CN112143041B - Elementary sequence structured cellulose-based nano-fluid ionic conductor material, and preparation method and application thereof - Google Patents
Elementary sequence structured cellulose-based nano-fluid ionic conductor material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a cellulose-based nano fluid ionic conductor material which is prepared from the following raw materials: cellulose, a cellulose solvent, and a first or second functional nanofiller. The material disclosed by the invention has excellent electrochemical properties and also has stronger mechanical stability. The invention also discloses a preparation method of the cellulose-based nano fluid ionic conductor material, which has the characteristics of low cost, simple process and environmental protection. The invention also discloses application of the cellulose-based nano-fluid ionic conductor material in a cellulose-based nano-fluid osmotic energy generator, and the application of natural high polymer materials in the fields of optics, electrics, energy storage and special functionalized biomedical materials is expanded.
Description
Technical Field
The invention relates to the field of nano-fluid, in particular to an elementary-sequence structured cellulose-based nano-fluid ionic conductor material, a preparation method and application thereof.
Background
In recent years, extensive attention has been paid to the study of nanofluidic ionic conductor systems, in which ions within nanofluidic channels exhibit transport behavior that is significantly different from that of ions in electrolyte solutions. This is determined by the height of the nanofluidic channel and the electric double layer formed by the channel. The rapid transmission of the ions is an ideal innovative energy utilization, and has great research value in biosensing, energy storage and conversion, water treatment and the like. The nano carbon material is commonly used for functionalized high polymer materials to obtain high polymer composite materials with special functions, is widely applied to the fields of energy conversion materials, energy storage materials, conductive materials, biomedical materials and the like, and is an ideal high value-added filler. Hu et al (J.Am.chem.Soc.2019,141,17830) extract nanocellulose from wood, and promote the nanocellulose to wrap graphene sheets with nanometer thickness to form a plurality of two-dimensional constraint spaces, thereby preparing a biomass nanofluidic channel. The invention prepares a high value-added functionalized cellulose-based material by doping nano carbon material graphene and carbon nano tubes in a cellulose solution respectively by utilizing a green solvent system (alkali/urea water system). The preparation process is simple and environment-friendly.
Most of the materials having nano-fluid channels in the past are composed of petroleum-based synthetic polymers such as polyethyleneimine, polyvinyl alcohol, polystyrene sulfonate and the like. However, they are non-renewable, non-degradable materials that have posed serious environmental problems in the long past; furthermore, although the preparation of ordered nanochannels has made great progress in laboratory conditions, high cost, complex and time consuming lithographic processes, atomic layer deposition and like manufacturing methods are often required and challenges remain in scalable commercial applications. Therefore, the design of an oriented nanostructure ionic membrane with excellent ion transport properties using the most abundant, low-cost and renewable cellulose materials in nature has yet to be developed. At present, some scientific researchers draw materials from nature, and design the nanometer fluid material by utilizing natural wood, thereby solving the problems of high cost, environmental pollution and the like. For example, litian et al (sci. adv.2019,5, u4238) produced a wood film with a nanofluidic effect from top to bottom using the naturally oriented nano-microstructure of wood; the picnic soldiers of the university of maryland and the like design a nano fluid wood film based on wood to realize low-heat recycling (nat. mater.2019,18,608) and salt concentration gradient osmotic power generation (adv. energy mater.2019, 1902590).
Therefore, there is a need to find a new elementary-structured cellulose-based nanofluid ionic conductor material and a preparation method thereof to overcome the above performance defects.
Disclosure of Invention
The invention is based on the extensive application of nano materials in the fields of energy conversion materials, energy storage materials, conductive materials, biomedical materials and the like. A cellulose-based nanofluid ion conductor material which is green, environment-friendly, renewable and degradable is prepared by doping a first functional nanofiller and/or a second functional nanofiller into a cellulose solution respectively and by a top-down strategy, namely, a method of dissolving cotton, chemically modifying and the like from a molecular chain level of cellulose, and the application of the cellulose-based nanofluid ion conductor material in the field of salt gradient concentration permeation power generation is realized.
One object of the present invention is to provide a cellular-structured cellulose-based nanofluid ionic conductor material, which is realized by the following technical means:
a cellulose-based nano fluid ionic conductor material is prepared from the following raw materials in parts by mass:
before the elementary-sequence structured cellulose-based nano-fluid ionic conductor material is prepared, oxidation treatment is needed;
the cellulose solvent comprises alkali, urea and water;
the first functional nano filler comprises one or two of carbon nano tubes or carboxylated carbon nano tubes;
the second functional nanofiller comprises one or more of graphene, graphene oxide, MXene, boron nitride nanoplatelets or hydroxylated boron nitride nanoplatelets.
Further, the cellulose solvent comprises the following components in parts by mass:
6-12 parts of alkali; 10-17 parts of urea; 71-84 parts of water.
Further, the first functional nano filler comprises the following components in parts by mass:
0.09-4 parts of carbon nano tubes; 0.09-10 parts of carboxylated carbon nanotubes.
Further, the second functional nano filler comprises the following components in parts by mass:
0.09-6 parts of graphene; 0.09-8 parts of graphene oxide; 0.09-8 parts of MXene; 0.09-8 parts of boron nitride nanosheets; 0.09-10 parts of hydroxylated boron nitride nanosheet.
The invention also aims to provide a preparation method of the elementary-sequence-structured cellulose-based nano-fluid ionic conductor material, which is realized by the following technical means:
a method for preparing a basic-sequence structured cellulose-based nano-fluid ionic conductor material comprises the following steps:
s1, dissolving cellulose in a cellulose solvent, doping a first or second functional nano filler into the cellulose solvent, and stirring to form a cellulose/nano element composite solution;
s2, centrifuging the composite solution, and adding a chemical cross-linking agent for reaction to generate a crude product;
s3, centrifuging and shaping the crude product to obtain alkali gel;
s4, stretching and orienting the alkali gel, and soaking the alkali gel in a coagulating bath for fixed orientation;
and S5, carrying out TEMPO oxidation treatment, water washing and drying on the oriented gel to obtain the nano-elementary-sequence structured cellulose-based nano-fluid ionic conductor material.
Further, in the S1, the stirring temperature is-20 ℃ to-10 ℃, and the stirring speed is 1000 ℃ and 5000 rpm.
Further, in the step S1, the stirring time is 2-10 min.
Further, the chemical crosslinking agent is selected from one or more of epichlorohydrin, epoxy chlorobutane, glutaraldehyde or polyethylene glycol glycidyl ether.
Further, the coagulation bath is selected from one or more of sulfuric acid, hydrochloric acid, citric acid, phytic acid, acetic acid, methanol, ethanol or water.
Another object of the present invention is to provide the application of the above elementary-sequence-structured cellulose-based nano-fluid ionic conductor material in a cellulose-based nano-fluid osmotic energy generator.
The invention has the beneficial effects that:
the invention discloses an element sequence structured cellulose-based nanofluid ion conductor material, which has excellent electrochemical properties and stronger mechanical stability due to the addition of functional nanofillers. The invention also discloses a preparation method of the element sequence structured cellulose-based nano fluid ionic conductor material, which has the characteristics of low cost, simple process and environmental protection. The invention also discloses application of the element sequence structured cellulose-based nano-fluid ion conductor material in a cellulose-based nano-fluid osmotic energy generator, and the invention expands the application of natural high polymer materials in the fields of optics, electrics, energy storage and special functionalized biomedical materials.
Drawings
FIG. 1 is a schematic diagram of the preparation of cellulose nanofluid ion conductor material with elementary structure in example 1 of the present invention;
FIG. 2 is a photograph of a cellulose/nano-element composite solution in example 1 of the present invention;
FIG. 3 is an SEM image of the elementary structured cellulose-based nanofluid ionic conductor material in example 1 of the present invention;
FIG. 4 is an AFM image of a primitive-structured cellulose-based nanofluid ionic conductor material in example 2 of the present invention;
FIG. 5 is a graph showing the measurement of the ionic conductivity of the elementary structured cellulose-based nanofluid ionic conductor material in KCl solutions with different concentrations, and the measurement of the structured cellulose/functional elementary composite membrane (comparative example 1) and the structured cellulose membrane (comparative example 2) in example 1 of the present invention;
fig. 6 is a graph of gradient salt concentration diffusion potential and diffusion current of the cellulose-based nano-fluid ionic conductor material in the application of the cellulose-based nano-fluid osmotic energy generator in the unit-sequence-structured cellulose-based nano-fluid ionic conductor material in example 3 of the invention.
Detailed Description
In the context of the present invention as described in the specification,
the term "MXene" refers to a class of two-dimensional inorganic compounds. These materials consist of transition metal carbides, nitrides or carbonitrides in a thickness of several atomic layers.
A source of cellulose selected from one or more of linter pulp, wood pulp, bamboo pulp and straw pulp;
the carbon nano tube is purchased from NANOCYYLTMModel NC 7000;
the carboxylated carbon nano tube is purchased from pioneer nano, and the model is XFM 72;
the graphene is purchased from pioneer nano and has the model of XF 001H;
the graphene oxide is purchased from pioneer nano and has the model of XF 002-3;
MXene is purchased from pioneer nanometer with the model of XFK 08;
the boron nitride nanosheet of the embodiment of the invention is purchased from pioneer nanometer, and the model is XFBN 03-1;
the hydroxylated boron nitride nanosheet provided by the embodiment of the invention is obtained by ultrasonic treatment (300W,1h) of the above boron nitride in isopropanol.
The components related to the embodiments of the present invention are all common commercial materials unless otherwise mentioned;
the TEMPO oxidation treatment adopts the following specific steps: 20g of hydrogel, 90g of deionized water, 0.010g of TEMPO (tetramethylpiperidine) and 0.2g of sodium bromide were mixed. 6.203g of sodium hypochlorite were mixed and oxidized for 2 hours while maintaining the pH of the solution at 10.
Example 1
An elementary-sequence structured cellulose-based nano-fluid ionic conductor material is prepared from the following raw materials in parts by mass:
wherein, before the elementary structured cellulose-based nano-fluid ionic conductor material is prepared, TEMPO oxidation treatment is needed.
The preparation method of the cellulose nanofluid ionic conductor membrane material with the elementary sequence structure comprises the following steps:
s1, according to parts by mass, 82 parts of a cellulose solvent (wherein 4.92 parts of sodium hydroxide, 8.2 parts of urea and 68.88 parts of deionized water are prepared), 0.09 part of a carbon nano tube (a first functional nano filler) is pre-cooled under cold hydrazine at the temperature of minus 20 ℃, 3 parts of cellulose wood pulp is added, and the mixture is stirred for 2min at 5000rpm to obtain a cellulose/nano element composite solution;
s2, then adding 0.05 part of chemical cross-linking agent epichlorohydrin, and stirring at constant temperature of-5 ℃ and 350rpm for 3 hours to obtain a chemically cross-linked crude product;
s3.0 ℃, 6000rpm, centrifuging for 5min, pouring into mold gel, standing at-5 ℃ for 5h, and shaping to obtain composite alkali gel;
s4, externally drawing the composite alkali gel (drawing strain is 160%), and then placing the composite alkali gel in a 10 wt% sulfuric acid coagulation bath for 1min to fix orientation to obtain the high-orientation cellulose/nano-element composite hydrogel;
s5, mixing 20g of composite cellulose hydrogel, 90g of deionized water, 0.010g of TEMPO (tetramethylpiperidine), 0.2g of sodium bromide and 6.203g of sodium hypochlorite, maintaining the pH value of the solution at 10, oxidizing for 1h, cleaning, clamping two ends of the cleaned solution, and performing limited drying at 25 ℃ to obtain the elementary structured cellulose nanofluid ionic conductor material.
Fig. 1 is a flow chart of a process for preparing a nano-elementary structured cellulose nanofluid ion conductor film material prepared in example 1 of the present invention, and illustrates that the present invention is a complicated bottom-up construction method for constructing a nano-elementary structured cellulose nanofluid ion conductor film material based on a bottom-up strategy, wherein the preparation process is simple and controllable, and is different from wood-based materials.
Fig. 2 is a photograph of the composite solution for preparing the cellulose-based nanofluid ionic conductor material in example 1 of the present invention, which shows that the cellulose solution in which the nano-elements are dispersed has good stability and good fluidity.
Fig. 3 is an SEM image of the cellulose-based nanofluid ion conductor material in example 1 of the present invention, which shows that the cellulose nanofluid ion conductor film is composed of dehydrated and dried nano-elements, and has a very dense structure, a flat surface, a high orientation, and a nano-scale ion channel.
Fig. 5 illustrates that the primitive-structure cellulose functional membrane prepared in example 1 has higher ion conductivity and is more favorable for ion selective transport than the non-chemically-modified structure composite membrane and the oriented cellulose membrane.
Example 2
An elementary-sequence structured cellulose-based nano-fluid ionic conductor material is prepared from the following raw materials in parts by mass:
wherein, before the elementary structured cellulose-based nano-fluid ionic conductor material is prepared, TEMPO oxidation treatment is needed.
The preparation method of the cellulose nanofluid ionic conductor membrane material with the elementary sequence structure comprises the following steps:
s1, according to the mass parts of 96.72 parts of cellulose solvent (wherein 11.61 parts of sodium hydroxide, 16.44 parts of urea and 68.67 parts of deionized water are prepared), 4 parts of carboxylated carbon nanotubes (first functional nano filler) are pre-cooled under cold hydrazine at the temperature of minus 10 ℃, 8 parts of cellulose cotton linter pulp is added, and the mixture is stirred for 2min at 5000rpm to obtain a cellulose/nano element composite solution;
s2, adding 2 parts of epoxy chlorobutane serving as a chemical crosslinking agent, and stirring at constant temperature of-10 ℃ and 500rpm for 1h to obtain a chemically crosslinked crude product;
s3.0 ℃, 6000rpm, centrifuging for 5min, pouring into a mold gel, standing for 3h at 10 ℃ for shaping to obtain composite alkali gel;
s4, externally drawing the composite alkali gel (drawing strain is 180%), and then placing the composite alkali gel in a 2 wt% phytic acid coagulation bath for 10min for fixing orientation to obtain the high-orientation cellulose/nano-element composite hydrogel;
s5, mixing 20g of composite cellulose hydrogel, 90g of deionized water, 0.010g of TEMPO (tetramethylpiperidine), 0.2g of sodium bromide and 6.203g of sodium hypochlorite, maintaining the pH value of the solution at 10, oxidizing for 1h, cleaning, clamping two ends of the solution, and performing limited drying at 25 ℃ to obtain the element-structured cellulose-based nanofluid ionic conductor material.
Fig. 4 is an AFM image of the cellulose-based nanofluid ionic conductor material in example 2 of the present invention, which shows that a functional cellulose membrane has a large number of nanofibers arranged in a long-range order, presents a highly oriented and highly densified structure, and provides superior transport performance for ions in a nanoscale channel.
Example 3
An elementary-sequence structured cellulose-based nano-fluid ionic conductor material is prepared from the following raw materials in parts by mass:
wherein, before the elementary structured cellulose-based nano-fluid ionic conductor material is prepared, TEMPO oxidation treatment is needed.
A method for preparing a cellulose nanofluid ionic conductor membrane material with elementary sequence structure comprises the following steps:
s1, according to the mass parts, 89.5 parts of a cellulose solvent (7.2 parts of lithium hydroxide, 13.4 parts of urea and 68.9 parts of deionized water) and 2 parts of graphene oxide (a second functional nano filler) are pre-cooled under cold hydrazine at the temperature of-15 ℃, 4 parts of cellulose cotton linter pulp is added, and the mixture is stirred at 1000rpm for 10min to obtain a cellulose/nano element composite solution;
s2, then adding 0.5 part of chemical cross-linking agent polyethylene glycol diglycidyl ether, stirring at constant temperature of-10 ℃ and 500rpm for 1.5h to obtain a chemically cross-linked crude product;
s3.0 ℃, 6000rpm, centrifuging for 5min, pouring into a mold gel, standing for 3h at 10 ℃ for shaping to obtain composite alkali gel;
s4, externally drawing the composite alkali gel (drawing strain is 200%), and then placing the composite alkali gel in absolute ethyl alcohol of a coagulating bath for 20min to fix orientation to obtain the high-orientation cellulose/nano-element composite hydrogel;
s5, mixing 20g of composite cellulose hydrogel, 90g of deionized water, 0.010g of TEMPO (tetramethylpiperidine), 0.2g of sodium bromide and 6.203g of sodium hypochlorite, maintaining the pH value of the solution at 10, oxidizing for 1h, cleaning, clamping two ends of the solution, and performing limited drying at 25 ℃ to obtain the element-structured cellulose-based nanofluid ionic conductor material.
Fig. 6 illustrates the diffusion voltage and diffusion current that the functional cellulose nanofluid film prepared in example 3 can generate under a 10-fold, 100-fold, 1000-fold salt concentration gradient. The simulation verifies the feasibility of the salt concentration gradient power generation.
Example 4
An elementary-sequence structured cellulose-based nano-fluid ionic conductor material is prepared from the following raw materials in parts by mass:
wherein, before the elementary structured cellulose-based nano-fluid ionic conductor material is prepared, TEMPO oxidation treatment is needed.
The preparation method of the cellulose nanofluid ionic conductor membrane material with the elementary sequence structure comprises the following steps:
s1, according to the mass parts, 86.9 parts of a cellulose solvent (wherein 5.2 parts of sodium hydroxide, 8.7 parts of urea and 73 parts of deionized water are prepared), 8 parts of MXene (a second functional nano filler) are pre-cooled under cold hydrazine at the temperature of minus 20 ℃,5 parts of cellulose cotton linter slurry is added, and the mixture is stirred at 6000rpm for 5min to obtain a cellulose/nano element composite solution;
s2, then adding 0.1 part of chemical cross-linking agent polyethylene glycol glycidyl ether, stirring at constant temperature of-5 ℃ and 350rpm for 3 hours to obtain a chemically cross-linked crude product;
s3.0 ℃, 6000rpm, centrifuging for 5min, pouring into mold gel, standing at-5 ℃ for 5h, and shaping to obtain composite alkali gel;
s4, externally drawing the composite alkali gel (drawing strain is 140%), and then placing the composite alkali gel in a 10 wt% hydrochloric acid coagulation bath for 1min to fix orientation to obtain the high-orientation cellulose/nano-element composite hydrogel;
s5, mixing 20g of composite cellulose hydrogel, 90g of deionized water, 0.010g of TEMPO (tetramethylpiperidine), 0.2g of sodium bromide and 6.203g of sodium hypochlorite, maintaining the pH value of the solution at 10, oxidizing for 1h, cleaning, clamping two ends of the cleaned solution, and performing limited drying at 25 ℃ to obtain the elementary structured cellulose nanofluid ionic conductor material.
Example 5
An elementary-sequence structured cellulose-based nano-fluid ionic conductor material is prepared from the following raw materials in parts by mass:
wherein, before the elementary structured cellulose-based nano-fluid ionic conductor material is prepared, TEMPO oxidation treatment is needed.
The preparation method of the cellulose nanofluid ionic conductor membrane material with the elementary sequence structure comprises the following steps:
s1, according to the mass parts, 93.3 parts of a cellulose solvent (5.6 parts of sodium hydroxide, 9.3 parts of urea and 78.4 parts of deionized water) and 0.6 part of boron nitride nanosheet (second functional nano filler) are pre-cooled under cold hydrazine at the temperature of minus 20 ℃,6 parts of cellulose cotton linter slurry is added, and the mixture is stirred at 4000rpm for 4min to obtain a cellulose/nano element composite solution;
s2, then adding 0.1 part of chemical cross-linking agent glutaraldehyde, stirring at constant temperature of-5 ℃ and 350rpm for 3 hours to obtain a chemically cross-linked crude product;
s3.0 ℃, 6000rpm, centrifuging for 5min, pouring into mold gel, standing at-5 ℃ for 5h, and shaping to obtain composite alkali gel;
s4, externally drawing the composite alkali gel (drawing strain is 170%), and then placing the composite alkali gel in a 10 wt% phytic acid coagulation bath for 10min for fixing orientation to obtain the high-orientation cellulose/nano-element composite hydrogel;
s5, mixing 20g of composite cellulose hydrogel, 90g of deionized water, 0.010g of TEMPO (tetramethylpiperidine), 0.2g of sodium bromide and 6.203g of sodium hypochlorite, maintaining the pH value of the solution at 10, oxidizing for 1h, cleaning, clamping two ends of the cleaned solution, and performing limited drying at 25 ℃ to obtain the elementary structured cellulose nanofluid ionic conductor material.
Example 6
An elementary-sequence structured cellulose-based nano-fluid ionic conductor material is prepared from the following raw materials in parts by mass:
wherein, before the elementary structured cellulose-based nano-fluid ionic conductor material is prepared, TEMPO oxidation treatment is needed.
The preparation method of the cellulose nanofluid ionic conductor membrane material with the elementary sequence structure comprises the following steps:
s1, according to the mass parts, 90.9 parts of a cellulose solvent (wherein 5.3 parts of sodium hydroxide, 9.1 parts of urea and 76.5 parts of deionized water are prepared), 3 parts of a hydroxylated boron nitride nanosheet (a second functional nano filler) are pre-cooled under cold hydrazine at the temperature of minus 20 ℃,6 parts of cellulose cotton linter slurry is added, and the mixture is stirred at 4000rpm for 4min to obtain a cellulose/nano element composite solution;
s2, then adding 0.1 part of chemical cross-linking agent epichlorohydrin, and stirring at constant temperature of-5 ℃ and 350rpm for 3h to obtain a chemically cross-linked crude product;
s3.0 ℃, 6000rpm, centrifuging for 5min, pouring into mold gel, standing at-5 ℃ for 5h, and shaping to obtain composite alkali gel;
s4, externally drawing the composite alkali gel (drawing strain is 160%), and then placing the composite alkali gel in a 10 wt% citric acid coagulation bath for 5min to fix orientation to obtain the high-orientation cellulose/nano-element composite hydrogel;
s5, mixing 20g of composite cellulose hydrogel, 90g of deionized water, 0.010g of TEMPO (tetramethylpiperidine), 0.2g of sodium bromide and 6.203g of sodium hypochlorite, maintaining the pH value of the solution at 10, oxidizing for 1h, cleaning, clamping two ends of the cleaned solution, and performing limited drying at 25 ℃ to obtain the elementary structured cellulose nanofluid ionic conductor material.
Comparative example 1
Comparative example 1 differs from example 1 in composition in that: comparative example 1 is a regenerated cellulose/functional element composite film without chemical modification, while example 1 is a structured cellulose/functional element composite film in which cellulose molecules are negatively charged by TEMPO oxidation treatment.
A preparation method of a structured cellulose/functional element composite membrane material comprises the following steps:
s1, according to parts by mass, 82 parts of a cellulose solvent (wherein 4.92 parts of sodium hydroxide, 8.2 parts of urea and 68.88 parts of deionized water are prepared), 0.09 part of a carbon nano tube (a first functional nano filler) is pre-cooled under cold hydrazine at the temperature of minus 20 ℃, 3 parts of cellulose wood pulp is added, and the mixture is stirred for 2min at 5000rpm to obtain a cellulose/nano element composite solution;
s2, then adding 0.05 part of chemical cross-linking agent epichlorohydrin, and stirring at constant temperature of-5 ℃ and 350rpm for 3 hours to obtain a chemically cross-linked crude product;
s3.0 ℃, 6000rpm, centrifuging for 5min, pouring into mold gel, standing at-5 ℃ for 5h, and shaping to obtain composite alkali gel;
s4, externally drawing the composite alkali gel (drawing strain is 160%), and then placing the composite alkali gel in a 10 wt% sulfuric acid coagulation bath for 1min to fix orientation to obtain the high-orientation cellulose/nano-element composite hydrogel;
s5, cleaning, clamping two ends, and carrying out limited-range drying at 25 ℃ to obtain the ordered cellulose/functional element composite membrane material.
Comparative example 2
Comparative example 2 differs from example 1 in composition in that: the composition of comparative example 2 is only regenerated cellulose, while the composition of example 1 contains regenerated cellulose and nano-functional elements.
A preparation method of a sequential cellulose membrane material comprises the following steps:
s1, preparing 82 parts of cellulose solvent (4.92 parts of sodium hydroxide, 8.2 parts of urea and 68.88 parts of deionized water) by mass, precooling at 20 ℃ under cold hydrazine, adding 3 parts of cellulose wood pulp, and stirring at 5000rpm for 2min to obtain a cellulose/nano-element composite solution;
s2, then adding 0.05 part of chemical cross-linking agent epichlorohydrin, and stirring at constant temperature of-5 ℃ and 350rpm for 3 hours to obtain a chemically cross-linked crude product;
s3.0 ℃, 6000rpm, centrifuging for 5min, pouring into mold gel, standing at-5 ℃ for 5h, and shaping to obtain alkali gel;
s4, drawing the alkali gel by external force (drawing strain is 160%), and then placing the alkali gel in a 10 wt% sulfuric acid coagulation bath for 1min to fix orientation to obtain the high-orientation cellulose hydrogel;
s5, cleaning, clamping two ends, and carrying out limited-range drying at 25 ℃ to obtain the ordered cellulose membrane material.
Test example
(1) Ion conductivity measurement of Nanoblement-sequenced cellulose Nanofluidic ion conductor membranes (example 1)
The test method comprises the following steps: formulation 10-6、10-5、10-4、10-3、10-2And 10-1M potassium chloride solutions with six concentrations, and respectively testing the conductivity values of the bulk solutions with the six concentrations. Then, the test was performed by soaking the test pieces in 10-6、10-5、10-4、10-3、10-2、10- 1The nanometer elementary sequence of the M potassium chloride solution constructs the conductivity of the cellulose nanofluid ion conductor membrane. Two parallel test probes are placed on both ends of a sample to be tested, then a certain potential is applied to both ends of the probes, and then the current passing through the sample is measured. And (5) making an I-V image by using the obtained current and potential, fitting, and then taking the slope as the conductivity. The calculation equation for the conductivity (λ) is as follows:
λ＝G(l/hw)
where G is the measured conductance (i.e., the slope of the I-V curve), l is the length of the composite film being measured, h is the height of the film being measured, and w is the width of the composite film being measured.
(2) Ion conductivity measurement of structured cellulose/functional element composite film (comparative example 1)
The test method comprises the following steps: two parallel test probes are arranged at two ends of a sample to be tested, and the sample is respectively soaked in 10-6、10-5、10-4、10-3、10-2、10-1The M potassium chloride solution then applies a certain potential across the probe, followed by measuring the current through the structured cellulose/functional primitive composite membrane. And (5) making an I-V image by using the obtained current and potential, fitting, and then taking the slope as the conductivity. The calculation equation for the conductivity (λ) is as follows:
λ＝G(l/hw)
where G is the measured conductance (i.e., the slope of the I-V curve), l is the length of the sequenced structured cellulose/functional primitive composite membrane, h is the height of the sequenced structured cellulose/functional primitive composite membrane, and w is the width of the sequenced structured cellulose/functional primitive composite membrane.
(3) Ion conductivity measurement of a structured cellulose film (comparative example 1)
The test method comprises the following steps: two parallel test probes are arranged at two ends of a sample to be tested, and the sample is respectively soaked in 10-6、10-5、10-4、10-3、10-2、10-1The M potassium chloride solution is then applied to a potential across the probe, followed by measurement of the current through the structured cellulose membrane. And (5) making an I-V image by using the obtained current and potential, fitting, and then taking the slope as the conductivity. The calculation equation for the conductivity (λ) is as follows:
λ＝G(l/hw)
where G is the measured conductance (i.e., the slope of the I-V curve), l is the length of the sequenced structured cellulose film, h is the height of the sequenced structured cellulose film, and w is the width of the sequenced structured cellulose film.
(4) Measurement of diffusion Voltage and diffusion Current at gradient salinity for Nanoblement-patterned cellulose nanofluid Ionic conductor membranes (example 1)
A set of system for mixing seawater (0.5M NaCl) and river water (0.01M NaCl) is designed, seawater and river water are respectively arranged on two sides, and a high-orientation functional cellulose nano-fluid material is arranged in the middle, so that certain voltage and current can be obtained. Firstly, cutting a functional cellulose membrane with the thickness of 0.1mm and the width of 1mm, and packaging with glue to ensure that two ends are exposed; secondly, respectively adding 0.5M electrolyte solution and 0.01M electrolyte solution into a left groove and a right groove of the double-groove electrochemical cell, and placing the functional membrane packaged by silica gel between the two grooves; finally, two testing electrodes of the digital source meter are respectively immersed into the two grooves, and the diffusion voltage and the diffusion current generated by the functional cellulose membrane are tested and recorded.
Table 1 ion conductivity data for different samples in corresponding electrolyte solutions
As can be seen from the table, example 1 has different degrees of advantage over comparative examples 1-2, as well as the bulk solution, in general, in conductivity at different solution concentrations.
Table 2 diffusion current and diffusion potential data of nano-elementary-structure cellulose ion conductor film at gradient concentration in example 3
Claims (9)
1. A method for preparing a basic-sequence structured cellulose-based nano-fluid ionic conductor material is characterized by comprising the following steps:
s1, dissolving a cellulose raw material in a cellulose solvent, doping a first or second functional nano filler into the cellulose raw material, and stirring to form a cellulose/nano element composite solution;
s2, centrifuging the composite solution, and adding a chemical cross-linking agent for reaction to generate a crude product;
s3, centrifuging and shaping the crude product to obtain cellulose alkali gel of the composite nanometer element;
s4, stretching, orienting and soaking the alkali gel in a coagulating bath for orientation fixation;
s5, performing TEMP0 oxidation treatment, water washing and drying on the oriented composite hydrogel to obtain an elementary-sequence structured cellulose-based nano-fluid ionic conductor material;
the elementary-sequence structured cellulose-based nano-fluid ionic conductor material is prepared from the following raw materials in parts by mass:
before the elementary-sequence structured cellulose-based nano-fluid ionic conductor material is prepared, oxidation treatment is needed;
the cellulose solvent comprises alkali, urea and water;
the first functional nano filler comprises one or two of carbon nano tubes or carboxylated carbon nano tubes;
the second functional nanofiller comprises one or more of graphene, graphene oxide, MXene, boron nitride nanoplatelets or hydroxylated boron nitride nanoplatelets.
2. The method for preparing the cellular-sequence cellulose-based nano-fluid ionic conductor material as claimed in claim 1, wherein the stirring temperature in S1 is-20 ℃ to-10 ℃, and the stirring speed is 1000-.
3. The method for preparing the cellular-sequence-structured cellulose-based nanofluid ionic conductor material according to claim 1, wherein in the step S1, the stirring time is 2-10 min.
4. The method for preparing the primitive-structured cellulose-based nanofluid ionic conductor material according to claim 1, wherein the chemical crosslinking agent is selected from one or more of epichlorohydrin, chloroepoxy butane, glutaraldehyde, or polyethylene glycol glycidyl ether.
5. The method for preparing the primitive-structured cellulose-based nanofluid ionic conductor material according to claim 1, wherein the coagulation bath is selected from one or more of sulfuric acid, hydrochloric acid, citric acid, phytic acid, acetic acid, methanol, ethanol, or water.
6. The method for preparing the cellular-sequence-structured cellulose-based nano-fluid ionic conductor material according to claim 1, wherein the cellulose solvent comprises the following components in parts by mass:
6-12 parts of alkali; 10-17 parts of urea; 61-84 parts of water.
7. The method for preparing the cellular-sequence-structured cellulose-based nano-fluid ionic conductor material according to claim 1, wherein the first functional nano-filler comprises the following components in parts by mass:
0.09-4 parts of carbon nano tubes; 0.09-10 parts of carboxylated carbon nanotubes.
8. The method for preparing the cellular-sequence-structured cellulose-based nano-fluid ionic conductor material according to claim 1, wherein the second functional nano-filler comprises the following components in parts by mass:
0.09-6 parts of graphene; 0.09-8 parts of graphene oxide; 0.09-8 parts of MXene; 0.09-8 parts of boron nitride nanosheets; 0.09-10 parts of hydroxylated boron nitride nanosheet.
9. The elementary-sequence structured cellulose-based nano-fluid ionic conductor material prepared by the method for preparing the elementary-sequence structured cellulose nano-fluid ionic conductor material according to any one of claims 1 to 8.
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