CN107840979A - A kind of preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane - Google Patents
A kind of preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane.The composite membrane is compound by the nano-cellulose of a diameter of 2~20nm, length for 100nm~5 μm and the hexagonal boron nitride nanosheet with superior dielectric performance, then is made after multi-valent metal salt solution soaks.Composite membrane provided by the invention has relatively low dielectric loss, and higher breakdown strength, energy storage density and energy storage efficiency, in addition, composite membrane also has good layer structure, and crosslinked rear thermal stability there has also been significant raising.The composite membrane will have wide and great potential application prospect in terms of dielectric stored energy application.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of crosslinking nano cellulose/hexagonal nanometer boron nitride
The preparation method of piece composite membrane.
Background technology
Cellulose is the natural polymer that reserves are the abundantest in nature, and this is provided extensively for the acquisition of nano-cellulose
General source, also make nano-cellulose that there is the advantage that cost is cheap and yield is big；In addition, nano-cellulose film it is flexible,
Light transmittance is high, compactness is good, is the ideal material as energy storage material substrate.At present, the raw material that prepared by nano-cellulose is to plant
Based on thing, and native cellulose is wrapped in plant cell wall in higher plant, has complicated connection function with cell membrane,
This can cause stripping cellulose more difficult, by the research of numerous researchers, it has been found that nano-cellulose is prepared more
Kind method, these methods mainly have Physical, chemical method and bioanalysis, but by mechanical phonograph recorder separation (Physical) or strong acid hydrolysis method
The nano-cellulose that the methods of (chemical method) obtains, the shortcomings of shorter fibre length, thickness skewness be present.
Hexagonal boron nitride has the layer structure similar to graphite, therefore it can be used for preparing the stratiform of high structural regularity
Polymer composites.In addition, the chemical stability of hexagonal boron nitride is good, itself breakdown strength is high, reachable 700kV/mm,
Therefore hexagonal boron nitride nanosheet is added into the breakdown strength that matrix can be increased substantially in matrix material as filler.By nanometer
Cellulose and hexagonal boron nitride nanosheet compound the advantages of can integrating the two, it is good to obtain layer structure, dielectric properties it is good with
The composite film material of excellent heat stability.
But the defects of inorganic filler can introduce structure is usually added at present so that compound lamellar spacing is larger.
The content of the invention
Present invention aims at providing, a kind of layer structure is good, and dielectric properties are good and the crosslinking nano of excellent heat stability
Cellulose/hexagonal boron nitride nanosheet composite membrane and preparation method thereof.
It is as follows using technical scheme to reach above-mentioned purpose：
A kind of preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane, comprises the following steps：
1) nano-cellulose (TOCN) dispersion liquid is prepared：
TEMPO and NaBr is added in deionized water, stirred to being completely dissolved, then adds native cellulose, NaClO,
It is 9~11 with NaOH solution regulation system pH value, filters, washs, is dried to obtain after 0.5~7h of oxidation reaction at 10~30 DEG C
Nano-cellulose, survey its water content；Add it to again in distilled water and disperseed to obtain nano-cellulose dispersion liquid, i.e. TOCN
Dispersion liquid；
2) hexagonal boron nitride nanosheet powder (BNNS) is prepared：
Hexagonal boron nitride material powder is mixed with triethanolamine, supernatant is taken after agitated, centrifugation, six sides nitridation is made
The dispersion liquid of boron；Deionized water is added in dispersion liquid again to be sufficiently mixed, and is filtered, washed；The product obtained after washing is again
It is scattered in deionized water, is placed in after being installed with centrifuge tube in liquid nitrogen and carries out snap frozen, finally puts the centrifuge tube freezed
Enter freeze drying box, be freeze-dried to powdered；
3) nano-cellulose/hexagonal boron nitride nanosheet (TOCN/BNNS) composite membrane is prepared：
Gained nano-cellulose dispersion liquid is mixed with gained hexagonal boron nitride nanosheet powder, then by mixed dispersion liquid
It is stirred, ultrasound, nano-cellulose/hexagonal boron nitride nanosheet composite membrane is made through casting film-forming and drying；
4) crosslinking nano cellulose/hexagonal boron nitride nanosheet (CLTOCN/BNNS) composite membrane) is prepared：
Polyvalent metal salt powder is added in deionized water, stirs to being well mixed, multi-valent metal salt solution is made；Again
Step 3 gained nano-cellulose/hexagonal boron nitride nanosheet laminated film is put into the multi-valent metal salt solution and soaks 0.1
~10h, after water washing, dry and crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane is made.
By such scheme, TEMPO, NaBr, native cellulose, NaClO are 1 in mass ratio in step 1:(1~10):(10-
100):(10-100)。
By such scheme, hexagonal boron nitride material powder is 1 in mass ratio with triethanolamine in step 2:(100~
1000)。
By such scheme, volume percent nano-cellulose dispersion liquid 80%~99% is pressed in step 3 mixed system, six
Square boron nitride nanosheet powder is 1%~20%.
By such scheme, native cellulose described in step 1 be cotton cellulose, wood pulp, flaxen fiber, bagasse, cocoanut shell,
One or more in the celluloses such as shuck, wheat straw, rice bar, bacteria cellulose or ascidian cellulose.
By such scheme, the dispersing mode in step 1 is mechanical agitation, ultrasound or high pressure water process.
By such scheme, nano-cellulose dispersion liquid concentration described in step 3 is 0.1~1% (mass concentration)；The nanometer
Cellulose diameter is in 2~20nm, length in 100nm~5 μm.
By such scheme, the concentration of multi-valent metal salt solution described in step 4 is 0.1~1mol/L.
By such scheme, drying temperature is 30~60 DEG C in step 3 and step 4.
By such scheme, the structure of multivalent metal salt is M in step 42+(A-)2Or M3+(A-)3, M in formula2+For Mg2+、Zn2+、
Cu2+Or Ca2+；M3+For Al3+、Cr3+Or Fe3+；A-For C1-Or NO3 -。
TEMPO methods prepare nano-cellulose and effectively, selectively can be catalyzed the primary hydroxyl group on cellulose C6 positions
It is oxidized to carboxyl.Under alkaline environment, the negative potential on nano-cellulose surface is enhanced so that is generated between nano-cellulose
Phase repulsive interaction, so as to weaken the interaction between nano-cellulose, nano-cellulose is finally set to divide from native cellulose
Separate out and；Multi-valent metal salt solution infusion method handles TOCN/BNNS composite membranes, is by the Na on the TOCN-COONa in TOCN films+Substituted with multivalent metal cation, multivalent metal cation can simultaneously with multiple-COO-Interact and form ionomer.
The present invention prepares nano-cellulose from TEMPO methods, and method is convenient and obtained nano-cellulose diameter is small and equal
It is even, this nano-cellulose and other polymers compound tense, humidification can be played；From itself having preferable dielectric properties
BNNS is added in nano-cellulose as filler, but the TOCN/BNNS composite membranes formed have fault of construction, dielectric properties
It is affected；Handled, then can reduced thin by being crosslinked (multi-valent metal salt solution infusion method) to TOCN/BNNS composite membranes again
Space in membrane material, increase its consistency, therefore the CLTOCN/BNNS composite membrane dielectric losses prepared are relatively low, have compared with
High breakdown strength, energy storage density and energy storage efficiency, additionally with good thermal stability.
The beneficial effects of the present invention are:
1st, the present invention preferably have the nano-celluloses of the TEMPO oxidative treatments of special diameter and length with by specific
The hexagonal boron nitride nanosheet that stripping means obtain is compound, then through CaCl2Soaked Deng multi-valent metal salt solution so that gained is compound
Thin film laminated structures void is reduced, consistency increase；The different volumes prepared than CLTOCN/BNNS composite membranes have compared with
Low dielectric loss, higher breakdown strength, energy storage density and energy storage efficiency；The composite membrane will have in terms of dielectric stored energy application
There is wide and great potential application prospect；
2nd, the present invention prepares few layer hexagonal boron nitride nanosheet by the use of triethanolamine as stripping solution, simple to operate, gently
Stir process, and obtained hexagonal boron nitride/triethanolamine dispersion stability is good, keeps more than nine months precipitation capacities
It is less；
3rd, it is physical process that the present invention, which mixes TOCN dispersion liquids with BNNS, is not chemically reacted, and technique is simple,
It is easy to operate, it is environmentally safe；Using multi-valent metal salt solution immersion TOCN/BNNS composite membranes this processing procedure, not only
Simple and convenient and cost is cheap；Whole technique is not high to equipment requirement, is advantageous to industrialized production.
Brief description of the drawings
Accompanying drawing 1：The SEM sectional drawings of pure TOCN films prepared by comparative example 1 of the present invention.
Accompanying drawing 2：Nano-cellulose/hexagonal boron nitride nanosheet composite membrane (TB04) prepared by comparative example 2 of the present invention
SEM sectional drawings.
Accompanying drawing 3：Crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane prepared by the embodiment of the present invention 1
(CLTB04) SEM sectional drawings.
Embodiment
Following examples further explain technical scheme, but not as limiting the scope of the invention.
Comparative example 1
Pure nano-cellulose film (pure TOCN films) is prepared, step is as follows:
Prepare TOCN dispersion liquids:0.01g TEMPO, 0.1g NaBr are taken, it is added in 1000mL deionized waters jointly,
Magnetic agitation 10min is sufficiently mixed it to be uniformly completely dissolved to TEMPO and NaBr under 300r/min, then into above-mentioned system
1g cotton linter is added, 0.1gNaClO is then added into system, system pH is kept by the NaOH solution that 0.1mol/L is added dropwise
It is worth for 9, is filtered the cellulose after oxidation after reacting 5h, then be washed with deionized more than 3 times, is dried to obtain TEMPO
Oxycellulose；Put it into again in beaker, add deionized water and disperseed, then mechanical agitation 6min and supersound process
12min, obtain the nano-cellulose dispersion liquid that concentration is 0.3%, i.e. 0.3%TOCN dispersion liquids；
Make pure TOCN films:0.3%TOCN dispersion liquids are first subjected to casting film-forming, and is dried to obtain concentration at 40 DEG C and is
0.3% pure TOCN films.
Pattern test, test knot are carried out to obtained TOCN dispersion liquids using DI Nanoscope IV AFMs
Fruit shows that a diameter of 3~4nm of the TOCN that this comparative example obtains, average length is 3 μm；Utilize HIOKI3532-50LCR dielectrics frequency
Dielectric constant, dielectric loss and the breakdown for the pure TOCN films that spectrometer and DDJ-50kV voltage breakdown experiment apparatus are prepared to this comparative example
Intensity is tested, and test result shows, the dielectric constant of pure TOCN films prepared by this comparative example under 1kHz frequencies is 10.8
Left and right, for dielectric loss 0.07 or so, breakdown strength is only 51.6kV/mm.Using STA449C thermogravimetric analyzers to heat endurance
It can be tested, test result shows, the temperature corresponding to pure TOCN films decomposition mechanism is 240.2 DEG C.
The SEM sectional drawings of the pure TOCN films prepared as shown in Figure 1 for this comparative example, as can be seen pure TOCN films internal structure
In layer structure, and more uniformly, structure closely, between cellulose only exists few gap.
Comparative example 2
Nano-cellulose/hexagonal boron nitride nanosheet composite membrane is prepared, step is as follows:
1) TOCN dispersion liquids processed:0.01g TEMPO, 0.1g NaBr are taken, it is added in 1000mL deionized waters jointly,
Magnetic agitation 10min is sufficiently mixed it to be uniformly completely dissolved to TEMPO and NaBr under 300r/min, then into above-mentioned system
1g cotton linter is added, 0.1gNaClO is then added into system, system pH is kept by the NaOH solution that 0.1mol/L is added dropwise
It is worth for 9, is filtered the cellulose after oxidation after reacting 5h, then be washed with deionized more than 3 times, is dried to obtain TEMPO
Oxycellulose；Put it into again in beaker, add deionized water and disperseed, then mechanical agitation 6min and supersound process
12min, obtain the nano-cellulose dispersion liquid that concentration is 0.3%, i.e. 0.3%TOCN dispersion liquids；
2) BNNS processed:30ml triethanolamines will be added in 0.3g hexagonal boron nitride material powders, are taken after agitated, centrifugation
Clear liquid, the dispersion liquid of hexagonal boron nitride is made；400ml deionized waters will be added in dispersion liquid to be sufficiently mixed, take out for four times again
Filter, washing；The product obtained after washing is redispersed in 100ml water, is placed in liquid nitrogen and is carried out quickly after being installed with centrifuge tube
Freezing, is finally put into freeze drying box by the centrifuge tube freezed, is freeze-dried to powdered.
3) TOCN/BNNS composite membranes processed:By the TOCN dispersion liquids of above-mentioned preparation and BNNS with volume ratio 98:2、96:4、92:
8 and 88:12 are blended and (are denoted as TB02, TB04, TB08 and TB12), and mixed dispersion liquid magneton then is stirred into 30min, ultrasound
4min, casting film-forming and the obtained TOCN/BNNS composite membranes of drying at 40 DEG C after being well mixed；Wherein, it is total to account for composite membrane by BNNS
2%, 4%, 8% and the 12% of volume.
Dielectric constant and the dielectric damage of the composite membrane prepared using HIOKI3532-50LCR dielectric and magnetics instrument to this comparative example
Consumption is tested, and the TB02 composite membranes dielectric constant that the preparation of this comparative example is measured under 1KHz frequencies is 11.4, and dielectric loss is
0.08, TB04 composite membrane dielectric constant is 9.14, dielectric loss 0.1, and TB08 composite membranes dielectric constant is 9.62, dielectric loss
It is 11.07 for 0.13, TB12 composite membranes dielectric constant, dielectric loss 0.18, composite membrane and the pure TOCN films of comparative example 1 can be drawn
Significantly increased compared to dielectric loss.
The SEM sectional drawings of the TB04 composite membranes of this comparative example preparation are illustrated in figure 2, composite membrane keeps contrast as can be seen
The layer structure of pure TOCN films in example 1, but there is a certain amount of space, structure is defective.
Embodiment 1
Crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane is prepared, step is as follows:
1) TOCN dispersion liquids processed:0.01gTEMPO, 0.1gNaBr are taken, it is added in 1000mL deionized waters jointly,
10 DEG C, magnetic agitation 10min is sufficiently mixed it to be uniformly completely dissolved to TEMPO and NaBr under 300r/min, then to above-mentioned body
1g cotton linter is added in system, 0.1g NaClO are then added into system, is kept by the NaOH solution that 0.1mol/L is added dropwise
System pH is 9, is filtered the cellulose after oxidation after reacting 5h at 10 DEG C, then is washed with deionized more than 3 times,
It is dried to obtain TEMPO oxycelluloses；Put it into again in beaker, add deionized water and disperseed, then mechanical agitation
6min and supersound process 12min, obtains the nano-cellulose dispersion liquid that concentration is 0.3%, i.e. 0.3%TOCN dispersion liquids；
2) BNNS processed::30ml triethanolamines will be added in 0.3g hexagonal boron nitride material powders, are taken after agitated, centrifugation
Supernatant, the dispersion liquid of hexagonal boron nitride is made；400ml deionized waters will be added in dispersion liquid to be sufficiently mixed, carry out four times again
Filter, washing；The product obtained after washing is redispersed in 100ml water, is placed in liquid nitrogen and is carried out soon after being installed with centrifuge tube
Quickly cooling is frozen, and the centrifuge tube freezed finally is put into freeze drying box, is freeze-dried to powdered.
3) TOCN/BNNS composite membranes processed:By the TOCN dispersion liquids of above-mentioned preparation and BNNS with volume ratio 96:4 are blended
(being denoted as TB04), mixed dispersion liquid magneton is then stirred into 30min, ultrasonic 4min, be well mixed rear casting film-forming and at 40 DEG C
TOCN/BNNS composite membranes are made in lower drying；
4) CLTOCN/BNNS composite membranes processed:By 11.1g CaCl2Powder is added in 1000ml deionized waters, and stirring is extremely
It is well mixed, 0.1mol/L CaCl is made2Salting liquid；TB04 laminated films are put into the above-mentioned CaCl of 150ml again2In salting liquid
Soak 2h, through water washing three times more than, at 40 DEG C dry after be made CLTOCN/BNNS composite membranes (being denoted as CLTB04).Wherein,
BNNS accounts for the 4% of composite membrane cumulative volume.
Using HIOKI3532-50LCR dielectric and magnetics instrument and DDJ-50KV voltage breakdown experiment apparatus to manufactured in the present embodiment
The dielectric properties of CLTB04 composite membranes are tested, and the dielectric loss for measuring composite membrane under 1KHz frequencies is 0.025, breakdown
Intensity is 384.2kV/mm, can show that CLTB04 films dielectric loss compared with the pure TOCN films of comparative example 1 reduces 64.3%, breakdown
Intensity improves 86.6%, and dielectric loss reduces 75% compared with the TB04 films of comparative example 2；Known breakdown strength, according still further to
Formula Umax=1/2 ε ε0CLTB04 is calculated in 380MVm in E2b-1Electric field in maximum energy storage density be up to 3.90J
cm-3, it is than the boiomacromolecule compound highest energy storage density (0.81Jcm that was once reported-3) high, also compare
Industrially conventional best dielectric macromolecule BOPP (2Jcm-3) high；In addition CLTB04 composite membranes are in 50~300MVm-1
Electric field under, the energy storage efficiency of film is more than 86%.Thermal stability is tested using STA449C thermogravimetric analyzers, surveyed
Composite membrane is obtained compared with pure TOCN films prepared by comparative example 1, the temperature corresponding to decomposition mechanism increases to 340 from 240 DEG C
DEG C (improving 100 DEG C).
The SEM sectional drawings of CLTB04 composite membranes manufactured in the present embodiment are illustrated in figure 3, six sides nitrogenize as can be seen from Figure
Boron can be well dispersed between nano-cellulose layer structure, keep the layer structure of pure TOCN films in comparative example 1, and relatively
TB04 composite membranes layer structure is even closer in comparative example 2, and more obvious, interlayer spacings also significantly reduce.
Embodiment 2
Crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane is prepared, step is as follows:
1) TOCN dispersion liquids processed:0.01gTEMPO, 0.01gNaBr are taken, it is added in 100mL deionized waters jointly,
30 DEG C, magnetic agitation 20min is sufficiently mixed it to be uniformly completely dissolved to TEMPO and NaBr under 600r/min, then to above-mentioned body
0.1g softwood bleached pulp is added in system, 1gNaClO is then added into system, by the NaOH solution that 0.5mol/L is added dropwise
It is 11 to keep system pH, is filtered the cellulose after oxidation after reacting 7h at 30 DEG C, then be washed with deionized 3 times
More than, it is dried to obtain TEMPO oxycelluloses；Put it into again in beaker, add deionized water and disperseed, then machinery stirs
Mix 6min and be ultrasonically treated 6min, obtain the nano-cellulose dispersion liquid that concentration is 0.5%, i.e. 0.5%TOCN dispersion liquids；
2) BNNS processed:30ml triethanolamines will be added in 0.3g hexagonal boron nitride material powders, are taken after agitated, centrifugation
Clear liquid, the dispersion liquid of hexagonal boron nitride is made；400ml deionized waters will be added in dispersion liquid to be sufficiently mixed, take out for four times again
Filter, washing；The product obtained after washing is redispersed in 100ml water, is placed in liquid nitrogen and is carried out quickly after being installed with centrifuge tube
Freezing, is finally put into freeze drying box by the centrifuge tube freezed, is freeze-dried to powdered.
3) TOCN/BNNS composite membranes processed:By the TOCN dispersion liquids of above-mentioned preparation and BNNS with volume ratio 98:2 are blended
It is blended and (is denoted as TB02), mixed dispersion liquid magneton is then stirred into 30min, ultrasonic 4min, casting film-forming after being well mixed
And dried at 40 DEG C and TOCN/BNNS composite membranes are made；
4) CLTOCN/BNNS composite membranes processed:By 11.1g CaCl2Powder is added in 1000ml deionized waters, and stirring is extremely
It is well mixed, 0.1mol/L CaCl is made2Salting liquid；TB02 laminated films are put into the above-mentioned CaCl of 150ml again2In salting liquid
Soak 2h, through water washing three times more than, at 40 DEG C dry after be made CLTOCN/BNNS composite membranes (being denoted as CLTB02).Wherein,
BNNS accounts for the 2% of composite membrane cumulative volume.
Composite membrane manufactured in the present embodiment is tested using method same as Example 1, surveyed under 1KHz frequencies
The dielectric loss for obtaining composite membrane is 0.03, breakdown strength 352.5kV/mm, can draw CLTB02 films and the pure TOCN films of comparative example 1
57.1% is reduced compared to dielectric loss, breakdown strength improves 85.4%, and dielectric loss drops compared with the TB02 films of comparative example 2
Low 62.5%；By the way that CLTB02 is calculated in 350MVm-1Electric field in maximum energy storage density be up to 3.40Jcm-3；
In addition CLTB02 composite membranes are in 50~300MVm-1Electric field under, the energy storage efficiency of film is more than 90%.The maximum of composite membrane point
Temperature corresponding to solution speed (improves 100 DEG C) at 340 DEG C or so than pure TOCN films.
Embodiment 3
Crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane is prepared, step is as follows:
1) TOCN dispersion liquids processed:0.02gTEMPO, 0.05gNaBr are taken, it is added in 1000mL deionized waters jointly,
15 DEG C, magnetic agitation 15min is sufficiently mixed it to be uniformly completely dissolved to TEMPO and NaBr under 400r/min, then to above-mentioned body
1g bacteria cellulose is added in system, 1.5gNaClO is then added into system, is protected by the NaOH solution that 0.2mol/L is added dropwise
System pH is held as 10, is filtered the cellulose after oxidation after reacting 6h at 15 DEG C, then be washed with deionized 3 times with
On, it is dried to obtain TEMPO oxycelluloses；Put it into again in beaker, add deionized water and disperseed, then mechanical agitation
6min and supersound process 12min, obtains the nano-cellulose dispersion liquid that concentration is 0.2%, i.e. 0.2%TOCN dispersion liquids；
2) BNNS processed:35ml triethanolamines will be added in 0.3g hexagonal boron nitride material powders, are taken after agitated, centrifugation
Clear liquid, the dispersion liquid of hexagonal boron nitride is made；400ml deionized waters will be added in dispersion liquid to be sufficiently mixed, take out for four times again
Filter, washing；The product obtained after washing is redispersed in 100ml water, is placed in liquid nitrogen and is carried out quickly after being installed with centrifuge tube
Freezing, is finally put into freeze drying box by the centrifuge tube freezed, is freeze-dried to powdered.
3) TOCN/BNNS composite membranes processed:By the TOCN dispersion liquids of above-mentioned preparation and BNNS with volume ratio 92:8 are blended
(being denoted as TB08), mixed dispersion liquid magneton is then stirred into 30min, ultrasonic 4min, be well mixed rear casting film-forming and at 35 DEG C
TOCN/BNNS composite membranes are made in lower drying；
4) CLTOCN/BNNS composite membranes processed:By 22.2g CaCl2Powder is added in 1000ml deionized waters, and stirring is extremely
It is well mixed, 0.2mol/L CaCl is made2Salting liquid；TB08 laminated films are put into the above-mentioned CaCl of 150ml again2In salting liquid
Soak 3h, through water washing three times more than, at 35 DEG C dry after be made CLTOCN/BNNS composite membranes (being denoted as CLTB08).Wherein,
BNNS accounts for the 8% of composite membrane cumulative volume.
Composite membrane manufactured in the present embodiment is tested using method same as Example 1, surveyed under 1KHz frequencies
The dielectric loss for obtaining composite membrane is 0.027, breakdown strength 368.9KV/mm, can draw CLTB08 films and 1 pure TOCN of comparative example
Film reduces 61.4% compared to dielectric loss, and breakdown strength improves 86%, and dielectric loss drops compared with the TB08 films of comparative example 2
Low 79.2%；By the way that CLTB08 is calculated in 370MVm-1Electric field in maximum energy storage density be up to 3.06Jcm-3；
In addition CLTB08 composite membranes are in 50~300MVm-1Electric field under, the efficiency for charge-discharge of film is more than 85%.
Embodiment 4
Crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane is prepared, step is as follows:
1) TOCN dispersion liquids processed:0.01g TEMPO, 0.06g NaBr are taken, it is added in 100mL deionized waters jointly,
Magnetic agitation 17min is sufficiently mixed it to be uniformly completely dissolved to TEMPO and NaBr under 25 DEG C, 450r/min, then to above-mentioned
0.1g ascidian cellulose is added in system, 0.6gNaClO is then added into system, it is molten by the NaOH that 0.3mol/L is added dropwise
It is 10 that liquid, which keeps system pH, is filtered the cellulose after oxidation after reacting 7h at 25 DEG C, then be washed with deionized 3
More than secondary, TEMPO oxycelluloses are dried to obtain；Put it into again in beaker, add deionized water and disperseed, it is then mechanical
Stir 6min and be ultrasonically treated 12min, obtain the nano-cellulose dispersion liquid that concentration is 0.1%, i.e. 0.1%TOCN dispersion liquids；
2) BNNS processed:35ml triethanolamines will be added in 0.3g hexagonal boron nitride material powders, are taken after agitated, centrifugation
Clear liquid, the dispersion liquid of hexagonal boron nitride is made；400ml deionized waters will be added in dispersion liquid to be sufficiently mixed, take out for four times again
Filter, washing；The product obtained after washing is redispersed in 100ml water, is placed in liquid nitrogen and is carried out quickly after being installed with centrifuge tube
Freezing, is finally put into freeze drying box by the centrifuge tube freezed, is freeze-dried to powdered.
3) TOCN/BNNS composite membranes processed:By the TOCN dispersion liquids of above-mentioned preparation and BNNS with volume ratio 88:12 are blended
(being denoted as TB12), mixed dispersion liquid magneton is then stirred into 30min, ultrasonic 4min, be well mixed rear casting film-forming and at 35 DEG C
TOCN/BNNS composite membranes are made in lower drying；
4) CLTOCN/BNNS composite membranes processed:By 22.2g CaCl2Powder is added in 1000ml deionized waters, and stirring is extremely
It is well mixed, 0.2mol/L CaCl is made2Salting liquid；TB12 laminated films are put into the above-mentioned CaCl of 200ml again2In salting liquid
Soak 3h, through water washing three times more than, at 35 DEG C dry after be made CLTOCN/BNNS composite membranes (being denoted as CLTB12).Wherein,
BNNS accounts for the 12% of composite membrane cumulative volume.
Composite membrane manufactured in the present embodiment is tested using method same as Example 1, surveyed under 1KHz frequencies
The dielectric loss for obtaining composite membrane is 0.029, breakdown strength 358.6KV/mm, can draw CLTB12 films and 1 pure TOCN of comparative example
Film reduces 58.6% compared to dielectric loss, and breakdown strength improves 85.6%, the dielectric loss compared with the TB12 films of comparative example 2
Reduce 83.9%；By the way that CLTB12 is calculated in 350MVm-1Electric field in maximum energy storage density be up to 2.97Jcm-3；In addition CLTB12 composite membranes are in 50~300MVm-1Electric field under, the efficiency for charge-discharge of film is more than 87%.
Claims (10)
1. a kind of preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane, it is characterised in that including following
Step：
1) nano-cellulose dispersion liquid is prepared：
TEMPO and NaBr is added in deionized water, stirred to being completely dissolved, then adds native cellulose, NaClO, is used
NaOH solution regulation system pH value is 9~11, filters, washs after 0.5~7h of oxidation reaction at 10~30 DEG C, being dried to obtain and receive
Rice cellulose, surveys its water content；Add it to again in distilled water and disperseed to obtain nano-cellulose dispersion liquid, be i.e. TOCN divides
Dispersion liquid；
2) hexagonal boron nitride nanosheet powder is prepared：
Hexagonal boron nitride material powder is mixed with triethanolamine, supernatant is taken after agitated, centrifugation, hexagonal boron nitride is made
Dispersion liquid；Deionized water is added in dispersion liquid again to be sufficiently mixed, and is filtered, washed；The product redisperse obtained after washing
In deionized water, it is placed in after being installed with centrifuge tube in liquid nitrogen and carries out snap frozen, is finally put into the centrifuge tube freezed cold
Freeze drying box, be freeze-dried to powdered；
3) nano-cellulose/hexagonal boron nitride nanosheet composite membrane is prepared：
Gained nano-cellulose dispersion liquid is mixed with gained hexagonal boron nitride nanosheet powder, then carried out mixed dispersion liquid
Stirring, ultrasound, nano-cellulose/hexagonal boron nitride nanosheet composite membrane is made through casting film-forming and drying；
4) crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane is prepared：
Polyvalent metal salt powder is added in deionized water, stirs to being well mixed, multi-valent metal salt solution is made；Again will step
Rapid 3 gained nano-cellulose/hexagonal boron nitride nanosheet laminated film be put into the multi-valent metal salt solution immersion 0.1~
10h, after water washing, dry and crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane is made.
2. the preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane as claimed in claim 1, its feature exist
TEMPO, NaBr, native cellulose, NaClO are 1 in mass ratio in step 1:(1~10):(10-100):(10-100).
3. the preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane as claimed in claim 1, its feature exist
Hexagonal boron nitride material powder is 1 in mass ratio with triethanolamine in step 2:(100~1000).
4. the preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane as claimed in claim 1, its feature exist
Volume percent nano-cellulose dispersion liquid 80%~99%, hexagonal boron nitride nanosheet powder are pressed in step 3 mixed system
End is 1%~20%.
5. the preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane as claimed in claim 1, its feature exist
In native cellulose described in step 1 be cotton cellulose, wood pulp, flaxen fiber, bagasse, cocoanut shell, shuck, wheat straw, rice
One or more in the celluloses such as bar, bacteria cellulose or ascidian cellulose.
6. the preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane as claimed in claim 1, its feature exist
Dispersing mode in step 1 is mechanical agitation, ultrasound or high pressure water process.
7. the preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane as claimed in claim 1, its feature exist
In nano-cellulose dispersion liquid concentration described in step 3 be 0.1~1% (mass concentration)；The nano-cellulose diameter 2~
20nm, length are in 100nm~5 μm.
8. the preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane as claimed in claim 1, its feature exist
In the concentration of multi-valent metal salt solution described in step 4 be 0.1~1mol/L.
9. the preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane as claimed in claim 1, its feature exist
Drying temperature is 30~60 DEG C in step 3 and step 4.
10. the preparation method of crosslinking nano cellulose/hexagonal boron nitride nanosheet composite membrane as claimed in claim 1, its feature
It is M in the structure of the multivalent metal salt in step 42+(A-)2Or M3+(A-)3, M in formula2+For Mg2+、Zn2+、Cu2+Or Ca2+；M3+For
Al3+、Cr3+Or Fe3+；A-For C1-Or NO3 -。
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| CN108610512A (en) * | 2018-04-28 | 2018-10-02 | 武汉理工大学 | A kind of high dielectric nano composite membrane of cellulose/layered nitride boron and preparation method thereof |
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| CN112316567A (en) * | 2020-10-19 | 2021-02-05 | 江苏大学 | Nanofiber filter membrane and preparation method and device thereof |
| CN112341648A (en) * | 2020-10-28 | 2021-02-09 | 南京先进生物材料与过程装备研究院有限公司 | Preparation method of nano composite film containing europium ion nano cellulose/modified graphene oxide |
| CN112341648B (en) * | 2020-10-28 | 2022-03-11 | 南京先进生物材料与过程装备研究院有限公司 | Preparation method of nano composite film containing europium ion nano cellulose/modified graphene oxide |
| CN114316376A (en) * | 2022-01-11 | 2022-04-12 | 陕西科技大学 | CNF/BNNS composite dispersion liquid, film and preparation method |
| CN114316376B (en) * | 2022-01-11 | 2022-12-27 | 陕西科技大学 | CNF/BNNS composite dispersion liquid, film and preparation method |
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