CN105118688B - A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/graphene film material - Google Patents
A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/graphene film material Download PDFInfo
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- CN105118688B CN105118688B CN201510566811.2A CN201510566811A CN105118688B CN 105118688 B CN105118688 B CN 105118688B CN 201510566811 A CN201510566811 A CN 201510566811A CN 105118688 B CN105118688 B CN 105118688B
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- 241000894006 Bacteria Species 0.000 title claims abstract description 122
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 99
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 90
- 239000000463 material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920002678 cellulose Polymers 0.000 claims abstract description 67
- 239000001913 cellulose Substances 0.000 claims abstract description 64
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 239000006185 dispersion Substances 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 230000000903 blocking effect Effects 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 15
- 239000007772 electrode material Substances 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 53
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 12
- 239000003990 capacitor Substances 0.000 description 9
- 229920000049 Carbon (fiber) Polymers 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 5
- 238000003828 vacuum filtration Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 241000255964 Pieridae Species 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229940101209 mercuric oxide Drugs 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910000474 mercury oxide Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- 229910001950 potassium oxide Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/graphene film material, the present invention relates to a kind of preparation method and applications of membrane material, the invention aims to solve, existing flexible electrode material preparation technology is complicated, cost is high, do not possess the problem of good stability and mechanical property, method is：Standby bacteria cellulose is prepared, prepares activated carbon fiber dispersion liquid；Prepare bacteria cellulose slurry；Composite dispersion liquid is prepared, bacteria cellulose slurry is filtered by vacuum film forming, composite dispersion liquid is then added and continues to filter drying, bacteria cellulose/activated carbon fiber/graphene film material is made, the materials application is in ultracapacitor.The present invention is produced on a large scale, and preparation technology is simple, cost is low, conducting membrane material stability and mechanical property are good, and being prepared into ultracapacitor has good capacitive character.The invention belongs to technical field of nano material.
Description
Technical field
The present invention relates to a kind of preparation method and applications of membrane material.
Background technology
Traditional energy sources is increasingly depleted, stimulates people to look for the alternative energy and effective energy storage
Device, and ultracapacitor has high power density and higher energy density, applied to hybrid electric vehicle, electric car, portable
The important field such as formula electronic equipment, enjoys people to favor always.
For today's society to the rapid growth of flexible, flexible equipment energy storage demand, it is of future generation inexpensive, soft that people are badly in need of research and development
Soft, flexible ultracapacitor, and electrode material is most important part.But existing flexible electrode material preparation technology
Complicated, cost height, does not possess good stability and mechanical property.Therefore, using one it is simple, effectively, environmental protection, suitable for rule
The preparation method of modelling production prepares high performance flexible electrode material and is even more important.
The content of the invention
It is high the invention aims to solve existing flexible electrode material preparation technology complexity, cost, do not possess good
Stability and mechanical property the problem of, there is provided a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material
And its application.
A kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material of the present invention, enters as follows
OK：
First, by bacteria cellulose shear it is blocking be immersed in supersound washing in deionized water, then carried out with after liquid nitrogen frozen
15~30h is freeze-dried, obtains standby bacteria cellulose；
2nd, standby bacteria cellulose is placed in tube furnace and carries out high temperature pyrolysis, produce activated carbon fiber, then to activity
Surfactant is added in carbon fiber, redisperse in deionized water, obtains activated carbon fiber dispersion liquid；
3rd, bacteria cellulose is sheared into blocking rear immersion supersound washing in deionized water, is subsequently placed in deionized water,
Stirring makes it be uniformly dispersed, and is then transferred in refiner and stirs, obtains bacteria cellulose slurry；
4th, surfactant is added into the graphene of acidifying, be then dispersed in deionized water, obtain graphene dispersion
Liquid；Graphene dispersing solution is added in activated carbon fiber dispersion liquid, stirring makes graphene and activated carbon fiber be uniformly dispersed, and obtains
To composite dispersion liquid；
5th, the bacteria cellulose slurry of step 3 is filtered by vacuum film forming, then adds composite dispersion liquid and continue to take out
Film forming is filtered, places into vacuum drying chamber and is dried, bacteria cellulose/activated carbon fiber/graphene film material is made；Wherein
The mass ratio of bacteria cellulose and the activated carbon fiber of step 2 is in bacteria cellulose/activated carbon fiber/graphene film material
(15~1.5):1；Bacteria cellulose and the stone being acidified in step 4 in bacteria cellulose/activated carbon fiber/graphene film material
The mass ratio of black alkene is 1:(0.02~0.2).
The application of bacteria cellulose/activated carbon fiber/graphene film material of the present invention refers to as application of electrode in super
In capacitor.
Activated carbon fiber has good chemical stability, electric conductivity and fake capacitance energy storage characteristic, it is considered to be Yi Zhongji
Potential electrode material for super capacitor.Bacteria cellulose, its film have hyperfine network structure, thin after cracking
Fungin can make carbon nano-fiber, gained activated carbon fiber function admirable.
Bacteria cellulose is obtained by the fermentation of microorganism, its function admirable, aboundresources, environment-friendly, film
With hyperfine network structure, high-crystallinity, high-purity, high mechanical properties, as a kind of emerging environmentally friendly material into
For the focus of domestic and international Material Field research, bacteria cellulose contains substantial amounts of hydroxyl, has good hydrophily, with other water
Hydrogenbond easily occurs for the macromolecule of dissolubility, thus bacteria cellulose has natural advantage as composite.
The unique two-dimensional structure of graphene and outstanding physical property, there is its application in ultracapacitor very big
Potentiality.Graphene has substantial amounts of interlayer structure compared with traditional porous carbon materials, causes it to have big specific surface area
Very high electric conductivity, so as to turn into the more promising electrode material of capacitor.
The present invention using it is a kind of it is inexpensive, it is environmentally friendly and can scale preparation method, pass through vacuum filtration, prepare
Go out membrane material and capacitor is assembled into this.Structure shows membrane material good mechanical performance, has good capacitive properties and excellent
Good recycling.Therefore, application of this membrane material in ultracapacitor has wide commercial promise.
Beneficial effects of the present invention：(1) spies such as the hyperfine network structure of bacteria cellulose and excellent mechanical property are utilized
Property, as base load nano active material, ultracapacitor self-supporting self-supporting flexible electrode can be prepared into；(2) it is sharp
Activated carbon fiber is prepared with the direct Pintsch process of the hyperfine network structure of bacteria cellulose；(3) it is produced on a large scale, preparation technology
Simply, energy-conservation, reaction condition be gentle, small toxicity, and raw material cost cheap and easy to get is low, membrane material stability and mechanical property are good；(4)
Directly being used as electrode of super capacitor has good capacitive character.
Brief description of the drawings
Fig. 1 is the photo of bacteria cellulose/activated carbon fiber/graphene film material prepared by embodiment 1；
The work prepared with bacteria cellulose/activated carbon fiber/graphene film material the electricity that Fig. 2 is obtained by embodiment 1
Cyclic voltammetry curve under different scanning speed of the pole in 6M potassium hydroxide electrolytes；Wherein a is 5mV/s, b 10mV/s, c
For 20mV/s, d 50mV/s；
The work prepared with bacteria cellulose/activated carbon fiber/graphene film material the electricity that Fig. 3 is obtained by embodiment 1
Constant current charge-discharge curve of the pole in 6M potassium hydroxide electrolytes；Wherein a is 1mA/cm2, b 2mA/cm2, c 5mA/cm2,
D is 10mA/cm2；
Fig. 4 is the work prepared with bacteria cellulose/activated carbon fiber/graphene film material obtained in embodiment 1
The AC impedance spectroscopy of electrode；
The work prepared with bacteria cellulose/activated carbon fiber/graphene film material the electricity that Fig. 5 is obtained by embodiment 2
Cyclic voltammetry curve under different scanning speed of the pole in 6M potassium hydroxide electrolytes；Wherein a is 5mV/s, b 10mV/s, c
For 20mV/s；
The work prepared with bacteria cellulose/activated carbon fiber/graphene film material the electricity that Fig. 6 is obtained by embodiment 2
Constant current charge-discharge curve of the pole in 6M potassium hydroxide electrolytes；Wherein a is 1mA/cm2, b 2mA/cm2, c 5mA/cm2,
D is 10mA/cm2；
The work prepared with bacteria cellulose/activated carbon fiber/graphene film material the electricity that Fig. 7 is obtained by embodiment 3
Cyclic voltammetry curve under different scanning speed of the pole in 6M potassium hydroxide electrolytes；Wherein a is 5mV/s, b 10mV/s, c
For 20mV/s；
The work prepared with bacteria cellulose/activated carbon fiber/graphene film material the electricity that Fig. 8 is obtained by embodiment 3
Constant current charge-discharge curve of the pole in 6M potassium hydroxide electrolytes；Wherein a is 1mA/cm2, b 2mA/cm2, c 5mA/cm2,
D is 10mA/cm2。
Embodiment
Technical solution of the present invention is not limited to the embodiment of act set forth below, in addition to each embodiment it
Between any combination.
Embodiment one：A kind of preparation of bacteria cellulose/activated carbon fiber/graphene film material of present embodiment
Method, carry out as follows：
First, by bacteria cellulose shear it is blocking be immersed in supersound washing in deionized water, then carried out with after liquid nitrogen frozen
15~30h is freeze-dried, obtains standby bacteria cellulose；
2nd, standby bacteria cellulose is placed in tube furnace and carries out high temperature pyrolysis, produce activated carbon fiber, then to activity
Surfactant is added in carbon fiber, redisperse in deionized water, obtains activated carbon fiber dispersion liquid；
3rd, the blocking rear immersion supersound washing in deionized water of bacteria cellulose shearing is got, is subsequently placed in deionized water
In, stirring makes it be uniformly dispersed, and is then transferred in refiner and stirs, obtains bacteria cellulose slurry；
4th, surfactant is added into the graphene of acidifying, be then dispersed in deionized water, obtain graphene dispersion
Liquid；Graphene dispersing solution is added in activated carbon fiber dispersion liquid, stirring makes graphene and activated carbon fiber be uniformly dispersed, and obtains
To composite dispersion liquid；
5th, the bacteria cellulose slurry of step 3 is filtered by vacuum film forming, then adds composite dispersion liquid and continue to take out
Film forming is filtered, places into vacuum drying chamber and is dried, bacteria cellulose/activated carbon fiber/graphene film material is made；Wherein
The mass ratio of bacteria cellulose and the activated carbon fiber of step 2 is in bacteria cellulose/activated carbon fiber/graphene film material
(15~1.5):1；Bacteria cellulose and the stone being acidified in step 4 in bacteria cellulose/activated carbon fiber/graphene film material
The mass ratio of black alkene is 1:(0.02~0.2).
Activated carbon fiber has good chemical stability, electric conductivity and fake capacitance energy storage characteristic, it is considered to be Yi Zhongji
Potential electrode material for super capacitor.Bacteria cellulose, its film have hyperfine network structure, thin after cracking
Fungin can make carbon nano-fiber, gained activated carbon fiber function admirable.
Bacteria cellulose is obtained by the fermentation of microorganism, its function admirable, aboundresources, environment-friendly, film
With hyperfine network structure, high-crystallinity, high-purity, high mechanical properties, as a kind of emerging environmentally friendly material into
For the focus of domestic and international Material Field research, bacteria cellulose contains substantial amounts of hydroxyl, has good hydrophily, with other water
Hydrogenbond easily occurs for the macromolecule of dissolubility, thus bacteria cellulose has natural advantage as composite.
The unique two-dimensional structure of graphene and outstanding physical property, there is its application in ultracapacitor very big
Potentiality.Graphene has substantial amounts of interlayer structure compared with traditional porous carbon materials, causes it to have big specific surface area
Very high electric conductivity, so as to turn into the more promising electrode material of capacitor.
Present embodiment using it is a kind of it is inexpensive, it is environmentally friendly and can scale preparation method, by vacuum filtration,
Prepare membrane material and capacitor is assembled into this.Structure shows membrane material good mechanical performance, has good capacitive properties
With excellent recycling.Therefore, application of this membrane material in ultracapacitor has wide commercial promise.
The beneficial effect of present embodiment：(1) the hyperfine network structure of bacteria cellulose and excellent mechanical property are utilized
Etc. characteristic, as base load nano active material, ultracapacitor self-supporting self-supporting flexible electrode can be prepared into；
(2) activated carbon fiber is prepared using the direct Pintsch process of the hyperfine network structure of bacteria cellulose；(3) it is produced on a large scale, makes
Standby technique is simple, energy-conservation, reaction condition are gentle, small toxicity, and raw material cost cheap and easy to get is low, membrane material stability and mechanical property
It is good；(4) being directly used as electrode of super capacitor has good capacitive character.
Freeze-drying is carried out in freeze drier in present embodiment, and bacteria cellulose is commercially available prod.
Embodiment two：Present embodiment is unlike embodiment one：Described bacteria cellulose is
Bacteria cellulose leftover pieces.It is other identical with embodiment one.
Embodiment three：Present embodiment is unlike embodiment one or two：It is super described in step 1
The condition of sound washing is ultrasonic time 10h, and each hour changes deionized water.Other and embodiment one or two-phase
Together.
Embodiment four：Unlike one of present embodiment and embodiment one to three：Described in step 2
The method of high temperature degradation be：Standby bacteria cellulose is placed in porcelain boat, is then placed in tube furnace；Argon is passed through into tube furnace
3~8h of gas or nitrogen, and using argon gas or nitrogen as protection gas；Tube furnace is warming up to 270 with 2~4 DEG C/min speed again
DEG C, then be warming up to 390 DEG C with 0.3~0.5 DEG C/min speed, then with 2~4 DEG C/min speed be warming up to 700 DEG C~
1100 DEG C, 2~4h is kept, then 400 DEG C are cooled to 3~5 DEG C/min speed, room temperature is finally naturally cooled to again, that is, completes.
It is other identical with one of embodiment one to three.
Embodiment five：Unlike one of present embodiment and embodiment one to four：Described in step 2
The method of high temperature degradation be：Standby bacteria cellulose is placed in porcelain boat, is then placed in tube furnace；Argon is passed through into tube furnace
Gas or nitrogen 6h, and using argon gas or nitrogen as protection gas, then tube furnace is warming up to 270 DEG C with 4 DEG C/min speed, then with
0.3 DEG C/min speed is warming up to 390 DEG C, is then warming up to 900 DEG C with 4 DEG C/min speed, keeps 2h, then with 5 DEG C/min
Speed be cooled to 400 DEG C, finally naturally cool to room temperature again, that is, complete other phases one of with embodiment one to four
Together.
Embodiment six：Unlike one of present embodiment and embodiment one to five：Described in step 2
Activated carbon fiber and surfactant mass ratio be 1:(0.3~3).Other phases one of with embodiment one to five
Together.
Embodiment seven：Unlike one of present embodiment and embodiment one to six：Described in step 3
Refiner in stir and refer under conditions of stir speed (S.S.) 10000rpm~15000rpm, 5min is stirred in refiner.Its
It is identical with one of embodiment one to six.
Embodiment eight：Unlike one of present embodiment and embodiment one to seven：Described in step 4
Acidifying graphene and surfactant mass ratio be 1:(0.25~1).One of other and embodiment one to seven
It is identical.
Embodiment nine：Unlike one of present embodiment and embodiment one to eight：Described surface
Activating agent is neopelex.It is other identical with one of embodiment one to eight.
Embodiment ten：Unlike one of present embodiment and embodiment one to nine：Described in step 4
The preparation method of graphene of acidifying be that graphene is ultrasonically treated 24h in the nitric acid that concentration is 64%, use deionized water
Washing, filter drying.It is other identical with one of embodiment one to nine.
Embodiment 11：The application of present embodiment bacteria cellulose/activated carbon fiber/graphene film material is
Refer to as application of electrode in ultracapacitor.
Beneficial effects of the present invention are verified by following examples：
The preparation method of embodiment 1, the present embodiment bacteria cellulose/activated carbon fiber/graphene film material, by following step
It is rapid to carry out：
First, by bacteria cellulose shear it is blocking be immersed in supersound washing 10h in deionized water, and change within each hour go from
Sub- water, freeze drier is transferred to after liquid nitrogen frozen and dries 20h, obtains standby bacteria cellulose；
2nd, standby bacteria cellulose is placed in porcelain boat, is then placed in tube furnace；Nitrogen is passed through into tube furnace and removes oxygen
6h, and as protection gas, tube furnace is warming up to 270 DEG C with 4 DEG C/min speed first, afterwards 0.3 DEG C/min speed liter
Then temperature is warming up to 900 DEG C to 390 DEG C with 4 DEG C/min speed, keep 2h；400 DEG C are cooled to 5 DEG C/min speed again,
Finally it is down to room temperature naturally again, produces activated carbon fiber, 15mg detergent alkylate sulphurs is then added into 50mg activated carbon fibers
Sour sodium, redisperse in deionized water, obtain activated carbon fiber dispersion liquid；
3rd, by the blocking rear immersion supersound washing 10h, and each hour is more in deionized water of 10g bacteria celluloses shearing
Deionized water is changed, is subsequently placed in deionized water, stirring makes it be uniformly dispersed, and is then transferred in refiner with per minute 12000
The speed turned, 5min is stirred, obtains bacteria cellulose slurry；
4th, 0.01g neopelexes are added in the graphene being acidified to 0.01g, is then dispersed in deionized water
In, obtain graphene dispersing solution；Graphene dispersing solution is added in activated carbon fiber dispersion liquid, stirring makes graphene and activity
Carbon fiber is uniformly dispersed, and obtains composite dispersion liquid；
5th, the bacteria cellulose slurry of step 3 is filtered by vacuum film forming, then adds composite dispersion liquid and continue to take out
Film forming is filtered, places into vacuum drying chamber and is dried, bacteria cellulose/activated carbon fiber/graphene film material is made.
The bacterial fibers in bacteria cellulose/activated carbon fiber/graphene film material after vacuum filtration and vacuum drying
The quality of element is 0.3g.
The photo of bacteria cellulose/activated carbon fiber/graphene film material manufactured in the present embodiment is as shown in Figure 1.
By bacteria cellulose/activated carbon fiber/graphene film material cutting of acquisition into 1.5cm × 2cm rectangles, directly
As ultracapacitor working electrode, platinized platinum is used as to electrode, and using mercury/mercuric oxide electrode as reference electrode, test self-supporting is soft
The capacitance characteristic of property membrane material electrode material.Test sample is labeled as BC-ACF-CN-1.
Electrode prepared by the bacteria cellulose/activated carbon fiber obtained to the present embodiment/graphene film material is in 6M hydrogen
The cyclic voltammetric performance test without sweep speed is carried out in potassium oxide electrolyte, as a result referring to Fig. 2.Show that difference is swept in figure
The activated carbon fiber of speed is in scanning potential region -0.9~0.2V, all the CV curves with quasi- rectangle.
Electrode prepared by the bacteria cellulose/activated carbon fiber obtained to the present embodiment/graphene film material is in 6M hydrogen
Constant current charge-discharge performance test is carried out in potassium oxide electrolyte, as a result referring to Fig. 3.From the figure 3, it may be seen that curve is shown well
Triangle, different multiplying lower curve are respectively provided with preferable symmetry.Maximum area specific capacitance reaches 1.15F/cm2, mass ratio electricity
It is about 237F/g to hold.Such as Fig. 4, in high frequency region, represent the deformation semi arch of electrode material charge-transfer resistance and represent electrode
X-axis intercept all very littles of material resistance, the straight line of y-axis is proximate in low frequency range, shows the intrinsic resistance of the electric capacity of electrode material
Anti- characteristic.
The preparation method of embodiment 2, the present embodiment bacteria cellulose/activated carbon fiber/graphene film material, by following step
It is rapid to carry out：
First, by bacteria cellulose shear it is blocking be immersed in supersound washing 10h in deionized water, and change within each hour go from
Sub- water, freeze drier is transferred to after liquid nitrogen frozen and dries 20h, obtains standby bacteria cellulose；
2nd, standby bacteria cellulose is placed in porcelain boat, is then placed in tube furnace；Nitrogen is passed through into tube furnace and removes oxygen
6h, and as protection gas, tube furnace is warming up to 270 DEG C with 4 DEG C/min speed first, afterwards 0.3 DEG C/min speed liter
Then temperature is warming up to 800 DEG C to 390 DEG C with 4 DEG C/min speed, keep 2h；400 DEG C are cooled to 5 DEG C/min speed again,
Finally it is down to room temperature naturally again, produces activated carbon fiber, 30mg detergent alkylate sulphurs is then added into 100mg activated carbon fibers
Sour sodium, redisperse in deionized water, obtain activated carbon fiber dispersion liquid；
3rd, by the blocking rear immersion supersound washing 10h, and each hour is more in deionized water of 10g bacteria celluloses shearing
Deionized water is changed, is subsequently placed in deionized water, stirring makes it be uniformly dispersed, and is then transferred in refiner with per minute 12000
The speed turned, 5min is stirred, obtains bacteria cellulose slurry；
4th, 0.005g neopelexes are added in the graphene being acidified to 0.02g, is then dispersed in deionized water
In, obtain graphene dispersing solution；Graphene dispersing solution is added in activated carbon fiber dispersion liquid, stirring makes graphene and activity
Carbon fiber is uniformly dispersed, and obtains composite dispersion liquid；
5th, the bacteria cellulose slurry of step 3 is filtered by vacuum film forming, then adds composite dispersion liquid and continue to take out
Film forming is filtered, places into vacuum drying chamber and is dried, bacteria cellulose/activated carbon fiber/graphene film material is made.
The bacterial fibers in bacteria cellulose/activated carbon fiber/graphene film material after vacuum filtration and vacuum drying
The quality of element is 0.3g.
By bacteria cellulose/activated carbon fiber/graphene film material cutting of acquisition into 1.5cm × 2cm rectangles, directly
As ultracapacitor working electrode, platinized platinum is used as to electrode, and using mercury/mercuric oxide electrode as reference electrode, test self-supporting is soft
The capacitance characteristic of property membrane material electrode material.Test sample is labeled as BC-ACF-CN-2.
Electrode prepared by the bacteria cellulose/activated carbon fiber obtained to the present embodiment/graphene film material is in hydrogen-oxygen
Change the cyclic voltammetric performance test carried out in potassium electrolyte without sweep speed, as a result referring to Fig. 5.Show that difference sweeps speed in figure
Activated carbon fiber in scanning potential region -0.9~0.2V, all CV curves with quasi- rectangle.
Electrode prepared by the bacteria cellulose/activated carbon fiber obtained to the present embodiment/graphene film material is in hydrogen-oxygen
Change and constant current charge-discharge performance test is carried out in potassium electrolyte, as a result referring to Fig. 6.It will be appreciated from fig. 6 that curve shows good three
Angular, different multiplying lower curve is respectively provided with preferable symmetry.Maximum area specific capacitance reaches 2.12F/cm2, quality specific capacitance
About 212F/g.
The preparation method of embodiment 3, the present embodiment bacteria cellulose/activated carbon fiber/graphene film material, by following step
It is rapid to carry out：
First, by bacteria cellulose shear it is blocking be immersed in supersound washing 10h in deionized water, and change within each hour go from
Sub- water, freeze drier is transferred to after liquid nitrogen frozen and dries 20h, obtains standby bacteria cellulose；
2nd, standby bacteria cellulose is placed in porcelain boat, is then placed in tube furnace；Nitrogen is passed through into tube furnace and removes oxygen
6h, and as protection gas, tube furnace is warming up to 270 DEG C with 4 DEG C/min speed first, afterwards 0.3 DEG C/min speed liter
Then temperature is warming up to 900 DEG C to 390 DEG C with 4 DEG C/min speed, keep 2h；400 DEG C are cooled to 5 DEG C/min speed again,
Finally it is down to room temperature naturally again, produces activated carbon fiber, 7.5mg detergent alkylate sulphurs is then added into 25mg activated carbon fibers
Sour sodium, redisperse in deionized water, obtain activated carbon fiber dispersion liquid；
3rd, by the blocking rear immersion supersound washing 10h, and each hour is more in deionized water of 10g bacteria celluloses shearing
Deionized water is changed, is subsequently placed in deionized water, stirring makes it be uniformly dispersed, and is then transferred in refiner with per minute 12000
The speed turned, 5min is stirred, obtains bacteria cellulose slurry；
4th, 0.006g neopelexes are added in the graphene being acidified to 0.006g, is then dispersed in deionization
In water, graphene dispersing solution is obtained；Graphene dispersing solution is added in activated carbon fiber dispersion liquid, stirring makes graphene and work
Property carbon fiber is uniformly dispersed, and obtains composite dispersion liquid；
5th, the bacteria cellulose slurry of step 3 is filtered by vacuum film forming, then adds composite dispersion liquid and continue to take out
Film forming is filtered, places into vacuum drying chamber and is dried, bacteria cellulose/activated carbon fiber/graphene film material is made.
The bacterial fibers in bacteria cellulose/activated carbon fiber/graphene film material after vacuum filtration and vacuum drying
The quality of element is 0.3g.
By bacteria cellulose/activated carbon fiber/graphene film material cutting of acquisition into 1.5cm × 2cm rectangles, directly
As ultracapacitor working electrode, platinized platinum is used as to electrode, and using mercury/mercuric oxide electrode as reference electrode, test self-supporting is soft
The capacitance characteristic of property membrane material electrode material.Test sample is labeled as BC-ACF-CN-3.
Electrode prepared by the bacteria cellulose/activated carbon fiber obtained to the present embodiment/graphene film material is in 6M hydrogen
The cyclic voltammetric performance test without sweep speed is carried out in potassium oxide electrolyte, as a result referring to Fig. 7.Show that difference is swept in figure
The activated carbon fiber of speed is in scanning potential region -0.9~0.2V, all the CV curves with quasi- rectangle.
Electrode prepared by the bacteria cellulose/activated carbon fiber obtained to the present embodiment/graphene film material is in hydrogen-oxygen
Change and constant current charge-discharge performance test is carried out in potassium electrolyte, as a result referring to Fig. 8.As shown in Figure 8, curve shows good three
Angular, different multiplying lower curve is respectively provided with preferable symmetry.Maximum area specific capacitance reaches 0.65F/cm2, quality specific capacitance
About 252F/g.
Embodiment 1~3 is using characteristics such as the hyperfine network structure of bacteria cellulose and excellent mechanical properties, as base
Bed load nano active material, ultracapacitor self-supporting self-supporting flexible electrode can be prepared into；Surpassed using bacteria cellulose
The direct Pintsch process of fine network structure prepares activated carbon fiber；It is produced on a large scale, preparation technology is simple, energy-conservation, reaction bar
Part is gentle, small toxicity, and raw material cost cheap and easy to get is low, membrane material stability and mechanical property are good；Directly it is used as ultracapacitor
Electrode has good capacitive character.
Claims (9)
1. a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material, it is characterised in that this method is by as follows
Step is carried out：
First, by bacteria cellulose shear it is blocking be immersed in supersound washing in deionized water, then with being freezed after liquid nitrogen frozen
15~30h is dried, obtains standby bacteria cellulose；
2nd, standby bacteria cellulose is placed in tube furnace and carries out high temperature pyrolysis, produce activated carbon fiber, it is then fine to activated carbon
Surfactant is added in dimension, redisperse in deionized water, obtains activated carbon fiber dispersion liquid；
3rd, it is another to take the blocking rear immersion supersound washing in deionized water of bacteria cellulose shearing, it is subsequently placed in deionized water, stirs
Mixing makes it be uniformly dispersed, and is then transferred in refiner and stirs, and obtains bacteria cellulose slurry；
4th, surfactant is added into the graphene of acidifying, be then dispersed in deionized water, obtain graphene dispersing solution；
Graphene dispersing solution is added in activated carbon fiber dispersion liquid, stirring makes graphene and activated carbon fiber be uniformly dispersed, and obtains
Composite dispersion liquid；
5th, the bacteria cellulose slurry of step 3 is filtered by vacuum film forming, then add composite dispersion liquid continue to filter into
Film, place into vacuum drying chamber and be dried, bacteria cellulose/activated carbon fiber/graphene film material is made；Wherein bacterium
In cellulose/activated carbon fiber/graphene film material the mass ratio of bacteria cellulose and the activated carbon fiber of step 2 for (15~
1.5):1；The graphene being acidified in bacteria cellulose/activated carbon fiber/graphene film material in bacteria cellulose and step 4
Mass ratio is 1:(0.02~0.2)；The method of wherein high temperature pyrolysis is：Standby bacteria cellulose is placed in porcelain boat, Ran Houfang
Enter tube furnace；3~8h of argon gas or nitrogen is passed through into tube furnace, and using argon gas or nitrogen as protection gas；Again by tube furnace with 2
~4 DEG C/min speed is warming up to 270 DEG C, then is warming up to 390 DEG C with 0.3~0.5 DEG C/min speed, then with 2~4 DEG C/
Min speed is warming up to 700 DEG C~1100 DEG C, keeps 2~4h, then is cooled to 400 DEG C with 3~5 DEG C of min speed, again finally
Room temperature is naturally cooled to, that is, is completed.
2. a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material according to claim 1, its
It is characterised by that described bacteria cellulose is bacteria cellulose leftover pieces.
3. a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material according to claim 1, its
The condition for the supersound washing being characterised by described in step 1 and step 3 is ultrasonic time 10h, and change within each hour go from
Sub- water.
4. a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material according to claim 1, its
The activated carbon fiber and the mass ratio of surfactant being characterised by described in step 2 are 1:(0.3~3).
5. a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material according to claim 1, its
It is characterised by the refiner described in step 3 that stirring refers under conditions of stir speed (S.S.) 10000rpm~15000rpm, even
5min is stirred in pulp grinder.
6. a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material according to claim 1, its
The graphene for the acidifying being characterised by described in step 4 and the mass ratio of surfactant are 1:(0.25~1).
A kind of 7. preparation side of bacteria cellulose/activated carbon fiber/graphene film material according to claim 1,4 or 6
Method, it is characterised in that described surfactant is neopelex.
8. a kind of preparation method of bacteria cellulose/activated carbon fiber/graphene film material according to claim 1, its
The preparation method of the graphene for the acidifying being characterised by described in step 4 be by graphene in the nitric acid that concentration is 64% it is ultrasonic
24h is handled, is washed with deionized, filters drying.
9. bacteria cellulose/activated carbon fiber/graphene film material that preparation method as claimed in claim 1 obtains is answered
With, it is characterised in that the bacteria cellulose/activated carbon fiber/graphene film material is as application of electrode in ultracapacitor.
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| CN105428080A (en) * | 2015-12-25 | 2016-03-23 | 哈尔滨工业大学 | Preparation method for bacterial cellulose based polypyrrole/graphene flexible electrode material and application thereof |
| CN105355450B (en) * | 2015-12-25 | 2017-11-17 | 哈尔滨工业大学 | A kind of preparation method and applications of nitrogen-doped carbon fiber/nitrogen-doped graphene/bacteria cellulose membrane material |
| CN105374574B (en) * | 2015-12-25 | 2018-07-03 | 哈尔滨工业大学 | A kind of preparation method and applications of cobalt hydroxide/graphene flexible electrode material |
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| CN105428091B (en) * | 2015-12-25 | 2018-04-24 | 哈尔滨工业大学 | A kind of preparation method and applications of bacteria cellulose graphene paper load nickel hydroxide flexible electrode material |
| CN105513835B (en) * | 2015-12-25 | 2018-07-03 | 哈尔滨工业大学 | A kind of preparation method and applications of nickel hydroxide/graphene flexible electrode material |
| CN105513834B (en) * | 2015-12-25 | 2018-02-02 | 哈尔滨工业大学 | A kind of preparation method and applications of bacteria cellulose graphene paper supported cobaltosic oxide flexible electrode material |
| CN106057495B (en) * | 2016-05-18 | 2019-01-18 | 哈尔滨万鑫石墨谷科技有限公司 | A kind of supercapacitor flexible electrode, preparation method and supercapacitor |
| CN106920700B (en) * | 2017-01-24 | 2019-01-15 | 中国科学院宁波材料技术与工程研究所 | A kind of graphene oxide/bacteria cellulose/carbon nano-tube compound film preparation method and applications of functionalization |
| CN108752794A (en) * | 2018-06-12 | 2018-11-06 | 台州学院 | A kind of carbon fiber and graphite alkene plastics pipe of high-strength light |
| CN110739462B (en) * | 2019-10-16 | 2022-05-24 | 南京林业大学 | Flexible carbon film substrate material and preparation method and application thereof |
| CN110797204A (en) * | 2019-10-28 | 2020-02-14 | 湖南大学 | Preparation of electroactive biomass-based conductive composite film and self-reinforced cellulose hydrogel and application of electroactive biomass-based conductive composite film and self-reinforced cellulose hydrogel to wearable supercapacitor |
| CN112080024A (en) * | 2020-08-24 | 2020-12-15 | 深圳市信维通信股份有限公司 | Composite diaphragm and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011864A (en) * | 2012-12-21 | 2013-04-03 | 中国科学技术大学 | Carbon nanofiber aerogel as well as preparation method and application thereof |
| CN103184586A (en) * | 2011-12-31 | 2013-07-03 | 中原工学院 | Preparation method of bacterial-cellulose-fiber-based nano-grade carbon fiber |
-
2015
- 2015-09-08 CN CN201510566811.2A patent/CN105118688B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103184586A (en) * | 2011-12-31 | 2013-07-03 | 中原工学院 | Preparation method of bacterial-cellulose-fiber-based nano-grade carbon fiber |
| CN103011864A (en) * | 2012-12-21 | 2013-04-03 | 中国科学技术大学 | Carbon nanofiber aerogel as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Freestanding bacterial cellulose-polypyrrole nanofibres paper electrodes for advanced energy storage devices;Shaohui Li et al;《Nano Energy》;20140819(第9期);第309页摘要、第311页左栏Experimental Section部分，图1 * |
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