CN111499998B - Preparation method of cellulose polyvinyl alcohol composite membrane and super capacitor based on phase inversion - Google Patents
Preparation method of cellulose polyvinyl alcohol composite membrane and super capacitor based on phase inversion Download PDFInfo
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- 239000001913 cellulose Substances 0.000 title claims abstract description 108
- 229920002678 cellulose Polymers 0.000 title claims abstract description 108
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 75
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 75
- 239000012528 membrane Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003990 capacitor Substances 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
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- 238000002791 soaking Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000001110 calcium chloride Substances 0.000 claims abstract description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
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- 239000003792 electrolyte Substances 0.000 claims description 20
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
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- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
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- 229910052739 hydrogen Inorganic materials 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
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- 238000010561 standard procedure Methods 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
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- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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Abstract
The invention discloses a preparation method of a cellulose polyvinyl alcohol composite membrane based on phase inversion and a preparation method of a super capacitor, wherein the preparation method comprises the following steps: preparing a cellulose solution by using sodium hydroxide, urea and cellulose raw materials; mixing a cellulose solution and a polyvinyl alcohol solution in proportion to form a film, wherein the cellulose in the film accounts for 10-25% of the solid content of the film; soaking the film in a mixed solution of calcium chloride and hydrochloric acid for regeneration, soaking the film in glycerol for plasticization, and finally drying the film to obtain the cellulose polyvinyl alcohol composite film. The invention takes cellulose as raw material, sodium hydroxide, urea and water as solvent, adopts the method of dissolution-regeneration and phase inversion to prepare the cellulose polyvinyl alcohol composite membrane, and compared with the traditional polyolefin material, the composite membrane has good tensile strength, elongation at break and hydrophilicity, and high porosity, liquid absorption rate and liquid retention rate. The super capacitor assembled by the composite film can show good electrochemical performance.
Description
Technical Field
The invention relates to the technical field of electrochemical materials, in particular to a preparation method of a cellulose polyvinyl alcohol composite membrane based on phase inversion and a method for preparing a super capacitor by using the cellulose polyvinyl alcohol composite membrane.
Background
With the increase of the usage amount of petrochemical resources and the reduction of reserves, the development of green renewable new energy gradually becomes a global consensus, and the development and utilization of biomass resources are paid extensive attention. The cellulose is a biomass resource with large amount, regeneration and environmental protection, has good film wettability, low price, light weight, low thermal shrinkage and strong mechanical property, and is expected to be applied to the field of super capacitor diaphragms. At present, the separators used in domestic supercapacitors mostly depend on the import from countries such as europe, the united states (Celgard corporation), japan (NKK corporation), and the like, and the separators used in the lower-end supercapacitors mostly adopt the common battery separators manufactured in China. Generally, battery separators are mainly made of polyolefin materials, although the battery separators have some excellent performances, a single material of the type has low surface energy and hydrophilicity, so that the wettability is poor, the impedance is high, the separators are mostly through holes, the porosity is low, the liquid absorption rate and the liquid retention rate are not high, and the battery separators are not beneficial to the charging and discharging process. The importance of the membrane system as the third pole of the super capacitor determines that the super capacitor has proper porosity and ionic conductivity, uniform pore diameter, high liquid absorption rate and liquid retention rate, mechanical properties, good electrochemical stability, chemical inertness, flame retardance, thermal stability and the like. From another point of view, in view of the current economic situation, the continuous development and utilization of petrochemical resources and the reduction of reserves will inevitably result in the over-high energy cost, which is mainly reflected in the increase of raw material cost, labor cost and environmental protection cost, while the price of market products is in the trend of decreasing. Moreover, the traditional diaphragm material may not fully satisfy the diversified requirements of people for the small size, light weight, large capacitance, portability, flexibility and the like of the portable electronic energy storage device in the future. Product and market demands suggest that the preparation and development of a novel replaceable, large-volume, renewable, low-price and environment-friendly diaphragm material for a super capacitor is of great significance, and the key step for solving the problem lies in the development of a novel material and a technical means. The membrane material prepared by utilizing the natural biomass cellulose has good wettability, low price, light weight, low thermal shrinkage, high porosity and mechanical properties, and is expected to be applied to the field of super capacitor membranes.
Disclosure of Invention
It is an object of the present invention to address at least the above-mentioned deficiencies and to provide at least the advantages which will be described hereinafter.
The invention also aims to provide a preparation method of the novel environment-friendly cellulose-polyvinyl alcohol composite diaphragm, and the composite diaphragm prepared by the method can solve the problems of low surface energy and hydrophilicity, poor wettability, high impedance, low liquid absorption rate and liquid retention rate and the like existing in the conventional battery diaphragm (polyolefin material) serving as a supercapacitor diaphragm.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing a phase-inversion-based cellulose polyvinyl alcohol composite membrane, comprising:
preparing a cellulose solution by using sodium hydroxide, urea and cellulose raw materials; preparing a polyvinyl alcohol solution; mixing a cellulose solution and a polyvinyl alcohol solution in proportion to form a film, wherein the cellulose in the film accounts for 10-25% of the solid content of the film; and soaking and regenerating the film by using a mixed solution of calcium chloride and hydrochloric acid, soaking and plasticizing by using glycerol, and finally drying to obtain the cellulose polyvinyl alcohol composite film.
In the technical scheme, the cellulose is used as a raw material, the sodium hydroxide, the urea and the water are used as solvents, and the cellulose polyvinyl alcohol composite membrane is prepared by adopting a dissolving-regenerating and phase-converting method.
Preferably, in the preparation method of the phase-inversion-based cellulose polyvinyl alcohol composite membrane, the mass percentage concentration of the cellulose solution is 2%; the mass percentage concentration of the polyvinyl alcohol solution is 9%; the cellulose in the film accounts for 20% of the solid content of the film. The composite membrane prepared under the proportion shows more pores, smaller pore diameter, more uniform pore structure, higher ultimate tensile stress and Young modulus, and contact angle less than 100 degrees, thus being beneficial to the absorption and permeation of electrolyte.
Preferably, in the preparation method of the phase-inversion-based cellulose polyvinyl alcohol composite membrane, the preparation method of the fiber raw material comprises the following steps:
crushing and screening straw or rice husk as a raw material to obtain straw powder;
placing the screened straw powder in a solution with a bath ratio of 50g/L for heating in water bath, adding 40g/L NaOH and 2g/L NaHSO3Controlling the temperature of the water bath at 90 ℃, heating for 4 hours, fully stirring the mixture during the heating, and filtering the mixture to obtain a solid matter;
mixing the obtained solid, 10g/L sodium chlorite and 5-6ml acetic acid, stirring and heating for 4 hours under the condition of a water bath at 70 ℃, adding 5-6ml acetic acid every 1 hour in the period; and (3) fully washing the solid after the water bath heating is finished, filtering, and fully drying in a drying oven at 60 ℃ to obtain the cellulose raw material.
In the scheme, straw or rice husk is used as a raw material, and NaHSO is added while sodium hydroxide water boiling is carried out3Then, sodium chlorite and acetic acid are used for heating treatment in a water bath. During the alkaline treatment, much of the lignocellulosic structure is destroyed and most of the hemicellulose and lignin components present in the straw feedstock are dissolved. Thus, in addition to some hard components which are difficult to remove from the cell walls during delignification, some loose material in the straw material can be easily removed, effectively increasing the percentage of cellulose content in the straw material. Furthermore, almost all silica content is removed during the alkali treatment. In thatIn the process of alkali treatment, the added bisulfite ions can perform addition reaction on carbonyl to generate sodium hydroxysulfonate, destroy a conjugated system, do not develop color any more and achieve the effect of primary bleaching, and in the bleaching process, the percentage of hemicellulose and lignin is further reduced, so that the percentage of cellulose components in a sample is increased, and the rice hull cellulose with the purity of 96 percent is generated. The results are shown in Table 2.
Preferably, in the preparation method of the phase-inversion-based cellulose polyvinyl alcohol composite membrane, the method specifically comprises the following steps:
1) taking a proper amount of dried straws or rice husks, cutting the dried straws or rice husks into small sections of 3-4 cm, crushing the small sections by using a universal crusher, screening the small sections by using a 40-mesh sieve, and separating straw powder;
2) placing the screened straw powder in a solution with a bath ratio of 50g/L for heating in water bath, adding a proper amount of 40g/L NaOH and 2g/L NaHSO3Controlling the temperature of the water bath at 90 ℃, heating for 4 hours, fully stirring during the heating so as to perform a good reaction, and filtering to obtain a solid matter;
3) adding 10g/L sodium chlorite and 5-6ml acetic acid into the obtained solid, stirring and heating for 4 hours under the condition of a water bath at 70 ℃, adding acetic acid every 1 hour in the process, and adding 5-6ml of acetic acid every time; fully washing the solid after the water bath heating is finished, filtering, fully drying in a drying oven at 60 ℃, and taking out the dried solid to obtain the cellulose raw material;
4) preparing an aqueous solution with NaOH content of 7% and urea content of 12%, weighing straw cellulose with required amount, and fully reacting the cellulose with the aqueous solution in a freezing tank at-12 ℃ to obtain a 2 wt% cellulose solution;
5) weighing PVA particles with a certain mass, and dissolving the PVA particles in a proper amount of distilled water under the water bath condition of more than 95 ℃ to obtain a 9 wt% PVA solution;
6) putting the obtained cellulose solution and PVA solution in a beaker according to a certain proportion, putting the beaker into a rotor, then putting the rotor on an electromagnetic stirrer, stirring the mixture for 20min, taking the mixture down, pouring the mixture into a glass tank, sucking bubbles by a dropper, then uniformly distributing the liquid in the glass tank, putting the glass tank into a vacuum drying oven with the temperature of 60 ℃ for drying, and taking the glass tank out after drying to obtain a film;
7) preparing 250ml of CaCl with the mass fraction of 5 percent in corresponding parts2And 3% HCl solution, soaking the film for 20min by using the solution, washing by using clear water, draining, soaking by using 150ml of 30% glycerol solution, taking out the film for 20min, washing, draining, placing the film in clear water for soaking overnight, taking out the film after soaking, and drying the film by using a vacuum freeze drying oven to obtain the cellulose polyvinyl alcohol composite film.
In the technical scheme, 10 wt% cellulose membrane (CP-10), 15 wt% cellulose membrane (CP-15), 20 wt% cellulose membrane (CP-20) and 25 wt% cellulose membrane (CP-25) are respectively prepared; wherein, the surface and the cross section of the cellulose-polyvinyl alcohol composite membrane show a porous structure, and the interior (CP-10, CP-15, CP-20) of the membrane shows more pores, the pore diameter is smaller, and the pore structure is more uniform (except the CP-25 membrane) along with the increase of the cellulose proportion. The ultimate tensile stress and Young's modulus of CP films increase from CP-10 to CP-20 as the cellulose-polyvinyl alcohol mass ratio increases, due to intermolecular and intramolecular hydrogen bonding interactions formed by O-H in the cellulose and PVA molecules. The decrease in ultimate tensile stress and Young's modulus of CP-25 is due to the decreased miscibility and compatibility with high cellulose mass ratios. For CP films, the contact angle is less than 100 ° after 6s, which favors the adsorption and permeation of the electrolyte. The contact angle of the CP film decreases from 10 wt% to 25 wt% as the cellulose mass ratio increases. The porosity of the CP film increased from 41.66% (CP-10) to 59.69% (CP-20) and then decreased to 48.14% (CP-25). CP-20 has the highest porosity compared to other membranes. The high porosity determines to some extent the electrolyte absorption properties of the membrane. The electrolyte absorption and porosity of CP films show the same trend: CP-20(281.26 wt%) > CP-15(199.71 wt%) > CP-25(170.20 wt%) > CP-10(157.39 wt%). The combination of good mechanical properties, uniform mesoporous structure, good hydrophilicity, high porosity and electrolyte absorption rate indicates that the supercapacitor assembled by the CP diaphragm can show good electrochemical properties.
Preferably, in the preparation method of the phase-inversion-based cellulose polyvinyl alcohol composite membrane, the volume ratio of the cellulose solution to the PVA solution is: a volume ratio of 50:100 or 75:94 or 100:89 or 125: 83.
A preparation method of a super capacitor, which utilizes the prepared cellulose polyvinyl alcohol composite membrane, comprises the following steps:
uniformly loading a mixture of 80 wt% of activated carbon, 10 wt% of acetylene black and 10 wt% of polytetrafluoroethylene on a nickel foam substrate to prepare a working electrode;
immersing the obtained working electrode and the cellulose polyvinyl alcohol composite membrane in 6M KOH solution for 48 hours, and then removing residual electrolyte on the electrode and the cellulose polyvinyl alcohol composite membrane by using filter paper; and (2) using a cellulose polyvinyl alcohol composite membrane as a diaphragm, and assembling by adopting an electrode-separator-electrode sandwich structure to obtain the super capacitor.
In the technical scheme, the supercapacitors SC-10, SC-15, SC-20 and SC-25 are respectively prepared from 10 wt% cellulose membrane (CP-10), 15 wt% cellulose membrane (CP-15), 20 wt% cellulose membrane (CP-20) and 25 wt% cellulose membrane (CP-25), wherein CV curves of all SCs are close to a typical rectangle. The CV curve of SC-20 is more similar to a typical rectangle than the CP-10, CP-15 and CP-25 assembled supercapacitors SC, which may be due to the low electrical conductivity and mass transfer resistance of the system. Even with the increase in scan rate to 300mV/s, the CV curve for SC-20 still resembles a typical rectangle, while the other SCs curves begin to change to fusiform. Furthermore, the CV curve for SC-20 shows an integrated area greater than the integrated areas for SC-10, SC-15 and SC-25. At different scan rates (5mV/s to 300mV/s), and the area specific capacitance of SC-20 was also greater than that of SC-10, SC15, and SC-25. The results of the EIS curves show that the equivalent series resistance of SC-20 is 0.57 Ω, which is smaller than the equivalent series resistances of SC-10(2.68 Ω), SC-15(1.90 Ω) and SC-25(2.34 Ω). SC-20 has a longer GCD time and a quasi-symmetrical shape compared to other SCs, indicating its excellent capacitive performance. The charge-discharge efficiency of SC-20 (98.62%) was higher than that of SC-10 (83.65%), SC-15 (90.20%) and SC-20 (85.54%) under the condition of 1A/g. Trend of specific capacitance of SCIs SC-20>SC-15>SC-25>SC-10. The specific capacitance of SC-20 is up to 134.41F g at 1A/g-1The GCD curve for SC-20 was close to an isosceles triangle and no significant IR drop was found, indicating that SC-20 has good reversibility and IV response. Even at a high scan rate of 10A/g, the IR drop for SC-20 was only 0.08V, lower than SC-10(0.3V), SC-15(0.18V) and SC-25 (0.22V). The energy density and power density of SC-20 were also greater than SC-10, SC-15 and SC-25 at different current densities of 0.5 to 10A/g. The capacitive performance of SC-20 was superior to other SCs, consistent with the porosity, electrolyte absorption, SEM, EIS, and CV analyses described above.
The invention at least comprises the following beneficial effects:
the cellulose-polyvinyl alcohol composite membrane (CP membrane) material prepared by the method is a thin membrane with certain tensile strength, good elongation at break, good lyophilic property, high porosity, high liquid absorption rate and liquid retention rate. The super capacitor assembled by the cellulose-polyvinyl alcohol composite membrane as the diaphragm has good electrochemical performance. In addition, the comparative experiment of the cellulose-polyvinyl alcohol composite membrane prepared by the invention and a commercial diaphragm shows beneficial performance.
The surface and the section of the cellulose-polyvinyl alcohol composite membrane prepared by the invention show a porous structure, and with the increase of the proportion of cellulose, the interior of the membrane shows more pores, the pore diameter is smaller, and the pore structure is more uniform.
The contact angle of the cellulose-polyvinyl alcohol composite membrane (CP membrane) prepared by the invention is less than 100 degrees after 6s, which is beneficial to the adsorption and permeation of electrolyte. The contact angle of the CP film decreases from 10 wt% to 25 wt% as the cellulose mass ratio increases. The porosity of the CP film increased from 41.66% to 59.69% and then decreased to 48.14%. The high porosity determines to some extent the electrolyte absorption properties of the membrane. The combination of good mechanical properties, uniform mesoporous structure, good hydrophilicity, high porosity and electrolyte absorption rate indicates that the supercapacitor assembled by the CP diaphragm can show good electrochemical properties.
In the Super Capacitor (SC) prepared by the invention, the CV curves of all SCs are close to a typical rectangle. The CV curve of SC-20 is more similar to a typical rectangle than the supercapacitor SC assembled by CP-10, CP-15 and CP-25, which may be due to the low conductivity and mass transfer resistance of the system. Even with the increase in scan rate to 300mV/s, the CV curve for SC-20 still resembles a typical rectangle, while the other SCs curves begin to change to fusiform. Furthermore, the CV curve for SC-20 shows an integrated area greater than the integrated areas for SC-10, SC-15 and SC-25. At different scan rates (5mV/s to 300mV/s), and the area specific capacitance of SC-20 was also greater than that of SC-10, SC15, and SC-25.
The results of the EIS curves show that the equivalent series resistance of SC-20 is 0.57 Ω, which is smaller than the equivalent series resistances of SC-10(2.68 Ω), SC-15(1.90 Ω) and SC-25(2.34 Ω).
SC-20 has a longer GCD time and a quasi-symmetrical shape compared to other SCs, indicating its excellent capacitive performance. The charge-discharge efficiency of SC-20 (98.62%) was higher than that of SC-10 (83.65%), SC-15 (90.20%) and SC-20 (85.54%) under the condition of 1A/g. The trend of the specific capacitance of SC is SC-20>SC-15>SC-25>SC-10. The specific capacitance of SC-20 is up to 134.41F g at 1A/g-1The GCD curve of SC-20 is close to an isosceles triangle and no significant IR drop is found, indicating that SC-20 has good reversibility and IV response. Even at a high scan rate of 10A/g, the IR drop for SC-20 was only 0.08V, lower than SC-10(0.3V), SC-15(0.18V) and SC-25 (0.22V). The energy density and power density of SC-20 were also greater than SC-10, SC-15 and SC-25 at different current densities of 0.5 to 10A/g. The capacitive performance of SC-20 was superior to other SCs, consistent with the porosity, electrolyte absorption, SEM, EIS, and CV analyses described above.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is an SEM plane (a) and a sectional view (b) of a cellulose polyvinyl alcohol composite film of the present invention, a contact angle (c), mechanical properties (d), porosity (e), and an electrolyte absorption amount (f);
FIG. 2 is a CV curve and an area specific capacitance of a supercapacitor assembled by the cellulose polyvinyl alcohol composite film according to the present invention;
FIG. 3 shows the GCD curve, EIS curve, specific mass capacitance, energy density and power density of a supercapacitor assembled with the cellulose-polyvinyl alcohol composite film according to the present invention.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example 1
1) Taking a proper amount of dried straws, cutting the straws into small sections of 3-4 cm, crushing the straws by using a universal crusher (the crushing time is about 30s each time), screening the straws by using a 40-mesh sieve, and separating the raw materials for preparing the cellulose required by the subsequent experiments.
2) Placing the screened powder in a solution with a bath ratio of 50g/L for water bath heating, adding a proper amount of 40g/L NaOH and 2g/L NaHSO into the solution3The reaction was carried out by heating the mixture for 4 hours while controlling the temperature of the water bath at 90 ℃ while sufficiently stirring the mixture for the reaction to proceed satisfactorily.
3) Filtering to remove solid, adding 10g/L sodium chlorite and 5-6ml acetic acid (commercial acetic acid with concentration of 36-38%), stirring and heating for 4 hours under 70 ℃ water bath condition, adding 5-6ml acetic acid every 1 hour. And (3) fully washing the solid after water bath heating, filtering, fully drying in a drying oven at 60 ℃, and taking out after drying to obtain the cellulose raw material required by the preparation of the film.
4) Preparation of a 2 wt% cellulose solution
Preparing an aqueous solution with NaOH content of 7% and urea content of 12%, weighing straw cellulose with required amount, and allowing the cellulose to fully react with the solution in a freezing tank at-12 deg.C to obtain a 2% cellulose solution.
5) Preparation of 9 wt% PVA solution
A certain mass of PVA particles is weighed and dissolved in a proper amount of distilled water under the condition of a water bath at the temperature of more than 95 ℃ to obtain a 9% PVA solution.
6) Preparation of cellulose polyvinyl alcohol composite film
Putting the PVA solution into a beaker, placing the beaker into a rotor, then placing the rotor on an electromagnetic stirrer, stirring the rotor for 20min, taking the PVA solution off, pouring the PVA solution into a glass tank, sucking bubbles by a dropper to uniformly distribute the liquid in the glass tank, placing the glass tank into a vacuum drying oven with the temperature of 60 ℃ for drying, and taking the glass tank out after drying. Preparing 250ml of 5% CaCl in corresponding parts2And soaking the film in 3% HCl solution for 20min, washing with clear water, draining, soaking in 30% glycerin solution 150ml, washing for 20min, draining, soaking in clear water overnight, taking out the film, and drying in a vacuum freeze drying oven to obtain the cellulose-polyvinyl alcohol composite film named CP-10.
Example 2
This example is different from example 1 in the amounts of cellulose and polyvinyl alcohol added in step (6) (see table 1 for details), and the composite film obtained is CP-15.
Example 3
This example is different from example 1 in the amount of cellulose and polyvinyl alcohol added in step (6) (see table 1 for details), and the composite film obtained is CP-20.
Example 4
The difference between this example and example 1 is the amount of cellulose and polyvinyl alcohol added in step (6) (see table 1 for details), and the composite membrane is CP-25.
TABLE 1 cellulose-polyvinyl alcohol composite film protocol
Comparative example
The chemical composition of the Rice Hulls (RH), delignified Rice Hulls (RHD) and bleached Rice Hulls (RHC) was determined according to ASTM and TAPPI standard methods and is shown in table 2.
Wherein the bleached Rice Hulls (RHC) are: the cellulose raw material obtained by the preparation method of the invention comprises the following steps: i.e. using rice hulls as raw materialCrushing and screening to obtain straw powder; placing the screened straw powder in a solution with a bath ratio of 50g/L for heating in water bath, adding 40g/L NaOH and 2g/L NaHSO3Controlling the temperature of the water bath at 90 ℃, heating for 4 hours, fully stirring the mixture during the heating, and filtering the mixture to obtain a solid matter; mixing the obtained solid, 10g/L sodium chlorite and 5-6ml acetic acid (the commercial acetic acid with the concentration of 36-38%), stirring and heating for 4 hours under the condition of a water bath at 70 ℃, adding 5-6ml acetic acid every 1 hour in the period; and (3) fully washing the solid after the water bath heating is finished, filtering, and fully drying in a drying oven at 60 ℃ to obtain the cellulose raw material.
Delignified Rice Hulls (RHD) are: compared with the bleached Rice Hull (RHC) above, no subsequent water bath bleaching with sodium chlorite and acetic acid was used, and the other steps were identical.
Rice Hulls (RH); untreated virgin rice hulls.
The cellulose content was obtained according to TAPPI standard T203 OS-61, the cellulose content was obtained according to ASTM standard ASTM D1104-56, and the lignin content was measured according to TAPPI standard T222 OS-83. The ash content of the silica was determined using thermogravimetric analysis (TGA) data. During rice hull combustion, cellulose and lignin are decomposed and removed, and the remaining rice hull ash typically contains almost 95% or more amorphous silica. The rice husk ash may remain in amorphous form with a combustion temperature of up to 900 ℃. On this basis, the composition of silica fume was obtained at a temperature of 900 ℃ because the remaining ash at this time was attributable to silica fume.
TABLE 2
Table 2 shows the chemical composition of the Rice Hulls (RH), delignified Rice Hulls (RHD) and bleached Rice Hulls (RHC). The results show that the bleached rice hulls obtained by the method of the invention remove amorphous components such as lignin, hemicellulose and silicon dioxide, and the cellulose content is obviously increased. During the alkaline treatment, a substantial amount of the lignocellulosic structure is destroyed and most of the hemicellulose and lignin components present in the straw feedstock are dissolved. Thus, in addition to some hard components which are difficult to remove from the cell walls during delignification, some loose material in the straw material can be easily removed, effectively increasing the percentage of cellulose content in the straw material. Furthermore, almost all silica content is removed during the alkali treatment. In the process of alkali treatment, the added bisulfite ions can perform addition reaction on carbonyl to generate sodium hydroxysulfonate, destroy a conjugated system, do not develop color any more and achieve the effect of primary bleaching, and in the bleaching process, the percentage of hemicellulose and lignin is further reduced, so that the percentage of cellulose components in a sample is increased, and the rice hull cellulose with the purity of 96 percent is generated.
Example 5
Assembling the super capacitor:
CP-10, CP-15, CP-20, and CP-25 were used as separators, respectively, and a mixture of 80 wt% of activated carbon, 10 wt% of acetylene black, and 10 wt% of polytetrafluoroethylene was uniformly loaded on an area of 1cm2To prepare a working electrode. The obtained electrode (AB) and separator were immersed in a 6M KOH solution for 48h, and then the residual electrolyte on the surfaces of the electrode and separator was removed using filter paper. The supercapacitor (electrode/separator/electrode) devices were assembled using a sandwich-like approach, denoted SC-10, SC-15, SC-20, SC-25, respectively.
Example 6
Electrochemical performance measurement of the supercapacitor:
the electrochemical properties of the supercapacitor SC were tested by using an electrochemical workstation. Electrochemical Impedance Spectroscopy (EIS) was performed at a frequency of 5mV in the frequency range of 0.01-100 kHz. Cyclic Voltammetry (CV) measurements were performed over different scan rate ranges (5mV/s to 200 mV/s). Constant current charge and discharge (GCD) measurements were obtained at current densities of 0.5 to 10A/g. The equivalent resistance is obtained from EIS measurements. The area capacitance was calculated from the CV curve. The mass specific capacitance, energy density and power density were calculated from the GCD curves. Cycling stability of SC was performed by GCD cycling test.
Test analysis
FIGS. 1a and 2b show the surface and cross-sectional microstructures of cellulose-polyvinyl alcohol composite films CP-10, CP-15, CP-20, and CP-25 at different ratios, respectively. The surface and cross section of the cellulose-polyvinyl alcohol composite membrane show a porous structure, and as the proportion of cellulose increases, the interior of the membrane (CP-10, CP-15, CP-20) shows more pores, smaller pore sizes, and a more uniform pore structure (except for CP-25 membrane). The upper surface and fracture surface of the CP-25 film appeared to be uneven and numerous deposits appeared. This phenomenon may be due to the excessive proportion of cellulose leading to a decrease in compatibility between the cellulose and PVA molecules.
As shown in FIG. 1d, the ultimate tensile stress and Young's modulus of the CP film increased to CP-20 as the cellulose/polyvinyl alcohol mass ratio increased from CP-10, due to intermolecular and intramolecular hydrogen bonding interactions formed by O-H in the cellulose and PVA molecules. The decrease in ultimate tensile stress and Young's modulus of CP-25 is due to the decreased miscibility and compatibility with high cellulose mass ratios.
The hydrophilicity and porosity of the separator directly affect the absorption of the electrolyte, which will affect the performance of the supercapacitor assembled from the separator. For CP films, the contact angle is less than 100 ° after 6s (fig. 1c), which favors the adsorption and permeation of the electrolyte. The contact angle of the CP film decreases from 10 wt% to 25 wt% as the cellulose mass ratio increases. This is due to the high hydrophilicity resulting from the large number of free hydroxyl groups in the cellulose molecules that do not form hydrogen bonds with the PVA molecules. As shown in FIG. 1e, the porosity of the CP film increased from 41.66% (CP-10) to 59.69% (CP-20) and then decreased to 48.14% (CP-25). CP-20 had the highest porosity compared to the other membranes, which is consistent with SEM analysis. The high porosity determines to some extent the electrolyte absorption properties of the membrane. Thus, as shown, the electrolyte absorption and porosity of the CP film showed the same trend (CP-20(281.26 wt%) > CP-15(199.71 wt%) > CP-25(170.20 wt%) > CP-10(157.39 wt%)). As can be seen in fig. 1, the combination of high mechanical properties, uniform mesoporous structure, good hydrophilicity, high porosity and electrolyte absorption rate indicates that the supercapacitor assembled with the CP separator may exhibit good electrochemical properties.
FIG. 2 shows CV curves for SC-10, SC-15, SC-20, and SC-25 at various scan rates of 5 to 300mV/s, with the CV curves for all SCs approximating a typical rectangle. The CV curve of SC-20 is more similar to a typical rectangle than the supercapacitor SC assembled by CP-10, CP-15 and CP-25, which may be due to the low conductivity and mass transfer resistance of the system. Even with the increase in scan rate to 300mV/s, the CV curve for SC-20 still resembles a typical rectangle, while the other SCs curves begin to change to fusiform. Furthermore, the CV curve for SC-20 shows an integrated area greater than the integrated areas for SC-10, SC-15 and SC-25. At different scan rates (5mV/s to 300mV/s), and the area specific capacitance of SC-20 was also greater than that of SC-10, SC15, and SC-25.
FIG. 3 is a GCD plot of SCs (SC-10, SC-15, SC-20, and SC-25) at different scan rates of 1.0, 2.0, and 10.0A/g. SC-20 has a longer GCD time and a quasi-symmetrical shape compared to other SCs, indicating its excellent capacitive performance. The charge-discharge efficiency of SC-20 (98.62%) was higher than that of SC-10 (83.65%), SC-15 (90.20%) and SC-20 (85.54%) under the condition of 1A/g. FIG. 3 shows that the trend of the specific capacitance of SC is SC-20>SC-15>SC-25>SC-10. The specific capacitance of SC-20 is up to 134.41F g at 1A/g-1The GCD curve for SC-20 was close to an isosceles triangle and no significant IR drop was found, indicating that SC-20 has good reversibility and IV response. Even at a high scan rate of 10A/g, the IR drop for SC-20 was only 0.08V, lower than SC-10(0.3V), SC-15(0.18V) and SC-25 (0.22V). The energy density and power density of SC-20 were also greater than SC-10, SC-15 and SC-25 at different current densities of 0.5 to 10A/g. The capacitive performance of SC-20 was superior to other SCs, consistent with the porosity, electrolyte absorption, SEM, EIS, and CV analyses described above.
The results of the EIS curves show that the equivalent series resistance of SC-20 is 0.57 Ω, which is smaller than the equivalent series resistances of SC-10(2.68 Ω), SC-15(1.90 Ω) and SC-25(2.34 Ω).
While embodiments of the invention have been disclosed above, it is not intended that they be limited to the applications set forth in the specification and examples. It can be applied to all kinds of fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art.
Claims (5)
1. A preparation method of a cellulose polyvinyl alcohol composite membrane based on phase inversion is characterized by comprising the following steps:
preparing a cellulose solution by using sodium hydroxide, urea and cellulose raw materials; preparing a polyvinyl alcohol solution; mixing a cellulose solution and a polyvinyl alcohol solution in proportion to form a film, wherein the cellulose in the film accounts for 10-25% of the solid content of the film; soaking and regenerating the film by using a mixed solution of calcium chloride and hydrochloric acid, soaking and plasticizing by using glycerol, and finally drying to obtain the cellulose polyvinyl alcohol composite film;
the preparation method of the cellulose raw material comprises the following steps:
crushing and screening straw or rice husk as a raw material to obtain straw powder;
placing the screened straw powder in a solution with a bath ratio of 50g/L for heating in water bath, adding 40g/L NaOH and 2g/L NaHSO3Controlling the temperature of the water bath at 90 ℃, heating for 4 hours, fully stirring the mixture during the heating, and filtering the mixture to obtain a solid matter;
mixing the obtained solid, 10g/L sodium chlorite and 5-6ml acetic acid, stirring and heating for 4 hours under the condition of a water bath at 70 ℃, adding 5-6ml acetic acid every 1 hour in the period; and (3) fully washing the solid after the water bath heating is finished, filtering, and fully drying in a drying oven at 60 ℃ to obtain the cellulose raw material.
2. The method for preparing the phase-inversion-based cellulose polyvinyl alcohol composite membrane according to claim 1, wherein the cellulose solution has a mass percentage concentration of 2%; the mass percentage concentration of the polyvinyl alcohol solution is 9%; the cellulose in the film accounts for 20% of the solid content of the film.
3. The method for preparing the phase inversion-based cellulose polyvinyl alcohol composite membrane according to claim 2, which specifically comprises:
1) taking a proper amount of dried straws or rice husks, cutting the dried straws or rice husks into small sections of 3-4 cm, crushing the small sections by using a universal crusher, screening the small sections by using a 40-mesh sieve, and separating straw powder;
2) placing the screened straw powder in a solution with a bath ratio of 50g/L for heating in a water bath, adding a proper amount of 40g/L NaOH and 2g/L NaHSO3Controlling the temperature of the water bath at 90 ℃, heating for 4 hours, fully stirring during the heating so as to perform a good reaction, and filtering to obtain a solid matter;
3) adding 10g/L sodium chlorite and 5-6ml acetic acid into the obtained solid, stirring and heating for 4 hours under the condition of a water bath at 70 ℃, adding acetic acid every 1 hour in the process, and adding 5-6ml of acetic acid every time; fully washing the solid after the water bath heating is finished, filtering, fully drying in a drying oven at 60 ℃, and taking out the dried solid to obtain the cellulose raw material;
4) preparing an aqueous solution with NaOH content of 7% and urea content of 12%, weighing straw cellulose with required amount, and fully reacting the cellulose with the aqueous solution in a freezing tank at-12 ℃ to obtain a 2 wt% cellulose solution;
5) weighing PVA particles with a certain mass, and dissolving the PVA particles in a proper amount of distilled water under the water bath condition of more than 95 ℃ to obtain a 9 wt% PVA solution;
6) putting the obtained cellulose solution and PVA solution in a beaker according to a certain proportion, putting the beaker into a rotor, then putting the rotor on an electromagnetic stirrer, stirring the mixture for 20min, taking the mixture down, pouring the mixture into a glass tank, sucking bubbles by a dropper, then uniformly distributing the liquid in the glass tank, putting the glass tank into a vacuum drying oven with the temperature of 60 ℃ for drying, and taking the glass tank out after drying to obtain a film;
7) preparing 250ml of CaCl with the mass fraction of 5 percent in corresponding parts2And 3% HCl solution, soaking the film for 20min, washing with clear water, draining, soaking with 30% glycerol solution 150ml, taking out after 20min, washing, draining, standing in clear water, soaking overnight, taking out the film, and drying the film with a vacuum freeze drying oven to obtain the final productCellulose polyvinyl alcohol composite membrane.
4. The method of claim 3, wherein the ratio of the cellulose solution to the PVA solution is: a volume ratio of 50:100 or 75:94 or 100:89 or 125: 83.
5. A preparation method of a supercapacitor, which is the cellulose polyvinyl alcohol composite film prepared by the preparation method of any one of claims 1 to 4, and is characterized by comprising the following steps:
uniformly loading a mixture of 80 wt% of activated carbon, 10 wt% of acetylene black and 10 wt% of polytetrafluoroethylene on a nickel foam substrate to prepare a working electrode;
immersing the obtained working electrode and the cellulose polyvinyl alcohol composite membrane in 6M KOH solution for 48h, and then removing residual electrolyte on the electrode and the cellulose polyvinyl alcohol composite membrane by using filter paper; and (2) using a cellulose polyvinyl alcohol composite membrane as a diaphragm, and assembling by adopting an electrode-separator-electrode sandwich structure to obtain the super capacitor.
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