CN107129592B - A kind of cellulosic polymer dielectric film and its preparation method and application - Google Patents
A kind of cellulosic polymer dielectric film and its preparation method and application Download PDFInfo
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Abstract
本发明提供了一种纤维素聚合物电解质膜及其制备方法和应用。本发明以纤维素作为原料，纤维素分子结构之间的重新组装和大量的介孔结构使其具有高的孔隙率、吸收与保持电解液的性能，提高了其离子电导率；纤维素分子链之间的大量氢键作用以及三维均相体系使其具有很好的力学性能。本发明提供的纤维素聚合物电解质膜能够进行反复折叠，表面柔韧性和透明性良好；具有丰富的介孔结构，孔径可调性，且随着调湿时间的延长，孔径变大，孔径更加均匀；孔隙率为71.78％，离子电导率为0.325s/cm，力学性能良好。本发明提供的纤维素聚合物电解质膜应用于柔性全固态超级电容器和微型超级电容器时，具有良好电化学性能和应用对象的可伸缩性。
The present invention provides a cellulose polymer electrolyte membrane and a preparation method and application thereof. The invention uses cellulose as a raw material, and the reassembly of cellulose molecular structures and a large number of mesoporous structures make it have high porosity, absorb and maintain the performance of electrolyte, and improve its ionic conductivity; cellulose molecular chain The large number of hydrogen bonds between them and the three-dimensional homogeneous system make them have good mechanical properties. The cellulose polymer electrolyte membrane provided by the invention can be folded repeatedly, has good surface flexibility and transparency; has abundant mesoporous structure, adjustable pore size, and with the prolongation of humidity conditioning time, the pore size becomes larger and the pore size becomes larger Uniform; the porosity is 71.78%, the ionic conductivity is 0.325s/cm, and the mechanical properties are good. When the cellulose polymer electrolyte membrane provided by the invention is applied to the flexible all-solid-state supercapacitor and the micro-supercapacitor, it has good electrochemical performance and scalability of the application object.
Description
Technical field
The present invention relates to dielectric film technical field more particularly to a kind of cellulosic polymer dielectric film and its preparation sides
Method and application.
Background technique
Polymer dielectric be it is a kind of it is novel be applied to flexible, portable and high performance energy storage device, such as surpass
Grade capacitor, lithium ion battery (Li-ion), lithium-sulfur cell (Li-S) and zinc and air cell (Zn-O2) etc. on-liquid in secondary cells
Electrolyte, with electrolyte and diaphragm dual function.
Polymer dielectric film is caused increasingly due to its high ionic conductivity, wide electrochemical window and safety in utilization
More concerns.Polymer dielectric film has the dual function of electrolyte and diaphragm, promotes portable and wearable electronics
The exploitation of the energy-storage system of equipment.So far, technical staff has done many effort to prepare high-performance gel polymer
Electrolyte and porous polymer electrolyte: it is grafted in poly- (arylene ether ketone) compound microporous polymer membranes and mixes in poly(ethylene glycol)
Enter chitosan-LiClO4Gel electrolyte is made, which shows good mechanical performance and low leaks, and
And when being integrated in solid-state electric double layer capacitor with high cyclical stability；Graphene oxide doped ionic gel electrolyte
It shows high ionic conductivity, all solid state SC is assembled using the gel electrolyte, shows high capacitance performance and good circulation
Stability.
However, traditional polymer dielectric is non-renewable, biological degradability is poor, mechanical performance is insufficient, ionic conductivity
Low, the solvent of non-green, complex steps and time-consuming is generally used in preparation method, this reduces all solid state SC to a certain extent
Chemical property and the supercapacitor for limiting its application in other energy storage devices, and assembling flexibility it is insufficient,
Its chemical property can be significantly seriously affected under bending state.It is therefore necessary to using it is a kind of it is novel, simple, conveniently, it is green
The method preparation that colour circle is protected has the electrostrictive polymer that renewable, complete biodegradable, high ionic conductivity, mechanical resistance can be strong
Film material is solved, and is applied to the energy storage devices such as supercapacitor and shows superior chemical property and flexible stability, it is full
The foot present age product intelligent, flexible, environmentally friendly theory.
Summary of the invention
The purpose of the present invention is to provide a kind of cellulosic polymer dielectric film and its preparation method and application, the present invention
The preparation method of offer is easy to operate, and the solvent used is green solvent, nontoxic, health environment-friendly, the raw material of use
Cellulose is complete renewable and biodegradable material.Cellulosic polymer dielectric film provided by the invention has excellent simultaneously
Different flexibility, mechanical property and chemical property.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of cellulosic polymer dielectric film, comprise the following steps:
Solvent and cellulose are mixed, raw material liquid phase mixture is obtained；
The raw material liquid phase mixture is de-gassed, degassing system is obtained；
After the degassing system is coated on carrier surface, carries out conditioning and replaced in displacement liquid again, obtained
Aquogel system；
The aquogel system is set between two microporous teflon membrans, drying process obtains cellulose membrane；
The cellulose membrane is adsorbed in the electrolytic solution, obtains cellulosic polymer dielectric film.
Preferably, the solvent is ionic liquid, the mixed solution of NaOH and urea or dimethyl acetamide and lithium chloride
Mixture.
Preferably, the mass ratio of the solvent and cellulose is (45~55): (1~5).
Preferably, the vacuum degree of the degassing process is 0.001~0.05MPa；
The time of the degassing process is 1~10h.
Preferably, the displacement liquid is water, ethyl alcohol or acetone.
Preferably, the displaced temperature is 20~40 DEG C；
The displaced time is 30~90min.
Preferably, the temperature of the drying is 50~70 DEG C；
The time of the drying is 10~15h.
Preferably, the electrolyte is alkali system electrolyte, acid electrolyte or salt system electrolyte.
The present invention also provides the cellulosic polymers that preparation method described in a kind of above-mentioned technical proposal any one obtains
Dielectric film.
The present invention also provides a kind of the answering in the capacitor of cellulosic polymer dielectric film described in above-mentioned technical proposal
With.
The present invention provides a kind of cellulosic polymer dielectric films and its preparation method and application.The present invention is with cellulose
As raw material, between cellulose molecular chain re-assemblying with a large amount of meso-hole structure make it have high porosity, water suction with
Water retention property improves its ion-conductance conductivity；The a large amount of hydrogen bond actions and three-dimensional formed between cellulose molecular chain are homogeneous
System makes it have good mechanical property.By the result of embodiment it is found that cellulosic polymer electrolyte provided by the invention
Film is able to carry out folding, and surface flexibility and the transparency are good；With meso-hole structure abundant, aperture adjustability, and with
The extension of damping time, aperture become larger, aperture is more uniform；Porosity is 71.78%, ionic conductivity 0.325s/cm；
Mechanical property has excellent chemical property using the all-solid-state supercapacitor of cellulosic polymer dielectric film assembling.
Current density be 0.5 peace/gram, biggest quality specific capacitance up to 120.6 methods/gram, even if under 10 peace/gram high current densities, still
With up to 81.4 methods/gram quality specific capacitance, present good high rate performance.Cyclical stability is prominent, 1 peace/gram electric current
Under density, after charge and discharge cycles 10000 times, quality specific capacitance still up to 100 methods/gram.More allow people glad, assembling it is complete
Solid-state super capacitor has shown superior flexibility, even if still keeping original under the conditions of bending angle is up to 180 DEG C
Chemical property, specific capacitance value remains unchanged.And cellulosic polymer dielectric film is in addition to that can assemble sandwich form
Flexible all-solid-state supercapacitor can be also used for assembling flexible miniature supercapacitor, equally show ideal electrification
Learn performance, it was demonstrated that the superiority of cellulosic polymer dielectric film performance and the scalability of application.
Detailed description of the invention
Fig. 1 is the translucent effect photo of cellulosic polymer dielectric film；
Fig. 2 is the SEM scanned photograph of cellulosic polymer dielectric film at room temperature after damping 0 hour；
Fig. 3 is the SEM scanned photograph of cellulosic polymer dielectric film at room temperature after damping 5 hours；
Fig. 4 is the SEM scanned photograph of cellulosic polymer dielectric film at room temperature after damping 10 hours；
Fig. 5 is the porosity and ionic conductivity of cellulosic polymer dielectric film；
Fig. 6 is the tensile stress-strain curve of cellulosic polymer dielectric film；
Fig. 7 is the cyclic voltammetry curve of cellulosic polymer dielectric film；
Fig. 8 is the constant current charge-discharge curve of cellulosic polymer dielectric film；
Fig. 9 is the AC impedance spectroscopy of cellulosic polymer dielectric film；
Figure 10 is specific capacitance of the cellulosic polymer dielectric film under different current densities；
Figure 11 is cellulosic polymer dielectric film charge and discharge cycles stability under 1 peace/gram current density；
Figure 12 is that the circulation of the lower 100 mv ss sweep speeds of the differently curved state of cellulosic polymer dielectric film lies prostrate
Pacify curve；
Figure 13 is all-solid-state flexible supercapacitor assembling schematic diagram；
Figure 14 is the circulation of 200 mv ss sweep speeds of cellulosic polymer dielectric film flexible miniature supercapacitor
Volt-ampere curve.
Specific embodiment
The present invention provides a kind of preparation methods of cellulosic polymer dielectric film, comprise the following steps:
Solvent and cellulose are mixed, raw material liquid phase mixture is obtained；
The raw material liquid phase mixture is de-gassed, degassing system is obtained；
After the degassing system is coated on carrier surface, carries out conditioning and replaced in displacement liquid again, obtained
Aquogel system；
The aquogel system is set between two microporous teflon membran microwell plates, drying process obtains fiber
Plain film；
The cellulose membrane is adsorbed in the electrolytic solution, obtains cellulosic polymer dielectric film.
The present invention mixes solvent and cellulose, obtains raw material liquid phase mixture.In the present invention, the solvent is excellent
It is selected as the mixed solution of ionic liquid, NaOH and urea or the mixture of dimethyl acetamide and lithium chloride.
In the present invention, the ionic liquid is preferably chlorination 1- butyl -3- methylimidazole chlorine ([Bmim] Cl), bromination 1-
Butyl -3- methylimidazole ([Bmim] Br) and 1- methyl -3- ethyl imidazol(e) tetrafluoroborate ([EMI] BF4) one of or it is several
Kind.
In the present invention, the mixed solution of the NaOH and urea is preferably the mixed aqueous solution of NaOH and urea；Wherein,
The mass concentration of NaOH is preferably 5~10%, and more preferably 7%；The mass concentration of urea is preferably 10~15%, more preferably
12%.
In the present invention, in the mixture of the dimethyl acetamide and lithium chloride dimethyl acetamide and lithium chloride matter
Amount is than being preferably (45~55): (1~5), more preferably 50:3.
In the present invention, the cellulose be preferably cotton cellulose, catkin cellulose, wood-cellulose, bamboo cellulose,
Flaxen fiber element, crop branch fiber element or sugarcane fibre element.In the present invention, the mass ratio of the solvent and cellulose is preferred
For (45~55): (1~5), more preferably (48~52): (2~3), most preferably 50:2.08.In the present invention, the fiber
The degree of polymerization of element is preferably 800~2000, and more preferably 1000~1600, most preferably 1400~1500.
In the present invention, the mixing preferably carries out under agitation, to reduce the viscosity of solvent, especially ionic liquid
The viscosity of body provides its mobility and wetability, accelerates the progress to the wetting of cellulose, swelling and dissolution.In the present invention,
The mixing speed is preferably 500~1000r/min, more preferably 800~900r/min, is most preferably selected as 850r/min.
In the present invention, the mixed temperature is preferably -15 DEG C (subzero 15 DEG C)~170 DEG C.Of the invention specific real
It applies in example, when the solvent is ionic liquid, the mixed temperature is preferably 70~100 DEG C, and more preferably 80~90 DEG C,
Most preferably 85 DEG C；The mixed time is preferably 20~40min, more preferably 25~35min, most preferably 30min.
In the specific embodiment of the invention, when the solvent is the mixed solution of NaOH and urea, the mixed temperature
Preferably -15 DEG C~-10 DEG C of degree, more preferably -13 DEG C~-11 DEG C, most preferably -12 DEG C；The mixed time is preferably 1
~10min, more preferably 2~8min, most preferably 5min.
It is described when the solvent is the mixture of dimethyl acetamide and lithium chloride in the specific embodiment of the invention
Mixed temperature is preferably 50~110 DEG C, more preferably 80~100 DEG C, most preferably 95 DEG C；The mixed time is preferably
20~70min, more preferably 30~60min, most preferably 50min.
After obtaining the raw material liquid phase mixture, the present invention is de-gassed the raw material liquid phase mixture, obtains
Degassing system.In the present invention, the temperature requirement of the degassing process is preferably consistent with the mixed temperature requirement, herein
No longer repeated.
In the present invention, the vacuum degree of the degassing process is preferably 0.001~0.05MPa, more preferably 0.01~
0.02MPa；The time of the degassing process is preferably 1~10h, more preferably 2~8h, most preferably 4~6h.In the present invention
In, the degassing process can remove the bubble in raw material liquid phase mixture, go out inside the transparent membrane for preventing the later period from preparing
Now a large amount of bubbles influence aesthetics, translucency, mechanical property, ionic conductivity, porosity, washing lotion performance and the guarantor's liquid of film
Performance.
After obtaining the degassing system, after the degassing system is coated on carrier surface by the present invention, conditioning is carried out
It is replaced in displacement liquid again, obtains aquogel system.The present invention does not have any particular/special requirement to the carrier, using this
Surface known to the technical staff of field is smooth, material is hydrophobic and the common carrier with certain degree of hardness.In the present invention
In specific embodiment, the carrier is specifically the silicon chip carrier of polishing.
The present invention particular/special requirement not any to the coating, can form film in carrier surface.In this hair
In bright specific embodiment, the coating is preferably rotary coating.In the present invention, coating of the degassing system in carrier surface
Thickness is preferably 1~2mm, more preferably 1.3~1.5mm.
In the present invention, the load is preferably had the carrier of degassing system to stand in air by the damping.At this
In invention, the humidity of the air is preferably 40~65%, and further preferably 50~60%；The time of the standing is preferably
5~8h, further preferably 6~7h.In the present invention, after the conditioning, the load has the carrier of degassing system
Humidity is preferably 10~30%, and further preferably 15~20%.
In the present invention, the displacement liquid is preferably water, ethyl alcohol or acetone.In the present invention, described replace specifically is
The carrier coated with degassing system is stood in displacement liquid, the solvent in displacement liquid molecule and degassing system carries out
Displacement.
In the present invention, the displaced temperature is preferably 20~40 DEG C, more preferably 25~35 DEG C, most preferably 30
℃；The displaced time is preferably 30~90min, more preferably 40~80min, most preferably 50~60min.
After obtaining the aquogel system, the aquogel system is set to two microporous teflon membrans by the present invention
Between, drying process obtains cellulose membrane.In the specific embodiment of the invention, the aperture of the microporous teflon membran is specific
It is 0.1 μm.In the present invention, between two microporous teflon membrans the thickness of aquogel system interlayer be preferably 2~
3mm, more preferably 2.2~2.8mm, most preferably 2.5~2.6mm.
The present invention applies a vertical effect in the dry progress, to obtained microporous teflon membran interlayer
Power, faying surface of the specific vertical force perpendicular to interlayer.In the specific embodiment of the invention, the vertical force is specially 50N.
In the present invention, the temperature of the drying is preferably 50~70 DEG C, and more preferably 55~65 DEG C, most preferably 60~
62℃；The time of the drying is preferably 10~15h, more preferably 12~13h.
After drying process obtains the cellulose membrane, the present invention adsorbs the cellulose membrane in the electrolytic solution, obtains fibre
Tie up plain polymer dielectric film.In the present invention, the electrolyte is preferably alkali system electrolyte, acid electrolyte or the electrolysis of salt system
Liquid.In the specific embodiment of the invention, alkali system electrolyte be preferably 6mol/L sodium hydroxide solution or potassium hydroxide it is molten
Liquid, the acid electrolyte are preferably 1mol/L sulfuric acid or hydrochloric acid, and salt system electrolyte is preferably 3mol/L metabisulfite solution
Or 1mol/L lithium chloride.
In the present invention, the absorption specifically carries out standing adsorption to submerge the cellulose membrane in the electrolytic solution；
The time of the absorption is preferably 20~30h, more preferably 22~28h, most preferably 24~26h.
Since the active group hydroxyl quantity of unformed shape cellulosic molecule surface exposure is more, in electrolyte soaking process
In, hydrogen bond action can be formed with hydrone first, generate swollen effect, aqueous solution intermediate ion passes through electrostatic effect and hydrogen bond respectively
Effect is adsorbed on cellulose molecular chain, it is therefore prevented that the loss of electrolyte improves the water retainability of fiber.
The present invention also provides the cellulosic polymers that preparation method described in a kind of above-mentioned technical proposal any one obtains
Dielectric film.
The present invention also provides a kind of the answering in the capacitor of cellulosic polymer dielectric film described in above-mentioned technical proposal
With.In the present invention, the capacitor can be specially all solid state capacitor and micro super capacitor.
Below with reference to embodiment to cellulosic polymer dielectric film provided by the invention and its preparation method and application into
Row detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
50g (0.286mol) [Bmim] Cl ionic liquid is added in the 250mL three-necked flask configured with condenser pipe, and
Mechanical stirring 10min under the conditions of 85 DEG C of oil bath.2.08g bamboo fiber element is added in the above three-necked flask, 85 DEG C of conditions
For lower mechanical stirring until cellulose is completely dissolved, system becomes clear viscous liquids, time 30min.It is poured into 100mL burning
Cup in be placed into temperature be 85 DEG C, vacuum degree be 0.01MPa vacuum drying phase in degassing process 6h, both final homogeneous transparent
[Bmim] Cl/ cellulose system.
[Bmim] Cl/ cellulose is homogeneously disposed in the silicon chip carrier of polishing using the method for rotary coating, coating thickness is
Then 2mm stands 6h in the air that humidity is 55% and carries out damping to the cellulose, so that the humidity of the cellulose reaches
25%.It is subsequently placed into 30 DEG C of distillation waters, after hydrone displaces [Bmim] Cl ionic liquid completely (60min), uniformly
Transparent aquagel is formed.Hydrogel is clipped between two 0.1 μm of PTFE microporous barrier, hydrogel thickness 3mm, loads 50N
Vertical is placed in 60 DEG C of air dry oven and handles the cellulose mesoporous film that 12h had both obtained flexible and transparent.
Dry cellulose mesoporous film is soaked in aqueous electrolyte (KOH solution of 6mol/L) and is taken out afterwards for 24 hours, and is wiped
Except the electrolyte of excess surface is to get the cellulosic polymer dielectric film with high ionic conductivity and mechanical property.
Active carbon, acetylene black and Kynoar are mixed according to the ratio of 8:1:1, obtain active material.Wherein, active
The specific surface area of charcoal is 2000 ± 100m2/ g, pore volume are 1~1.2cm3/g。
By 2~3mg active material be coated on foam nickel surface, after being handled 8 hours at 80 DEG C, use small-sized tablet press machine with
The pressure of 20MPa is pressed 5 minutes, and working electrode is obtained.
The cellulosic polymer dielectric film that working electrode and embodiment 1 are obtained uses the form of three layers of sandwich configuration
(working electrode // dielectric film // working electrode) dresses up capacitor: by a piece of work after the wetting of the KOH solution of 6mol/L
Make electrode, excess surface electrolyte is absorbed using filter paper；Dielectric film is covered in the working electrode active material surface；It will in addition
Working electrode (with active material one facing to dielectric film) after wetting is covered onto dielectric film；Using hot melt adhesive pair
Assembled supercapacitor is packaged processing (using special sealing machine), as shown in figure 13.Figure 13 is capacitor assembling
Schematic diagram.
The present invention observes the microstructure of cellulose mesoporous film using field emission scanning electron microscope (SEM)；Using bubble
Platen press tests cellulose mesoporous film highest probability pore-size distribution；It is mesoporous using highly sensitive omnipotent mechanics machine test cellulose
Polymer dielectric film mechanical stretching mechanics performance；It is mesoporous using electrochemical workstation AC impedance (EIS) method evaluation cellulose
The ionic conductivity of dielectric film；Using the cyclic voltammetry curve (CV) of electrochemical workstation, constant current charge-discharge curve
(GCD) and AC impedance (EIS) evaluation flexible super capacitor chemical property.
The translucent effect photo of cellulosic polymer dielectric film is as shown in Figure 1.As shown in Figure 1, the cellulose polymerization
Object dielectric film is able to carry out folding, and surface flexibility is good；It still can be clear through the cellulosic polymer dielectric film
The clear complexion for seeing plant shows transparent good.
Damping (humidity 60%) is distinguished at room temperature after 0 hour, 5 hours and 10 hours, cellulosic polymer electrolyte
The SEM scanned photograph difference of film is as shown in figs. 2 to 4.By Fig. 2~4 it is found that cellulosic polymer dielectric film has Jie abundant
Pore structure, aperture adjustability, and as the extension of damping time, aperture become larger, aperture is more uniform.
The porosity and ionic conductivity of cellulosic polymer dielectric film are as shown in Figure 5.As shown in Figure 5, cellulose is poly-
The porosity of polymer electrolyte membrane is 71.78%, ionic conductivity 0.325s/cm.
The tensile stress-strain curve of cellulosic polymer dielectric film is as shown in Figure 6.It will be appreciated from fig. 6 that the cellulose
Polymer dielectric film has excellent mechanical property.
The cyclic voltammetry curve of cellulosic polymer dielectric film is as shown in Figure 7.As shown in Figure 7, cellulosic polymer electricity
The CV curve for solving plasma membrane has good symmetry between reversal density range, shows ion adsorption desorption good reversibility, has
There are high bulking value and chemical property.
The constant current charge-discharge curve of cellulosic polymer dielectric film is as shown in Figure 8.As shown in Figure 8, cellulose polymerize
The GCD curve of object dielectric film has symmetrical isosceles triangle charging and discharging curve, shows that its chemical property is reversible, coulomb effect
Rate is high, and almost without voltage drop, chemical property is good.
The AC impedance spectroscopy of cellulosic polymer dielectric film is as shown in Figure 9.As shown in Figure 9, cellulosic polymer electricity
The intercept of the high-frequency region curve EIS curve and X-coordinate axle that solve plasma membrane is small, only 0.45 ohm, shows to assemble using this material
Supercapacitor equivalent series resistance it is low, good conductivity improves the cyclical stability and high current high rate performance of capacitor；
The EIS curve of low frequency region is approximately perpendicular to X-coordinate axle, shows using all solid state super of cellulosic polymer dielectric film assembling
Grade capacitor chemical property has high specific capacitance value close to perfect condition.
Specific capacitance of the cellulosic polymer dielectric film under different current densities is as shown in Figure 10.As shown in Figure 10, when
Current density be 0~10 peace/gram when, quality specific capacitance be 80~120 methods/gram, show that cellulosic polymer dielectric film has
Good high current charge-discharge high rate performance.
Cellulosic polymer dielectric film charge and discharge cycles stability under 1 peace/gram current density is as shown in figure 11.By scheming
11 it is found that circulation 10000 times after, quality specific capacitance can still reach 100 methods/gram, show cellulosic polymer be electrolysed
Plasma membrane has excellent stable circulation performance.
CV figure of the cellulosic polymer dielectric film under 100 mv ss sweep speeds.As shown in Figure 12, bending folding
Almost without influence, chemical property remains unchanged the CV figure of overlay cellulosic polymer dielectric film, presents ideal electricity
Stable chemical performance.
Figure 14 be cellulosic polymer dielectric film assembling flexible miniature supercapacitor flexibility with it is differently curved
CV curve graph under state, sweep speed are 200 mv ss.As shown in Figure 14, micro super capacitor has flexible well
Property with strong mechanical mechanics property；Bending angle is that the CV curve under 0 DEG C, 90 DEG C and 180 DEG C state is almost overlapped, table
Its bright excellent electrochemical state stability.
Embodiment 2
By the mixed solution of 50g NaOH and urea, (mass concentration of NaOH is 8%, 13%) mass concentration of urea is
It is added in 250mL three-necked flask, and mechanical stirring 20min under the conditions of ice bath (- 12 DEG C).2.08g cotton cellulose is added
Enter into the above three-necked flask, for mechanical stirring under the conditions of -12 DEG C until cellulose is completely dissolved, system becomes clear viscous liquid
Body, time 5min.Homogeneous transparent NaOH/ urea/cellulose system can be obtained.
NaOH/ urea/cellulose is homogeneously disposed in the silicon chip carrier of polishing using the method for rotary coating, coating thickness is
Then 2mm stands 5h in the air that humidity is 60% and carries out damping to the cellulose, so that the humidity of the cellulose reaches
25%.It is subsequently placed into 30 DEG C of distillation waters, after about 60min, homogeneous transparent hydrogel is formed.Hydrogel is clipped in two
Between 0.1 μm of PTFE microporous barrier, hydrogel thickness 3mm loads 50N vertical, is placed in 60 DEG C of air dry oven
Middle processing 12h had both obtained the cellulose mesoporous film of flexible and transparent.
Dry cellulose mesoporous film is soaked in aqueous electrolyte (KOH solution of 6mol/L) and is taken out afterwards for 24 hours, and is wiped
Except the electrolyte of excess surface is to get the cellulosic polymer dielectric film with high ionic conductivity and mechanical property.
Embodiment 3
By the mixture (matter of dimethyl acetamide and lithium chloride of 50g dimethyl acetamide and lithium chloride (DMAC/LiCl)
Amount is than being 50:3) it is added in the 250mL three-necked flask configured with condenser pipe, and the mechanical stirring under the conditions of 95 DEG C of oil bath
25min.2.08g sugarcane fibre element is added in the above three-necked flask, mechanical stirring under the conditions of 95 DEG C is until cellulose is complete
Dissolution, system become clear viscous liquids, time 50min.Being poured into 100mL beaker and being placed into temperature is 85 DEG C, very
Reciprocal of duty cycle be 0.01MPa vacuum drying phase in degassing process 6h, both final homogeneous transparent (DMAC/LiCl/ cellulose system.
Using the method for rotary coating by (DMAC/LiCl/ cellulose is homogeneously disposed in the silicon chip carrier of polishing, coating thickness
For 2mm, 6h is then stood in the air that humidity is 55%, damping is carried out to the cellulose, so that the humidity of the cellulose reaches
25%.It is subsequently placed into 30 DEG C of distillation waters, is displaced completely (after DMAC/LiCl ionic liquid (60min), after hydrone
Even transparent aquagel is formed.Hydrogel is clipped between two 0.1 μm of PTFE microporous barrier, hydrogel thickness 3mm, is loaded
50N vertical is placed in 60 DEG C of air dry oven and handles the cellulose mesoporous film that 12h had both obtained flexible and transparent.
Dry cellulose mesoporous film is soaked in aqueous electrolyte (KOH solution of 6mol/L) and is taken out afterwards for 24 hours, and is wiped
Except the electrolyte of excess surface is to get the cellulosic polymer dielectric film with high ionic conductivity and mechanical property.
As seen from the above embodiment, the present invention provides a kind of cellulosic polymer dielectric film and preparation method thereof and answer
With.For the present invention using cellulose as raw material, mutual prehensile and a large amount of meso-hole structure between cellulose molecular chain make its tool
There are high porosity, water suction and water retention property, improves its ion-conductance conductivity；The a large amount of hydrogen formed between cellulose molecular chain
Key effect and three-dimensional homogeneous system make it have good mechanical property.By the result of embodiment it is found that provided by the invention
Cellulosic polymer dielectric film is able to carry out folding, and surface flexibility and the transparency are good；With mesoporous knot abundant
Structure, aperture adjustability, and as the extension of damping time, aperture become larger, aperture is more uniform；Porosity is 71.78%, ion
Conductivity is 0.325s/cm, ideal mechanical property.The all solid state super capacitor assembled using cellulosic polymer dielectric film
Device has excellent chemical property.Current density be 0.5 peace/gram, biggest quality specific capacitance up to 120.6 methods/gram, even if 10
Under peace/gram high current density, still have up to 81.4 methods/gram quality specific capacitance, present good high rate performance.Circulation
Stability is prominent, under 1 peace/gram current density, after charge and discharge cycles 10000 times, quality specific capacitance still up to 100 methods/gram.More
Make people glad, the all-solid-state supercapacitor of assembling has shown superior flexibility, even if being up to 180 in bending angle
Under the conditions of DEG C, original chemical property is still kept, specific capacitance value remains unchanged.And cellulosic polymer dielectric film in addition to
The flexible all-solid-state supercapacitor that sandwich form can be assembled can be also used for assembling flexible miniature supercapacitor, together
Sample has shown ideal chemical property, it was demonstrated that the superiority of cellulosic polymer dielectric film performance and application
Scalability.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
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| CN110724307B (en) * | 2019-09-10 | 2021-11-30 | 沈阳化工大学 | Preparation method of renewable cellulose conductive film with stable flexible conductivity |
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