CN110117000A - A kind of bulk carbon nano-fiber aeroge and preparation method thereof - Google Patents
A kind of bulk carbon nano-fiber aeroge and preparation method thereof Download PDFInfo
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- CN110117000A CN110117000A CN201910519121.XA CN201910519121A CN110117000A CN 110117000 A CN110117000 A CN 110117000A CN 201910519121 A CN201910519121 A CN 201910519121A CN 110117000 A CN110117000 A CN 110117000A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
Abstract
The present invention provides a kind of carbon nano-fiber aeroge and preparation method thereof, the carbon nano-fiber aeroge is in a length of 8~450mm, the sheet that width is 8~450mm and thickness is 8~40mm.The preparation method includes the following steps: S1) bacteria cellulose is soaked in the aqueous solution containing inorganic ammonium salt, form the bacteria cellulose aquagel of inorganic ammonium salt dipping；S2) bacteria cellulose aquagel that the inorganic ammonium salt impregnates is placed in -20~-60 DEG C and is freezed, is then freeze-dried, bacteria cellulose aeroge is obtained；S3 the bacteria cellulose aeroge) is obtained into carbon nano-fiber aeroge after 600 DEG C~1400 DEG C pyrolysis.The carbon nano-fiber aeroge yield of the preparation method is higher than 10%.
Description
Technical field
The invention belongs to technical field of nano material more particularly to a kind of bulk carbon nano-fiber aeroge and its preparation sides
The carbon nano-fiber aeroge yield of method, the preparation method is higher than 10%.
Background technique
Carbon aerogels have noticeable special performance, including low bulk density, bigger serface, hole knot abundant
Structure, high conductivity, good mechanical performance, stable chemical property and Environmental compatibility.Carbon aerogels are in environmental protection, electrification
Learning energy stores and conversion, polymer science and advanced sensors field has great application potential.
In the preparation method of carbon aerogels common at present, or use toxic predecessor as raw material (such as resorcinol
And formaldehyde) or require complicated equipment and technology (such as CVD method), or require expensive assembling primitive (such as CNT and graphite
Alkene), these limitations show the preparation methods of carbon aerogels, and there are also further development spaces.Nearest many researchers start from life
Substance prepares high performance three-dimensional manometer carbon aerogels.Bacteria cellulose can pass through as a kind of typical biological material
The method of microbial fermentation carries out industrial production, have cheap, source is wide, it is environmentally friendly, the advantages such as can be prepared on a large scale, be
It is a kind of for manufacturing the desirable feedstock of functional three-dimensional carbon aerogels.
Cellulose nano-fibrous to be converted into carbon nano-fiber after bacteria cellulose pyrolysis, being formed has three-dimensional crosslinked network
The carbon aerogels of structure.But carbon nano-fiber aeroge is usually prepared using bacterial fibers at present, bacterium is fine in pyrolytic process
Dimension element is decomposed into volatile small-molecule substance, so that the carbon nano-fiber aeroge yield obtained is very low, normally below
10%, and volume contraction is serious, not only increases the cost for preparing carbon aerogels, and to the serious waste of resource, limit
The extensive use of the derivative carbon nano-fiber aeroge of bacteria cellulose, therefore it is necessary to find the method for promoting carbon yield.
In addition, carbon nano-fiber aeroge obtained in currently available technology is usually all powdery or small block-like, because
This expectation obtains a kind of big blocky such as length and width in 50mm or more, thick existing to improve in the carbon nano-fiber aeroge of 8mm or more
Have the mechanical performance and processability of the carbon nano-fiber aeroge in technology, so as to for broad-area electrode material,
The fields such as continuous polymer packing material, large volume mechanics sensor.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of big blocky carbon nano-fiber aeroges and preparation method thereof.
The carbon nano-fiber aeroge yield of preparation method of the present invention is higher than 10%.
The present invention provides a kind of carbon nano-fiber aeroge, fiber in the carbon nano-fiber aeroge includes 50~
The carbon of 97wt%, the hydrogen of 0.3~5wt%, the oxygen of 1~40wt%, the nitrogen of 0.3~5wt%, 0.3~5wt% phosphorus, wherein institute
Carbon nano-fiber aeroge is stated in a length of 8~450mm, the sheet that width is 8~450mm and thickness is 8~40mm, by diameter 10-
The carbon nano-fiber of 100nm is constituted, and has crosslinking node between fiber, and node is fixed, what formation not can be rotated or slide
Three-dimensional crosslinked network structure, fiber surface are in amorphous carbon structure；The carbon nano-fiber aeroge density is 3~25mg cm-3, conductivity is 0.001-10S cm-1, specific surface area is 300~900m2g-1。
In addition, the present invention provides a kind of preparation methods of the carbon nano-fiber aeroge of high yield, comprising:
S1) bacteria cellulose is soaked in the aqueous solution containing inorganic ammonium salt, the bacterium for forming inorganic ammonium salt dipping is fine
Tie up hydrogel；
S2) bacteria cellulose aquagel that the inorganic ammonium salt impregnates is placed in -20~-60 DEG C and is freezed, is then carried out
Freeze-drying, obtains bacteria cellulose aeroge；
S3 the bacteria cellulose aeroge) is obtained into carbon nano-fiber aeroge after 600 DEG C~1400 DEG C pyrolysis.
Preferably, the solution containing inorganic ammonium salt is ammonium dihydrogen phosphate aqueous solution.
Preferably, in the step S1) in, the bacteria cellulose is soaked in the ammonium dihydrogen phosphate that temperature is 50~80 DEG C
In aqueous solution, while being stirred in soaking process.
Preferably, the concentration of the ammonium dihydrogen phosphate aqueous solution is 0.1~1000mmol/L, and soaking time is 3~7
It.
Preferably, in the step S2) in, it is described to freeze to include that bacteria cellulose is soaked in the cooling ethyl alcohol of liquid nitrogen
In.
Preferably, the freeze-off time is 10~40min.
Preferably, the freeze-drying uses the freeze drier for having heating plate.
Preferably, the heating temperature of the heating plate in a vacuum chamber be 40~70 DEG C, and the freeze-drying when
Between be 3~5 days.
Preferably, the bacteria cellulose in the step S1) before dipping in (10~500) × (10~500) × (10~
50)mm3Sheet, and in step s3 pyrolysis after obtain carbon nano-fiber aeroge be in (8~450) × (8~450)
× (8~40) mm3Sheet.
Detailed description of the invention
Fig. 1 is the digital photograph that carbon nano-fiber aeroge is prepared by pure bacteria cellulose, and left side is bacteria cellulose gas
Gel, right side are carbon nano-fiber aeroge；
Fig. 2 is the thermogravimetric curve for adulterating the bacteria cellulose of different inorganic ammonium salts；
Fig. 3 is the digital photograph of bulk carbon nano-fiber aeroge obtained in the embodiment of the present invention 1, and left side is doping phosphorus
The bacteria cellulose aeroge of acid dihydride ammonium, right side are carbon nano-fiber aeroge；
Fig. 4 is the digital photograph of carbon nano-fiber aeroge obtained in the embodiment of the present invention 2, and left side is doping phosphoric acid two
The bacteria cellulose aeroge of hydrogen ammonium, right side are carbon nano-fiber aeroge；
Fig. 5 is the stereoscan photograph of carbon nano-fiber aeroge obtained in the embodiment of the present invention 3；
It in compression strain is 30%, 50% and that Fig. 6, which is carbon nano-fiber aeroge obtained in the embodiment of the present invention 3,
Load-deformation curve when 80%；
Fig. 7 is that carbon nano-fiber aeroge obtained in the embodiment of the present invention 3 recycles 20,000 times under 80% compression strain
Load-deformation curve；
Fig. 8 is compression curve of the carbon nano-fiber aeroge at -100 DEG C obtained in the embodiment of the present invention 3；
Fig. 9 is compression curve of the carbon nano-fiber aeroge at 300 DEG C obtained in the embodiment of the present invention 3；
Figure 10 is compression curve of the carbon nano-fiber aeroge at 500 DEG C obtained in the embodiment of the present invention 3.
Specific embodiment
Below in conjunction with drawings and examples of the invention, clear, complete description is carried out to embodiment of the present invention.
Firstly, the present invention provides a kind of big blocky carbon nano-fiber aeroge, in the carbon nano-fiber aeroge
Fiber includes the carbon of 50~97wt%, the hydrogen of 0.3~5wt%, the oxygen of 1~40wt%, the nitrogen of 0.3~5wt%, 0.3~5wt%
Phosphorus, wherein the carbon nano-fiber aeroge be in a length of 8~450mm, the sheet that width is 8~450mm and thickness is 8~40mm,
It is made of the carbon nano-fiber of diameter 10-100nm, has crosslinking node between fiber, is formed complete tough and tensile (that is, node is solid
Fixed, not can be rotated or slide) three-dimensional crosslinked network structure, fiber surface is in amorphous carbon structure.
The density of the carbon nano-fiber aeroge is 3~25mg cm-3, for example, can be 3~20mg cm-3, and
From the aspect of preparing ultralight adsorbent material, preferably 3~15mg cm-3, more preferable 3-10mg cm-3。
The conductivity of the carbon nano-fiber aeroge is 0.001-10S cm-1, for example, can be 0.01-10S cm-1,
From the aspect of preparing electrode material and conductive filler, preferably 0.1-10S cm-1, more preferably 1-10S cm-1。
The specific surface area of the carbon nano-fiber aeroge is 300~900m2g-1, for example, can be 400~900m2g-1,
From the aspect of high surface area catalysts, preferably 500~900m2g-1, more preferably 700~900m2g-1。
In the present invention, term " big blocky " refers to that length is generous in the sheet of 8mm or more, and preferably length and width are in 50mm or more
Sheet.
Secondly, the present invention provides a kind of preparation method of carbon nano-fiber aeroge derived from bacteria cellulose, it is described
Method includes the following steps:
S1) bacteria cellulose is soaked in the aqueous solution containing inorganic ammonium salt, the bacterium for forming inorganic ammonium salt dipping is fine
Tie up hydrogel；
S2) bacteria cellulose aquagel that the inorganic ammonium salt impregnates is placed in -20~-60 DEG C and is freezed, is then carried out
Freeze-drying, obtains bacteria cellulose aeroge；And
S3 the bacteria cellulose aeroge) is obtained into carbon nano-fiber aeroge after 600 DEG C~1400 DEG C pyrolysis.
In the present invention, the example of the inorganic ammonium salt include ammonium chloride, ammonium sulfate, ammonium dihydrogen phosphate, etc..
In the present invention, the term " freezing ", which refers to, is frozen into ice cube for bacteria cellulose aquagel；Term " the freezing
It is dry " refer to that the bacteria cellulose ice cube freezed is placed in freeze drier, the lyophilization under cryogenic vacuum state.
In the present invention, term " bacteria cellulose " is a kind of marketable material, and there is no special limits in the present invention
System.Moreover, inventors believe that, bacterium will not influence invention effect of the invention in " bacteria cellulose ", because commercially available thin
Fungin has eliminated internal bacterium before factory.
One the present invention provides the preparation method of carbon nano-fiber aeroge derived from a kind of bacteria cellulose is specific
Example, comprising: S1) bacteria cellulose is soaked in the solution containing ammonium dihydrogen phosphate, make ammonium dihydrogen phosphate well into thin
In the network structure of fungin；S2) the bacteria cellulose aquagel for impregnating ammonium dihydrogen phosphate is placed in the cooling ethyl alcohol of liquid nitrogen
Among, freeze bacteria cellulose aquagel, be then freeze-dried, obtains bacteria cellulose aeroge；It S3) will be described thin
Fungin aeroge obtains carbon nano-fiber aeroge after carrying out high temperature pyrolysis.
In the present invention, it is preferred to which bacteria cellulose is first passed through deacidification processing；The deacidification processing is preferably in deionization
Deacidification is impregnated in water, and bacteria cellulose is more preferably soaked in the deionized water of warm (for example, 50~80 DEG C) and is removed
Acid；The time for impregnating deacidification is preferably 4~7 days, and needs replacement deionized water daily.
After deacidification processing, bacteria cellulose is preferably cut into suitably sized, application after the suitably sized basis
Or the size of test determines, preferably (10~500) × (10~500) × (10~50) mm3, more preferably (10~320)
× (10~240) × (10~30) mm3, it is further preferably (10~120) × (10~60) × (10~20) mm3。
Then, the bacteria cellulose with suitable dimension is soaked in the aqueous solution containing ammonium salt, wherein ammonium salt concentration
For 0.1~1000mmol/L；The solution is Warm soloution, for example, 50~80 DEG C, and preferably, is carried out in soaking process
Stirring.Preferably, the time of the immersion be 5~10 days so that the aqueous solution containing ammonium salt well into arrive bacteria cellulose
In.In other embodiments provided by the invention, the concentration of inorganic ammonium salt is preferably in the solution containing inorganic ammonium salt
0.5mmol/L。
In the specific embodiment of the present invention, the bacteria cellulose with suitable dimension is soaked in containing phosphoric acid
In the aqueous solution of ammonium dihydrogen；The concentration containing ammonium dihydrogen phosphate aqueous solution is preferably 0.1~1000mmol/L, more preferably
0.5~500mmol/L is further preferably 0.5~200mmol/L, most preferably 0.5~100mmol/L；Provided by the invention one
In a little embodiments, the concentration of the ammonium dihydrogen phosphate aqueous solution is preferably 100mmol/L；In some embodiments provided by the invention
In, the concentration of the ammonium dihydrogen phosphate aqueous solution is preferably 10mmol/L；It is described to impregnate preferably in warm ammonium dihydrogen phosphate water
It impregnates and stirs in solution, soaking time is preferably 5~10 days, is made containing ammonium dihydrogen phosphate aqueous solution well into bacterial fibers
The inside of element.
In refrigerating process, preferably ethyl alcohol is mixed with liquid nitrogen, preferably by the smooth expansion of bacteria cellulose, it is cold to be soaked in liquid nitrogen
But in ethyl alcohol.After bacteria cellulose freezes, preferably the ethyl alcohol that bacteria cellulose surface speckles with is cleaned, then carries out freezing and does
It is dry, obtain bacteria cellulose aeroge.Preferably -20~-60 DEG C of the cooling ethyl alcohol temperature of the liquid nitrogen, more preferably -30~-
40℃；The cooling time is 10~40min, preferably 20~30min.The freeze-drying is preferably cold with heating plate
It is carried out in lyophilizer, because bulk bacteria cellulose aquagel can be dried using heating plate, general freezer drying process, no
The dry bulk bacteria cellulose of energy, such as length and width are in the bacteria cellulose of 50mm or more；The temperature of cold-trap when the freeze-drying
Preferably -80 DEG C~-40 DEG C, more preferably -60 DEG C~-40 DEG C；The pressure when freeze-drying is preferably 0.01~
0.06mbar, more preferably 0.03~0.05mbar are further preferably 0.04mbar；Vacuum chamber heating plate temperature in the drying process
Preferably 40~70 DEG C, more preferably 50~60 DEG C of degree.The time of the freeze-drying is preferably 3~5 days.
The bacteria cellulose aeroge by freeze-drying is subjected to high temperature pyrolysis；The high temperature pyrolysis is preferably being protected
It is carried out in shield atmosphere；The protective atmosphere is protective atmosphere well known to those skilled in the art, is preferably nitrogen in the present invention
Gas and/or argon gas；The bacterial cellulose gel, which is preferably disposed in ceramic boat, carries out high temperature pyrolysis；The high temperature pyrolysis preferably exists
It is carried out in tube furnace；The heating rate of the high temperature pyrolysis is preferably 2~10 DEG C/min, because of the heating rate temperature of high temperature pyrolysis
Rate is too fast, will form more volatile materials, leads to the reduction of carbon aerogels yield；More preferably 3~8 DEG C/min, further preferably
For 4~6 DEG C/min, most preferably 5 DEG C/min；The temperature of the high temperature pyrolysis is preferably 600 DEG C~1400 DEG C, more preferably
800 DEG C~1200 DEG C；The time of the high temperature pyrolysis is preferably 1~3h, that is, be warming up to heat preservation 1 after the temperature of high temperature pyrolysis~
3h, more preferably 2h.
After high temperature pyrolysis, 400 DEG C~600 DEG C are preferably cooled to, 450 DEG C~550 DEG C is more preferably cooled to, further preferably drops
Temperature is to 500 DEG C, then is down to room temperature naturally, obtains carbon nano-fiber aeroge；The rate of the cooling is preferably 4~6 DEG C/min,
More preferably 5 DEG C/min.In the present invention, in the high temperature pyrolysis and temperature-fall period, normal pressure is kept in tube furnace.
Bacteria cellulose (standby BC replacement sometimes below) is decomposed into volatile small-molecule substance in pyrolytic process, so that
The carbon nano-fiber aeroge yield of acquisition is very low, and carbon nano-fiber aeroge volume contraction is serious, limits the extensive of it
Using.As shown in Figure 1, one block of pure BC aeroge is after pyrolysis, mass excess is only 6%, and volume is remaining as 10%.Pass through difference
Inorganic salts comparison discovery, ammonium dihydrogen phosphate have best promotion effect relative to ammonium sulfate and ammonium chloride, as shown in Figure 2,
When the molal weight of the fire retardants such as ammonium dihydrogen phosphate, ammonium sulfate and ammonium chloride and BC ratio are 1mmol/g, pure BC, ammonium dihydrogen phosphate
The carbon nano-fiber aeroge (being substituted sometimes with CNFA below) of impregnated sample, ammonium sulfate impregnated sample and ammonium chloride impregnated sample
Yield is respectively 7.3wt%, 31.4wt%, 26.4wt% and 19.0wt%.Calculation of yield formula of the CNFA for BC are as follows:
Here ωBCRefer to the actual mass fraction of BC in dipping BC aeroge.
Therefore, inventors believe that, the present invention uses inorganic ammonium salt (especially phosphorus in the case where being not bound by any theory
Acid dihydride ammonium) as the catalyst to change the route of bacteria cellulose fibre pyrolysis, effectively facilitate dehydration, make the gaseous state of loss with
Carbon-to-oxygen ratio declines in liquid product, and the carbon residue surplus after being pyrolyzed bacteria cellulose improves, and finally makes carbon nano-fiber aeroge
Yield improve.When impregnating bulk bacteria cellulose, using warm ammonium dihydrogen phosphate, and often stirs, phosphorus can be made
Acid dihydride ammonium is well into bacteria cellulose network structure；It is impregnated using room temperature solution, will lead to phosphoric acid inside bacteria cellulose
Ammonium dihydrogen content is lower, the yield decline of carbon aerogels.
In the case where being not bound by any theory, inventors believe that, in the present invention using liquid nitrogen and alcohol mixeding liquid into
Row freezing, can avoid the fragmentation in refrigerating process with bacteria cellulose aquagel uniform decrease in temperature.Directly use liquid nitrogen frozen bacterium
Cellulose, bacteria cellulose icing is too fast, will lead to bacteria cellulose rupture；Bacteria cellulose is placed in refrigerator and is freezed, by
The squeezing action crystallized in freezing process, bacteria cellulose can be squeezed into film, destroy original shape.By bacterial fibers
Mourning card can prepare the complete aeroge of fritter in the cooling walls of beaker of liquid nitrogen, but (length and width are equal for freezing bulk bacteria cellulose
Greater than 40mm) Shi Yiran fragmentation.When being freezed using the cooling ethyl alcohol of liquid nitrogen, the bacteria cellulose of smooth expansion uniformly drops
Temperature can obtain the complete aeroge of bulk；It is unable to complete freezing when ethyl alcohol temperature excessively high (such as -10 DEG C), ethyl alcohol temperature is too low
When (such as -70 DEG C), bacteria cellulose icing is too fast to be ruptured, therefore the ethyl alcohol temperature preferably -20~-60 that liquid nitrogen is cooling
℃。
In freezing dry process, when bacterial fibers pixel volume is larger, internal ice cannot distil completely, lead to airsetting
Glue can not be dried thoroughly in common freeze-drying, still aqueous after dry for a long time, lead to volume contraction.The present invention, which uses to have, to be added
The freeze drier of heat function is lyophilized, and vacuum chamber temperature of heating plate is preferably 40~70 DEG C in drying process, can will be big
Block bacteria cellulose is completely dried.
By freeze above with drying means collective effect, complete bulk bacteria cellulose aeroge can be obtained；Again
By pyrolysis, the bulk carbon nano-fiber aeroge of structural integrity can be obtained.The dipping, freezing and drying steps are must
It wants, the larger size carbon nano-fiber aeroge of structural integrity can just be prepared.
In addition, the present invention is using bacteria cellulose and inorganic ammonium salt (especially ammonium dihydrogen phosphate) as presoma, raw material
Cheap and easy to get, method is simple, is easy to be mass produced, and carbon nanoporous aerogel yield obtained improves, and improves raw material utilization
Rate effectively reduces cost；The carbon nano-fiber aeroge shape that the present invention obtains remains intact, since ammonium dihydrogen phosphate is promoted
The residual quantity of carbon in pyrolysis, therefore carbon nanofiber networks are more tough and tensile, and the aeroge is made to have excellent compression restorative
Energy and temperature stability, are conducive to various subsequent processing and application；The hetero atoms such as nitrogen phosphorus, miscellaneous original are introduced during synthesis
The carbon nano-fiber aeroge of son doping can be used as fuel cell redox reactions catalyst, it is also possible to make supercapacitor etc.
Electrode material.
The present invention also provides a kind of carbon nano-fiber aeroge of above method preparation, the carbon nano-fiber aeroges
Yield be higher than 10%, even higher than 15%, be higher than 20%, also be even as high as 33% or more.Carbon Nanowire prepared by the present invention
It is high to tie up aeroge yield, shape remains intact, and has excellent compression reaction performance and temperature stability；Aeroge contain nitrogen,
The hetero atoms such as phosphorus can be used for adsorbent material, sensor material, catalyst backbone, electrode material and polymer composites.
Compared with prior art, the present invention is used as catalyst by addition inorganic ammonium salt (especially ammonium dihydrogen phosphate), changes
The route for having become bacteria cellulose fibre pyrolysis, improves the yield of carbon nano-fiber aeroge, can obtain complete bulk
Carbon nano-fiber aeroge controls density, the conductivity of carbon nano-fiber aeroge by adjusting the solution concentration of inorganic ammonium salt
And the properties such as gap, prepare the carbon nano-fiber aeroge of different densities and mechanical performance；In addition, herein in connection with making in the present invention
It is freezed with the cooling ethyl alcohol of liquid nitrogen, the fragmentation in refrigerating process can be avoided with bacteria cellulose aquagel uniform decrease in temperature；Together
When, the present invention uses the freeze drier with heating function to be lyophilized, and can obtain bulk bacteria cellulose aeroge；And
And the present invention, using bacteria cellulose and inorganic ammonium salt (especially ammonium dihydrogen phosphate) as presoma, raw material is cheap and easy to get, side
Method is simple, is easy to be mass produced, and carbon nanoporous aerogel yield obtained improves, and improves raw material availability, is effectively reduced
Cost；The carbon nano-fiber aeroge shape that the present invention obtains remains intact, and is conducive to various subsequent processing and application；Most
Afterwards, the hetero atoms such as nitrogen phosphorus are introduced during synthesis, the carbon nano-fiber aeroge of Heteroatom doping can be used as fuel cell
Redox reactions catalyst, it is also possible to make the electrode material of supercapacitor etc..
Embodiment
In order to further illustrate the present invention, with reference to embodiments to derived from a kind of bacteria cellulose provided by the invention
Carbon nano-fiber aeroge and preparation method thereof is described in detail.
Reagent used in following embodiment is commercially available, wherein bacteria cellulose purchase has from hundred million moral food of Hainan
Limit company.
Embodiment 1
Take 320 × 240 commercially available × 20mm3Bacteria cellulose is large stretch of, impregnates 7 days in 60 DEG C of deionized water,
And deionized water is replaced daily.The bacteria cellulose sheet after acid will be gone to be cut into 280 × 220 × 20mm3Sheet it is stand-by.
10mmol/L ammonium dihydrogen phosphate aqueous solution is configured, is placed in 55 DEG C of baking oven, wherein by bacteria cellulose sheet
It impregnates 5 days, is during which stirred continuously solution.
Ethyl alcohol is mixed with liquid nitrogen, regulates and controls ethyl alcohol temperature at -35 DEG C or so, by the large stretch of smooth expansion of bacteria cellulose, leaching
Bubble freezes 25min, is during which continuously added liquid nitrogen and guarantees low temperature；Then ethyl alcohol is cleaned, bacteria cellulose is transferred to freeze-drying
4 days dry in machine, condenser temperature is -60 DEG C, pressure 0.04mbar, and vacuum chamber temperature of heating plate is 60 DEG C.
Bacteria cellulose/ammonium dihydrogen phosphate mixing aeroge that freeze-drying obtains is placed in ceramic boat, is then put
Enter tube furnace；Nitrogen is passed through into tube furnace as protection gas, tube furnace first is warming up to 800 DEG C with the rate of 5 DEG C/min, protects
Hold 2h；500 DEG C are cooled to the rate of 5 DEG C/min again, is finally down to room temperature naturally, obtains the carbon nano-fiber airsetting of black
Glue, the carbon nano-fiber aeroge yield are 25%, as shown in Figure 3.The size of obtained carbon nano-fiber aeroge
For long 230 × wide by 170 × thickness 15mm3。
Embodiment 2
Take one piece of 320 × 240 commercially available × 10mm3Bacteria cellulose is large stretch of, impregnates 7 in 60 DEG C of deionized water
It, and deionized water is replaced daily.The bacteria cellulose sheet after acid will be gone to be cut into 100 × 60 × 10mm3Small pieces it is stand-by.
10mmol/L ammonium dihydrogen phosphate aqueous solution is configured, is placed in 55 DEG C of baking oven, bacterial fibers plain piece is soaked wherein
Bubble 3 days, is during which stirred continuously solution.
Ethyl alcohol is mixed with liquid nitrogen, regulates and controls ethyl alcohol temperature at -35 DEG C or so, by the smooth expansion of bacteria cellulose small pieces, leaching
Bubble freezes 20min, is during which continuously added liquid nitrogen and guarantees low temperature；Then ethyl alcohol is cleaned, bacteria cellulose is transferred to freeze-drying
3 days dry in machine, condenser temperature is -60 DEG C, pressure 0.04mbar, and vacuum chamber temperature of heating plate is 50 DEG C.
Bacteria cellulose/ammonium dihydrogen phosphate mixing aeroge that freeze-drying obtains is placed in ceramic boat, is then put
Enter tube furnace；Nitrogen is passed through into tube furnace as protection gas, tube furnace first is warming up to 800 DEG C with the rate of 5 DEG C/min, protects
Hold 2h；500 DEG C are cooled to the rate of 5 DEG C/min again, is finally down to room temperature naturally, obtains the carbon nano-fiber airsetting of black
Glue, the carbon nano-fiber aeroge yield are 28%, as shown in Figure 4.The size of obtained carbon nano-fiber aeroge
For long 85 × wide by 50 × thickness 8mm3。
Embodiment 3
Take one piece of 320 × 240 commercially available × 12mm3Bacteria cellulose is large stretch of, impregnates 10 days in deionized water, and
Replacement deionized water daily.The bacteria cellulose sheet after acid will be gone to be cut into 25 × 15 × 12mm3Fritter it is stand-by.
10mmol/L ammonium dihydrogen phosphate aqueous solution is configured, is placed in 55 DEG C of baking oven, bacteria cellulose is impregnated 5 wherein
It, is during which stirred continuously solution.
Ethyl alcohol is mixed with liquid nitrogen, regulates and controls ethyl alcohol temperature at -35 DEG C or so, by the smooth expansion of fritter bacteria cellulose, leaching
Bubble freezes 15min, then cleans ethyl alcohol, bacteria cellulose is transferred to drying 3 days in freeze drier, condenser temperature is -55
DEG C, pressure 0.04mbar.
The bacteria cellulose aeroge that freeze-drying obtains is placed in ceramic boat, tube furnace is then placed in；To tube furnace
In be passed through nitrogen as protection gas, tube furnace first is warming up to 800 DEG C with the rate of 5 DEG C/min, keeps 2h；Again with 5 DEG C/min
Rate be cooled to 500 DEG C, be finally down to room temperature naturally, obtain the carbon nano-fiber aeroge of black, the carbon nano-fiber gas
Gel yield is 33%.The size of obtained carbon nano-fiber aeroge is long 20 × wide by 12 × thickness 9mm3。
Carbon nano-fiber aeroge quality obtained in embodiment 3 accounts for the 33.2% of bacteria cellulose aeroge quality,
Density is 6.2mg/cm3, conductivity 0.021S/cm.
Carbon nano-fiber aeroge obtained in embodiment 3 is observed using field emission scanning electron microscope, is tied
Fruit is referring to Fig. 5.The carbon nano-fiber aeroge that embodiment 3 obtains as shown in Figure 5 by 15~30nm of diameter carbon nano-fiber structure
At intermediate there are many cross-linked structures.
Mechanical test is carried out to carbon nano-fiber aeroge obtained in embodiment 3, Fig. 6 is that carbon provided in this embodiment is received
Rice fiber aeroge compresses 30%, 50% and 80% compressive stress strain curve, which can restore to the original state.Fig. 7 is
The carbon nano-fiber aeroge that embodiment 3 provides, the compressive stress strain curve in 80% strain compression circulation, the airsetting
Glue can bear 20,000 compression circulations, and it is only 6% that shape, which changes, and it is only 7% that maximum stress, which changes, shows it with good
Good compression reaction performance.
Carbon nano-fiber aeroge obtained in embodiment 3 is thermomechanically tested, Fig. 8-10 is what embodiment 3 provided
Compression stress strain curve of the carbon nano-fiber aeroge at -100 DEG C, 300 DEG C and 500 DEG C, the aeroge is in extreme temperature
Lower compression still resilient, has excellent temperature stability, this is because having complete tough and tensile three inside aeroge
Dimension graphitization network structure.
Embodiment 4
Take one piece of 320 × 240 commercially available × 12mm3Bacteria cellulose is large stretch of, impregnates 10 days in deionized water, and
Replacement deionized water daily.The bacteria cellulose sheet after acid will be gone to be cut into 25 × 15 × 12mm3Fritter it is stand-by.
10mmol/L ammonium sulfate solution is configured, is placed in 55 DEG C of baking oven, bacteria cellulose is impregnated wherein 5 days,
Period is stirred continuously solution.
Ethyl alcohol is mixed with liquid nitrogen, regulates and controls ethyl alcohol temperature at -35 DEG C or so, by the smooth expansion of bacteria cellulose, impregnates and freeze
15min is tied, ethyl alcohol is then cleaned, bacteria cellulose is transferred to drying 3 days in freeze drier, condenser temperature is -55 DEG C, pressure
It is by force 0.04mbar.
The bacteria cellulose aeroge that freeze-drying obtains is placed in ceramic boat, tube furnace is then placed in；To tube furnace
In be passed through nitrogen as protection gas, tube furnace first is warming up to 800 DEG C with the rate of 5 DEG C/min, keeps 2h；Again with 5 DEG C/min
Rate be cooled to 500 DEG C, be finally down to room temperature naturally, obtain the carbon nano-fiber aeroge of black, the carbon nano-fiber gas
Gel yield is 27%.
Carbon nano-fiber aeroge quality obtained in embodiment 4 accounts for the 27.0% of bacteria cellulose aeroge quality,
Density is 6.8mg/cm3, conductivity 0.025S/cm.The size of obtained carbon nano-fiber aeroge be it is long by 20 ×
Wide by 11 × thickness 8mm3。
Embodiment 5
Take one piece of 320 × 240 commercially available × 12mm3Bacteria cellulose is large stretch of, impregnates 10 days in deionized water, and
Replacement deionized water daily.The bacteria cellulose sheet after acid will be gone to be cut into 25 × 15 × 12mm3Fritter it is stand-by.
10mmol/L aqueous ammonium chloride solution is configured, is placed in 55 DEG C of baking oven, bacteria cellulose is impregnated wherein 5 days,
Period is stirred continuously solution.
Ethyl alcohol is mixed with liquid nitrogen, regulates and controls ethyl alcohol temperature at -35 DEG C or so, by the smooth expansion of bacteria cellulose, impregnates and freeze
15min is tied, ethyl alcohol is then cleaned, bacteria cellulose is transferred to drying 3 days in freeze drier, condenser temperature is -55 DEG C, pressure
It is by force 0.04mbar.
The bacteria cellulose aeroge that freeze-drying obtains is placed in ceramic boat, tube furnace is then placed in；To tube furnace
In be passed through nitrogen as protection gas, tube furnace first is warming up to 800 DEG C with the rate of 5 DEG C/min, keeps 2h；Again with 5 DEG C/min
Rate be cooled to 500 DEG C, be finally down to room temperature naturally, obtain the carbon nano-fiber aeroge of black, the carbon nano-fiber gas
Gel yield is 18%.The size of obtained carbon nano-fiber aeroge is long 17 × wide by 10 × thickness 8mm3。
Carbon nano-fiber aeroge quality obtained in embodiment 5 accounts for the 17.6% of bacteria cellulose aeroge quality,
Density is 5.7mg/cm3, conductivity 0.019S/cm.
Industrial applicability
Carbon nano-fiber aeroge yield of the invention is high, and shape remains intact, with excellent compression reaction performance and
Temperature stability；Aeroge contains the hetero atoms such as nitrogen, phosphorus, can be used for adsorbent material, sensor material, catalyst backbone, electricity
Pole material and polymer composites, thus there is potential industrial use.
Claims (10)
1. a kind of carbon nano-fiber aeroge, the fiber in the carbon nano-fiber aeroge includes the carbon of 50~97wt%, 0.3
The hydrogen of~5wt%, the oxygen of 1~40wt%, the nitrogen of 0.3~5wt%, 0.3~5wt% phosphorus, wherein the carbon nano-fiber gas
Gel is in a length of 8~450mm, the sheet that width is 8~450mm and thickness is 8~40mm, by the carbon nano-fiber of diameter 10-100nm
It constitutes, there is crosslinking node, and node is fixed between fiber, form the three-dimensional crosslinked network structure that not can be rotated or slide,
Fiber surface is in amorphous carbon structure；The carbon nano-fiber aeroge density is 3~25mg cm-3, conductivity 0.001-
10S cm-1, specific surface area is 300~900m2 g-1。
2. a kind of preparation method of carbon nano-fiber aeroge, described method includes following steps:
S1) bacteria cellulose is soaked in the aqueous solution containing inorganic ammonium salt, forms the bacteria cellulose of inorganic ammonium salt dipping
Hydrogel；
S2) bacteria cellulose aquagel that the inorganic ammonium salt impregnates is placed in -20~-60 DEG C and is freezed, is then freezed
It is dry, obtain bacteria cellulose aeroge；
S3 the bacteria cellulose aeroge) is obtained into carbon nano-fiber aeroge after 600 DEG C~1400 DEG C pyrolysis.
3. preparation method according to claim 2, wherein the solution containing inorganic ammonium salt is that ammonium dihydrogen phosphate is water-soluble
Liquid.
4. preparation method according to claim 2, in the step S1) in, the bacteria cellulose is soaked in temperature and is
In 50~80 DEG C of ammonium dihydrogen phosphate aqueous solution, while being stirred in soaking process.
5. preparation method according to claim 3, wherein the concentration of the ammonium dihydrogen phosphate aqueous solution be 0.1~
1000mmol/L, and soaking time is 3~7 days.
6. preparation method according to claim 2 or 3, in the step S2) in, it is described to freeze to include by bacteria cellulose
It is soaked in the cooling ethyl alcohol of liquid nitrogen.
7. preparation method according to claim 2 or 3, wherein the freeze-off time is 10~40min.
8. preparation method according to claim 2 or 3, wherein the freeze-drying is dry using the freezing with heating plate
Dry machine.
9. preparation method according to claim 8, wherein the heating temperature of the heating plate in a vacuum chamber is 40~70
DEG C, and the time of the freeze-drying is 3~5 days.
10. preparation method according to claim 2 or 3, wherein the bacteria cellulose in the step S1) before dipping is in
(10~500) × (10~500) × (10~50) mm3Sheet, and in step s3 pyrolysis after obtain carbon Nanowire
Tieing up aeroge is in (8~450) × (8~450) × (8~40) mm3Sheet.
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| CN114590794A (en) * | 2022-03-09 | 2022-06-07 | 中国科学技术大学 | Compressible carbon nanofiber aerogel, and preparation method and application thereof |
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Application publication date: 20190813 |