheme material of type, energy-storage battery, in terms of have good application prospect.But this method obtains
The three-dimensional grapheme material specific surface area obtained is smaller, and template and graphene uniform cladding are more difficult, are formed after removing removing template
Hole be mostly closed pore, be unfavorable for the diffusion of mass transfer in electrochemical system.
Preparing three-dimensional grapheme material by self-assembling method as presoma using graphene oxide can realize prepared by magnanimity.Such as
Patent CN105645402A forms sulfonated graphene using graphene oxide as presoma, by sulfonated reaction, afterwards and polyhydroxy
Freeze-drying obtains ordered laminar three-dimensional structure grapheme material after based compound hydro-thermal reaction, but due to introducing function base
Group, this method technique is more complex, the period is long, energy consumption is higher, and the grapheme material conductivity of acquisition is lower.
Summary of the invention
Based on this, the object of the present invention is to provide a kind of three-dimensional structure graphenes and its carbon source self-template catalytic pyrolysis to prepare
Method.
Specific technical solution is as follows:
The preparation method of three-dimensional structure graphene, includes the following steps:
(1) it will be mixed by pretreated macroreticular resin with metal ion saline solution, and dry, must adsorb after stirring
The resin of metal ion；
(2) resin of the adsorbing metal ions is crushed, transitional mould filling agent is then added, mixing is equal
It is even；
(3) product that step (2) obtains is added in reaming agent solution, is dried after stirring；
(4) product that step (3) obtains is heat-treated in atmosphere of inert gases；
(5) product obtained step (4) carry out pickling, filtering, drying to get the three-dimensional structure graphene.
In wherein some embodiments, the macroreticular resin is to have porous, big grid knot as carbon source and self-template
The resin of structure.Such as, the macroreticular resin includes one in macroporous ion exchange resin, macroporous absorption type resin and its intermediate
Kind or two kinds or more of mixture.
In wherein some embodiments, the concentration of metal cation salt is 0.01mol/L- in the metal ion saline solution
Saturated concentration (preferably 0.1-0.5mol/L)；The metal cation salt is selected from ferric trichloride, iron ammonium sulfate, ferric sulfate, iron
Potassium cyanide, potassium ferrocyanide, nitroso iron nacn, ferric nitrate, ironic citrate, ferrous sulfide, ferric oxalate, cobalt chloride, sulfuric acid
Cobalt, cobalt nitrate, natrium cobaltinitrosum, cobalt acetate, cobalt potassium nitrite, nickel acetate, nickel sulfate, ammonium nickel sulfate, nickel chloride, nickel nitrate,
One or more of nickel oxalate, nickelous bromide.
In wherein some embodiments, the amount ratio of the metal cation salt and the resin is 0.04mol-3.2mol:
1kg。
In wherein some embodiments, the amount ratio of the metal cation salt and the resin is 0.04mol-2mol:
1kg。
In wherein some embodiments, the transitionality mould filling agent is calcium hydroxide, calcium oxide, one in calcium carbonate
Kind is several；It is described transitionality mould filling agent by grind or ball milling in a manner of be mixed into step (1) products therefrom；The mistake
The mass ratio of the agent of crossing property mould filling and the resin is 0.1~10kg/kg (preferably 0.5-2kg/kg).
In wherein some embodiments, the expanding agent be one of potassium hydroxide, sodium hydroxide or calcium hydroxide or
Several (preferably using potassium hydroxide)；The expanding agent is mixed into step in the form that alcohol saturated solution or suspension are stirred
Suddenly in (2) resulting material；The mass ratio of the expanding agent and the resin is 0.1~5kg/kg (preferably 0.5-2kg/kg).
In wherein some embodiments, the transitionality mould filling agent: the expanding agent: the mass ratio of the resin is
0.1-10:0.1-5:1.
In wherein some embodiments, the process of thermal treatment parameter are as follows: heated with the heating rate of 1-10 DEG C/min
To 500 DEG C -1100 DEG C, and 0.1-6h is kept the temperature at such a temperature, then room temperature is down to 1-10 DEG C/min rate of temperature fall.
In wherein some embodiments, which is characterized in that in step (5), the acid used in the pickling is hydrochloric acid or nitre
Acid, soaking time 24-72h；The temperature of the drying is 60 DEG C -250 DEG C, and the time of the drying is 24-72h.
It is a further object of the present invention to provide the three-dimensional structure graphenes that above-mentioned preparation method is prepared.
Above-mentioned preparation method is using from a wealth of sources, low-cost porous macroreticular resin as carbon source and self-template, with mistake
Metal is crossed as low temperature graphitization catalyst, and add the filling of a certain amount of vestibule transitionality and activation filler and
/ expanding agent is made, by being pyrolyzed, realizes in-situ carburization, graphitization and increasing, the reaming of carbon source and self-template, then clearly
Non- carbon residue is washed off, the porous form the few-layer graphene alkene powder body material of three-dimensional structure is prepared into.Three-dimensional grapheme of the present invention
Material in micropore (aperture ﹤ 2nm), mesoporous (2~50nm), macropore (> 50nm) and micron order macroscopic pores multi-layer open pore oneself
Support construction has pore structures at different levels and distribution controllable, and the number of plies is few, large specific surface area, porosity are high and conductivity is high, density
It is low, be not easy the features such as stacking again, have a extensive future.Described preparation is simple, etches without later period template, non-carbon
Residue easy-clear, low in cost, part material is Ke Xunhuanliyong, it is easy to accomplish large-scale production.
(1) above-mentioned preparation method simple process etches, non-carbon residue easy-clear, low in cost, portion without later period template
Divide raw material can be recycled, it is easy to accomplish large-scale production；
(2) above-mentioned preparation method uses the transition metal such as iron, cobalt, nickel as low temperature graphitization catalyst, in lower temperature
Degree is lower to realize higher level of graphitization；
(3) the porous macroreticular resin in above-mentioned preparation method has both two functions of carbon source and self-template, is aided with and added
The agent of crossing property mould filling and make/expanding agent, so that the original porous form of resin is maintained, increased during catalytic pyrolysis and
Expansion by Rational choice resin and adjustment resin, transitional mould filling agent, makes the/ratio of expanding agent three, controllable
The structure and distribution in multi-layer hole in three-dimensional structure grapheme material；
(4) the three-dimensional structure grapheme material that above-mentioned preparation method obtains has few number of plies, large specific surface area, porosity high
With conductivity is high, density is low, is not easy the advantages that stacking again.
Detailed description of the invention
Fig. 1 be 1 sample of embodiment phenogram ((a) be X-ray diffraction analysis figure spectrum (XRD)；(b) Raman (Raman) figure
Spectrum；(c) scanning electron microscope (SEM) figure；(d) transmission electron microscope (TEM) figure；(e) BET graph of pore diameter distribution)；
Fig. 2 is phenogram ((a) SEM figure of 2 sample of embodiment；(b) BET graph of pore diameter distribution)；
Fig. 3 is phenogram ((a) SEM figure of 3 sample of embodiment；(b) BET graph of pore diameter distribution)；
Fig. 4 is phenogram ((a) SEM figure of 4 sample of embodiment；(b) BET graph of pore diameter distribution).
Specific embodiment
To facilitate the understanding of the present invention, below by invention is more fully described.But the present invention can be with many
Different form is realized, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes pair
The understanding of the disclosure is more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
Embodiment 1
A kind of preparation method of three-dimensional structure graphene of the present embodiment, includes the following steps:
(1) the pretreated macroporous acrylic cation exchanger resin of 50g is added to 200ml concentration is 0.2mol/L
Cobalt chloride solution in, be put into 80 DEG C of stirring in water bath after stirring 2h and be evaporated, continue to be put into the dry 12h of 80 DEG C of air dry ovens,
Obtain the resin of absorption cobalt ions；
(2) step (1) products therefrom is crushed, 50g calcium hydroxide powder is added, ground and mixed is uniform；
(3) 50g potassium hydroxide is dissolved in 400ml dehydrated alcohol and forms potassium hydroxide/ethanol solution, it will be obtained by step (2)
Product is added in potassium hydroxide/ethanol solution, is put into 80 DEG C of oil bath stirring evaporations, and object to be mixed is put into 80 in after starchiness
DEG C baking oven continues dry 12h, crushes again after dry；
(4) step (3) products therefrom is put into high temperature furnace, is heat-treated in nitrogen atmosphere, with the heating rate of 2 DEG C/min
800 DEG C are risen to, 2h is kept the temperature, is naturally cooling to room temperature；
(5) step (4) the products therefrom hydrochloric acid solution of 1mol/L is impregnated into 36h, filtered, dry 36h, continues at 60 DEG C
8h is dried at 150 DEG C to get 1 sample of embodiment (Fig. 1) is arrived.
XRD (Fig. 1 a) analysis the result shows that, the degree of graphitization of 1 sample of embodiment obtained through the above steps is enough
It is high.Raman (Fig. 1 b) and TEM (Fig. 1 d) analysis the result shows that, 1 sample of embodiment is 3~4 layers of form the few-layer graphene alkene.SEM (figure
It 1c) analyzes result and BET (Fig. 1 e) test result shows that there are porous three-dimensional structures in 1 sample of embodiment, including is a large amount of mutual
Micropore (≤2nm of perforation), mesoporous (2~50nm) and macropore (50~100nm)；1 sample specific surface area of embodiment is 2298m2/
G, total pore volume are up to 1.68cm3/ g, the accounting highest of intermediary hole are 1.27cm3/g。
Embodiment 2
A kind of preparation method of three-dimensional structure graphene of the present embodiment, includes the following steps:
(1) the pretreated macroporous acrylic system adsorptive resin of 50g is added to the chlorine that 200ml concentration is 0.2mol/L
Change in cobalt aqueous solution, be put into 80 DEG C of stirring in water bath after stirring 2h and be evaporated, continues to be put into the dry 12h of 80 DEG C of air dry ovens, obtain
Adsorb the resin of cobalt ions；
(2) step (1) products therefrom is crushed, 50g calcium hydroxide powder is added, ground and mixed is uniform；
(3) 50g potassium hydroxide is dissolved in 400ml dehydrated alcohol and forms potassium hydroxide/ethanol solution, it will be obtained by step (2)
Product is added in potassium hydroxide/ethanol solution, is put into 80 DEG C of oil bath stirring evaporations, and object to be mixed is put into 80 in after starchiness
DEG C baking oven continues dry 12h, crushes again after dry；
(4) step (3) products therefrom is heat-treated in nitrogen atmosphere, rises to 800 DEG C with the heating rate of 2 DEG C/min,
2h is kept the temperature, room temperature is naturally cooling to；
(5) step (4) the products therefrom hydrochloric acid solution of 1mol/L is impregnated into 36h, filtering, 60 DEG C of dry 36h continue
150 DEG C of dry 8h to get arrive 2 sample of embodiment (Fig. 2).
SEM (Fig. 2 a) analysis the result shows that, 2 sample of embodiment equally exists the micron order hole being largely mutually communicated and sub-micro
Meter level hole.BET (Fig. 2 b) test result shows that 2 sample specific surface area of embodiment is 1962m2/ g, total pore volume are up to
1.48cm3/ g, intermediary hole pore volume are 1.19cm3/g。
Embodiment 3
A kind of preparation method of three-dimensional structure graphene of the present embodiment, includes the following steps:
(1) the pretreated macroporous acrylic cation exchanger resin of 50g is added to 200ml concentration is 0.2mol/L
Cobalt chloride solution in, be put into 80 DEG C of stirring in water bath after stirring 2h and be evaporated, continue to be put into the dry 12h of 80 DEG C of air dry ovens,
Obtain the resin of absorption cobalt ions；
(2) step (1) products therefrom is crushed, 50g calcium carbonate powder is added, ground and mixed is uniform；
(3) 50g potassium hydroxide is dissolved in 400ml dehydrated alcohol and forms potassium hydroxide/ethanol solution, it will be obtained by step (2)
Product is added in potassium hydroxide/ethanol solution, is put into 80 DEG C of oil bath stirring evaporations, and object to be mixed is put into 80 in after starchiness
DEG C baking oven continues dry 12h, crushes again after dry；
(4) step (3) products therefrom is heat-treated in nitrogen atmosphere, heating rate is 2 DEG C/min, rises to 800 DEG C, is protected
Warm 2h, is naturally cooling to room temperature；
(5) step (4) the products therefrom hydrochloric acid solution of 1mol/L is impregnated into 36h, filtering, 60 DEG C of dry 36h continue
150 DEG C of dry 8h to get arrive 3 sample of embodiment (Fig. 3).
SEM (Fig. 3 a) analysis the result shows that, 3 sample of embodiment is also to be made of a large amount of micron orders and submicron order aperture.
BET test result shows that 3 sample specific surface area of embodiment is 2026m2/ g, total pore volume are up to 1.40cm3/ g, intermediary hole hole
Volume is 1.16cm3/g。
Embodiment 4
A kind of preparation method of three-dimensional structure graphene of the present embodiment, includes the following steps:
(1) the pretreated macroporous acrylic cation exchanger resin of 50g is added to 200ml concentration is 0.2mol/L
Nickel acetate aqueous solution in, be put into 80 DEG C of stirring in water bath after stirring 2h and be evaporated, continue to be put into 80 DEG C of air dry ovens dry
12h obtains the resin of absorption nickel ion；
(2) step (1) products therefrom is crushed, 50g calcium hydroxide powder is added, ground and mixed is uniform；
(3) 50g potassium hydroxide is dissolved in 400ml dehydrated alcohol and forms potassium hydroxide/ethanol solution, it will be obtained by step (2)
Product is added in potassium hydroxide/ethanol solution, is put into 80 DEG C of oil bath stirring evaporations, and object to be mixed is put into 80 in after starchiness
DEG C baking oven continues dry 12h, crushes again after dry；
(4) step (3) products therefrom is heat-treated in nitrogen atmosphere, heating rate is 2 DEG C/min, rises to 800 DEG C, is protected
Warm 2h, is naturally cooling to room temperature；
(5) step (4) the products therefrom hydrochloric acid solution of 1mol/L is impregnated into 36h, filtering, 60 DEG C of dry 36h continue
150 DEG C of dry 8h to get arrive 4 sample of embodiment (Fig. 4).
SEM (Fig. 4 a) analysis the result shows that, 4 sample of embodiment equally exists the micron order hole being largely mutually communicated and sub-micro
Meter level hole.BET test result shows that 4 sample specific surface area of embodiment is 2330m2/ g, total pore volume are up to 1.62cm3/ g,
Intermediary hole pore volume is 1.21cm3/g。
Embodiment 5
A kind of preparation method of three-dimensional structure graphene of the present embodiment, includes the following steps:
(1) the pretreated macroporous acrylic cation exchanger resin of 50g is added to 200ml concentration is 0.2mol/L
Cobalt chloride aqueous solution in, be put into 80 DEG C of stirring in water bath after stirring 2h and be evaporated, continue to be put into 80 DEG C of air dry ovens dry
12h obtains the resin of absorption cobalt ions；
(2) step (1) products therefrom is crushed, 25g calcium hydroxide powder is added, ground and mixed is uniform；
(3) 25g potassium hydroxide is dissolved in 200ml dehydrated alcohol and forms potassium hydroxide/ethanol solution, it will be obtained by step (2)
Product is added in potassium hydroxide/ethanol solution, is put into 80 DEG C of oil bath stirring evaporations, and object to be mixed is put into 80 in after starchiness
DEG C baking oven continues dry 12h, crushes again after dry；
(4) step (3) products therefrom is heat-treated in nitrogen atmosphere, heating rate is 2 DEG C/min, rises to 800 DEG C, is protected
Warm 2h, is naturally cooling to room temperature；
(5) step (4) the products therefrom hydrochloric acid solution of 1mol/L is impregnated into 36h, filtering, 60 DEG C of dry 36h continue
150 DEG C of dry 8h to get arrive 5 sample of embodiment.
BET test result shows that 5 sample specific surface area of embodiment is 1981m2/ g, total pore volume are up to 1.72cm3/ g,
Intermediary hole pore volume is 1.16cm3/g。
Embodiment 6
A kind of preparation method of three-dimensional structure graphene of the present embodiment, includes the following steps:
(1) the pretreated macroporous acrylic cation exchanger resin of 50g is added to 200ml concentration is 0.2mol/L
Cobalt chloride aqueous solution in, be put into 80 DEG C of stirring in water bath after stirring 2h and be evaporated, continue to be put into 80 DEG C of air dry ovens dry
12h obtains the resin of absorption cobalt ions；
(2) step (1) products therefrom is crushed, 50g calcium hydroxide powder is added, ground and mixed is uniform；
(3) 25g potassium hydroxide is dissolved in 300ml dehydrated alcohol and forms potassium hydroxide/ethanol solution, it will be obtained by step (2)
Product is added in potassium hydroxide/ethanol solution, is put into 80 DEG C of oil bath stirring evaporations, and object to be mixed is put into 80 in after starchiness
DEG C baking oven continues dry 12h, crushes again after dry；
(4) step (3) products therefrom is heat-treated in nitrogen atmosphere, heating rate is 2 DEG C/min, rises to 800 DEG C, is protected
Warm 2h, is naturally cooling to room temperature；
(5) step (4) the products therefrom hydrochloric acid solution of 1mol/L is impregnated into 36h, filtering, 60 DEG C of dry 36h continue
150 DEG C of dry 8h to get arrive 6 sample of embodiment.
BET test result shows that 6 sample specific surface area of embodiment is 1342m2/ g, total pore volume are up to 1.43cm3/ g,
Intermediary hole pore volume is 1.34cm3/g。
Embodiment 7
A kind of preparation method of three-dimensional structure graphene of the present embodiment, includes the following steps:
(1) the pretreated macroporous acrylic cation exchanger resin of 50g is added to 200ml concentration is 0.2mol/L
Cobalt chloride aqueous solution in, be put into 80 DEG C of stirring in water bath after stirring 2h and be evaporated, continue to be put into 80 DEG C of air dry ovens dry
12h obtains the resin of absorption cobalt ions；
(2) step (1) products therefrom is crushed, 25g calcium hydroxide powder is added, ground and mixed is uniform；
(3) 50g potassium hydroxide is dissolved in 300ml dehydrated alcohol and forms potassium hydroxide/ethanol solution, it will be obtained by step (2)
Product is added in potassium hydroxide/ethanol solution, is put into 80 DEG C of oil bath stirring evaporations, and object to be mixed is put into 80 in after starchiness
DEG C baking oven continues dry 12h, crushes again after dry；
(4) step (3) products therefrom is heat-treated in nitrogen atmosphere, heating rate is 2 DEG C/min, rises to 800 DEG C, is protected
Warm 2h, is naturally cooling to room temperature；
(5) step (4) the products therefrom hydrochloric acid solution of 1mol/L is impregnated into 36h, filtering, 60 DEG C of dry 36h continue
150 DEG C of dry 8h to get arrive 7 sample of embodiment.
BET test result shows that 7 sample specific surface area of embodiment is 2321m2/ g, total pore volume are up to 1.42cm3/ g,
Intermediary hole pore volume is 1.21cm3/g。
Embodiment 8
A kind of preparation method of three-dimensional structure graphene of the present embodiment, includes the following steps:
(1) the pretreated macroporous acrylic cation exchanger resin of 50g is added to 200ml concentration is 0.2mol/L
Cobalt chloride aqueous solution in, be put into 80 DEG C of stirring in water bath after stirring 2h and be evaporated, continue to be put into 80 DEG C of air dry ovens dry
12h obtains the resin of absorption cobalt ions；
(2) step (1) products therefrom is crushed, 50g calcium hydroxide powder is added, ground and mixed is uniform；
(3) 100g potassium hydroxide is dissolved in 800ml dehydrated alcohol and forms potassium hydroxide/ethanol solution, it will be obtained by step (2)
Product is added in potassium hydroxide/ethanol solution, is put into 80 DEG C of oil bath stirring evaporations, and object to be mixed is put into 80 in after starchiness
DEG C baking oven continues dry 12h, crushes again after dry；
(4) step (3) products therefrom is heat-treated in nitrogen atmosphere, heating rate is 2 DEG C/min, rises to 800 DEG C, is protected
Warm 2h, is naturally cooling to room temperature；
(5) step (4) the products therefrom hydrochloric acid solution of 1mol/L is impregnated into 36h, filtering, 60 DEG C of dry 36h continue
150 DEG C of dry 8h to get arrive 8 sample of embodiment.
BET test result shows that 8 sample specific surface area of embodiment is 2571m2/ g, total pore volume are up to 1.92cm3/ g,
Intermediary hole pore volume is 1.57cm3/g。
Embodiment 9
A kind of preparation method of three-dimensional structure graphene of the present embodiment, includes the following steps:
(1) the pretreated macroporous acrylic cation exchanger resin of 50g is added to 200ml concentration is 0.2mol/L
Cobalt chloride aqueous solution in, be put into 80 DEG C of stirring in water bath after stirring 2h and be evaporated, continue to be put into 80 DEG C of air dry ovens dry
12h obtains the resin of absorption cobalt ions；
(2) step (1) products therefrom is crushed, 100g calcium hydroxide powder is added, ground and mixed is uniform；
(3) 50g potassium hydroxide is dissolved in 400ml dehydrated alcohol and forms potassium hydroxide/ethanol solution, it will be obtained by step (2)
Product is added in potassium hydroxide/ethanol solution, is put into 80 DEG C of oil bath stirring evaporations, and object to be mixed is put into 80 in after starchiness
DEG C baking oven continues dry 12h, crushes again after dry；
(4) step (3) products therefrom is heat-treated in nitrogen atmosphere, heating rate is 2 DEG C/min, rises to 800 DEG C, is protected
Warm 2h, is naturally cooling to room temperature；
(5) step (4) the products therefrom hydrochloric acid solution of 1mol/L is impregnated into 36h, filtering, 60 DEG C of dry 36h continue
150 DEG C of dry 8h to get arrive 9 sample of embodiment.
BET test result shows that 9 sample specific surface area of embodiment is 2136m2/ g, total pore volume are up to 2.33cm3/ g,
Intermediary hole pore volume is 1.98cm3/g
Embodiment 10
The present embodiment is with 1 difference of embodiment: heating rate is 5 DEG C/min, other processing steps in heat treatment process
And heat treatment process is same as Example 1, BET is analyzed the result shows that 10 sample specific surface area of embodiment is about 2034m2/ g, always
Pore volume is 1.46cm3/ g, intermediary hole pore volume are 0.99cm3/g。
Embodiment 11
The present embodiment is with 1 difference of embodiment: in heat treatment process holding temperature be 700 DEG C, other processing steps and
Heat treatment process is same as Example 1, and BET is analyzed the result shows that 11 sample specific surface area of embodiment is about 1294m2/ g, total hole
Volume is 0.99cm3/ g, intermediary hole pore volume are 0.45cm3/g。
Embodiment 12
The present embodiment is with 1 difference of embodiment: in heat treatment process holding temperature be 900 DEG C, other processing steps and
Heat treatment process is same as Example 1, and BET is analyzed the result shows that 12 sample specific surface area of embodiment is about 1153m2/ g, total hole
Volume is 1.15cm3/ g, intermediary hole pore volume are 1.04cm3/g。
Embodiment 13
The present embodiment is with 1 difference of embodiment: soaking time is 1h, other processing steps and Re Chu in heat treatment process
It is same as Example 1 to manage program, BET is analyzed the result shows that 13 sample specific surface area of embodiment is about 1810m2/ g, total pore volume
For 1.33cm3/ g, intermediary hole pore volume are 0.84cm3/g。
Embodiment 14
The present embodiment is with 1 difference of embodiment: soaking time is 4h, other processing steps and Re Chu in heat treatment process
It is same as Example 1 to manage program, BET is analyzed the result shows that 14 sample specific surface area of embodiment is about 2470m2/ g, total pore volume
For 2.01cm3/ g, intermediary hole pore volume are 1.74cm3/g。
Embodiment 15
The present embodiment is with 1 difference of embodiment: the metal salt solution in step (1) is the iron chloride of identical molal weight
Solution, other processing steps and heat treatment process are same as Example 1, and BET is analyzed the result shows that 15 sample specific surface of embodiment
Product is about 2333m2/ g, total pore volume 1.77cm3/ g, intermediary hole pore volume are 1.50cm3/g。
The results list of embodiment 1-15 is as follows:
The BET test result enumerated from above table can be seen that replacement different carbon source, filler type and catalysis stone
Inkization metal salt (embodiment 2-4, embodiment 15), obtains having hierarchical porous structure under relative mass ratio unanimous circumstances
Three-dimensional structure grapheme material；By regulation filler, the ratio of expanding agent and resin three are made, it can be achieved that three-dimensional structure stone
The regulation (embodiment 5-9) of black alkene material specific surface area, pore volume and mesoporous ratio；By regulating and controlling heat treatment temperature and time,
(embodiment 10-14) is advanced optimized to three-dimensional structure grapheme material microstructure to achievable.
Comparative example 1
This comparative example is with 1 difference of embodiment: it does not carry out step 2 (grinding of calcium hydroxide powder is not added), it is other
Processing step and heat treatment process are same as Example 1, and BET is analyzed the result shows that 1 sample specific surface area of comparative example is about
1892m2/ g, total pore volume 0.72cm3/ g, intermediary hole pore volume are only 0.13cm3/ g, micropore pore volume 0.59cm3/g。
Comparative example 2
This comparative example is with 1 difference of embodiment: not carrying out step 3 (potassium hydroxide solution is not added), other techniques
Step and heat treatment process are same as Example 1, and BET is analyzed the result shows that 2 sample specific surface area of comparative example is about 756m2/ g,
Total pore volume is 1.06cm3/ g, intermediary hole pore volume are 0.88cm3/g。
Comparative example 1 the result shows that, only be added make expanding agent potassium hydroxide in the case where, obtained grapheme material compares table
Area is higher, but pore volume is smaller, shows that material intermediary hole accounts for that smaller, micropore is more；Comparative example 2 the result shows that, only
In the case where filler is added, although specific surface area is lower, pore volume is significantly greater than 1 sample of comparative example, shows filler
The hole left after removal is based on mesoporous；Based on this, the method that embodiment 1 uses while filler is added and makes expanding agent is obtained
The grapheme material obtained is provided simultaneously with higher specific surface area and biggish pore volume, and has micropore, mesoporous and micron order hole
3-dimensional multi-layered grade pore structure, in terms of compensating for individually addition filler or making the resulting grapheme material microstructure of expanding agent
Deficiency.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (11)
1. the preparation method of three-dimensional structure graphene, which comprises the steps of:
(1) it will be mixed by pretreated macroreticular resin with metal ion saline solution, and be dried after stirring, obtain adsorbing metal
The resin of ion；
(2) resin of the adsorbing metal ions is crushed, transitional mould filling agent is then added, is uniformly mixed；
(3) product that step (2) obtains is added in reaming agent solution, is dried after stirring；
(4) product that step (3) obtains is heat-treated in atmosphere of inert gases；
(5) product obtained step (4) carry out pickling, filtering, drying to get the three-dimensional structure graphene.
2. preparation method according to claim 1, which is characterized in that the macroreticular resin is as carbon source and self-template
The resin for having porous, big network.
3. preparation method according to claim 2, which is characterized in that the macroreticular resin includes macropore amberlite
The mixture of one or both of rouge, macroporous absorption type resin and its intermediate or more.
4. preparation method according to claim 1, which is characterized in that metal cation salt in the metal ion saline solution
Concentration be 0.1-0.5mol/L；The amount ratio of the metal cation salt and the resin is 0.04mol-3.2mol:1kg；Institute
It states metal cation salt and is selected from ferric trichloride, iron ammonium sulfate, ferric sulfate, the potassium ferricyanide, potassium ferrocyanide, nitroso iron cyaniding
Sodium, ferric nitrate, ironic citrate, ferrous sulfide, ferric oxalate, cobalt chloride, cobaltous sulfate, cobalt nitrate, natrium cobaltinitrosum, cobalt acetate, Asia
One or more of Fischer's yellow, nickel acetate, nickel sulfate, ammonium nickel sulfate, nickel chloride, nickel nitrate, nickel oxalate, nickelous bromide.
5. preparation method according to claim 1, which is characterized in that it is described transitionality mould filling agent be calcium hydroxide,
One or more of calcium oxide, calcium carbonate；It is described transitionality mould filling agent by grind or ball milling in a manner of be mixed into step
(1) in products therefrom；The mass ratio of the transitionality mould filling agent and the resin is 0.1~10kg/kg.
6. preparation method according to claim 1, which is characterized in that the expanding agent be potassium hydroxide, sodium hydroxide or
One or more of calcium hydroxide；The expanding agent is mixed into step in the form that alcohol saturated solution or suspension are stirred
Suddenly in (2) resulting material；The mass ratio of the expanding agent and the resin is 0.1~5kg/kg.
7. preparation method according to claim 1-6, which is characterized in that the transitionality mould filling agent: institute
State expanding agent: the mass ratio of the resin is 0.1-10:0.1-5:1.
8. preparation method according to claim 1-6, which is characterized in that the process of thermal treatment parameter are as follows:
Be heated to 500 DEG C -1100 DEG C with the heating rate of 1-10 DEG C/min, and keep the temperature 0.1-6h at such a temperature, then with 1-10 DEG C/
Min rate of temperature fall is down to room temperature.
9. preparation method according to claim 8, which is characterized in that the process of thermal treatment parameter are as follows: with 1-10 DEG C/
The heating rate of min is heated to 800 DEG C, and keeps the temperature 2-6h at such a temperature, then is down to room temperature with 1-10 DEG C/min rate of temperature fall.
10. preparation method according to claim 1-6, which is characterized in that in step (5), adopted in the pickling
Acid is hydrochloric acid or nitric acid, soaking time 24-72h；The temperature of the drying is 60 DEG C -250 DEG C, the time of the drying
For 24-72h.
11. the three-dimensional structure graphene that any one of the claim 1-10 preparation method is prepared.
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| CN112117417A (en) * | 2019-06-19 | 2020-12-22 | 广州汽车集团股份有限公司 | Battery diaphragm, preparation method thereof and lithium-sulfur battery |
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| CN104528696A (en) * | 2014-12-16 | 2015-04-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method for graphene and graphene |
| CN105923623A (en) * | 2016-04-19 | 2016-09-07 | 广西大学 | Preparation method of graphene powder with three-dimensional hierarchical porous structure |
| CN105936503A (en) * | 2016-04-26 | 2016-09-14 | 中山大学 | Three-dimensional graphitized carbon material rich in continuous mesoporous structure and preparation method thereof |
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| CN104528696A (en) * | 2014-12-16 | 2015-04-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method for graphene and graphene |
| CN105923623A (en) * | 2016-04-19 | 2016-09-07 | 广西大学 | Preparation method of graphene powder with three-dimensional hierarchical porous structure |
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