CN113862992B - Composite electrogenesis fiber based on sodium alginate and preparation method thereof - Google Patents
Composite electrogenesis fiber based on sodium alginate and preparation method thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 118
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 69
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 69
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000001913 cellulose Substances 0.000 claims abstract description 31
- 229920002678 cellulose Polymers 0.000 claims abstract description 31
- 239000002121 nanofiber Substances 0.000 claims abstract description 18
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- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 122
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 76
- 229910021389 graphene Inorganic materials 0.000 claims description 52
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- 230000001112 coagulating effect Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000015271 coagulation Effects 0.000 claims description 11
- 238000005345 coagulation Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
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- 229910002804 graphite Inorganic materials 0.000 claims description 9
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- 239000000843 powder Substances 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002041 carbon nanotube Substances 0.000 description 15
- 229910021393 carbon nanotube Inorganic materials 0.000 description 15
- 230000005611 electricity Effects 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 238000009987 spinning Methods 0.000 description 1
- 239000002407 tissue scaffold Substances 0.000 description 1
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- 238000002166 wet spinning Methods 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic System
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/04—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of alginates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a sodium alginate-based composite electrogenesis fiber and a preparation method thereof, which have the characteristics of improving the water absorption performance of the fiber in the air, absorbing water in the air to become moist and ionizing a large amount of hydrogen ions, and accumulating the hydrogen ions to one section of the fiber along with the movement of water molecules along the fiber so as to generate voltage; the materials used for preparing the fibers belong to materials which can be purchased or prepared in a laboratory, the preparation cost is low, the preparation method is simple and convenient, and the preparation period is short; the fiber taking sodium alginate as a matrix has better toughness, torsion resistance and tensile strength, has strong plasticity, and can be woven into different shapes for application; the graphitized carboxylated multi-wall carbon nano-tube and cellulose nano-fiber are added to strengthen and stabilize the generated voltage. None of these added chemical components is corrosive, making the fiber more skin friendly.
Description
Technical Field
The invention relates to the field of micro-energy recovery and electricity generation, in particular to a sodium alginate-based composite electricity generation fiber and a preparation method thereof.
Background
In recent years, intelligent wearable devices are rapidly developed and are widely focused, and meanwhile, development of new materials and microelectronic elements is also driven. The power supply and the conductive material are very important in intelligent wearable equipment, and at present, a plurality of intelligent wearable equipment use batteries as power supplies, so that the intelligent wearable equipment has larger power supplies, additional circuits and other equipment, and is inconvenient to wear. Therefore, it is of great importance to find conductive materials that are capable of generating a stable usable voltage in an air environment.
Because the wearable equipment is closely contacted with the human body, the working environment is mostly the atmospheric environment, so the material of the wearable equipment is required to have higher skin-friendly property, flexibility and sensitivity and can continuously work.
The research shows that the sodium alginate and cellulose nano-fiber has strong hydrophilicity and flexibility, no toxicity and biocompatibility, can bear various macromolecular compounds, and has been applied to a plurality of aspects such as tissue scaffolds, medicines, fabrics and the like.
Graphene oxide is an oxide of graphene, generally represented by a graphene oxide solution, which is brown yellow in color, and common products on the market are in powder, flake and solution forms. In addition, the graphene oxide solution has large specific surface area, good dispersibility and good humidity-sensitive characteristic, so that the graphene oxide solution becomes an ideal sensor material and has wide application in the field of flexible sensors.
Researches show that the fiber-form material can be applied to the preparation of electrodes, has good conductivity and torsion performance and has wide application occasions. The patent application number is as follows: 201711461931.1, patent application name: in the patent application of the fiber electrode material and the preparation method thereof, the prepared fiber electrode has good conductivity and catalysis, and the obtained fiber is soft and elastic, thereby not only meeting the requirements of serving as a counter electrode in DSSCs, but also meeting the application under complex environments such as bending or torsion.
The patent application number is: 201811580418.9 patent application name: in the patent application of the preparation method of the graphene/polyethylene glycol antistatic nylon fiber, polyethylene glycol modified graphene is obtained through esterification reaction of carboxyl on oxidized graphene and hydroxyl of polyethylene glycol, the modified graphene and nylon 6 solution are subjected to blending reaction, and the graphene polyvinyl alcohol nylon fiber is obtained through spinning by using melt spinning equipment, so that the graphene/polyethylene glycol nylon fiber is obtained, and the composite antistatic system with excellent permanent antistatic performance is obtained.
In summary, in the existing graphene oxide application, the application and the suggestion of generating electricity by combining the graphene oxide material with the sodium alginate fiber material are not available.
Disclosure of Invention
The invention aims to solve the technical problems: the invention aims to solve the defects in the prior art and provides a composite electricity generating fiber capable of generating stable and usable voltage in air and a preparation method thereof;
the technical scheme of the invention is as follows: the invention discloses a preparation method of a sodium alginate-based composite electrogenesis fiber, which comprises the following steps:
step one, preparing 2-4wt% sodium alginate solution, 10-20mg/mL graphene oxide solution, 2-8mg/mLCNT solution, 2-4mol/L lithium chloride solution and 5-15wt% CaCl 2 Is used for the fiber coagulating bath;
step two, taking the sodium alginate solution and the graphene oxide solution prepared in the step one, and taking cellulose nanofibers, and uniformly mixing the cellulose nanofibers according to the proportion of 55-70% of sodium alginate solution, 10-15% of graphene oxide solution and 15-33% of cellulose nanofibers; wherein the sum of the percentages of the sodium alginate solution, the graphene oxide solution and the cellulose nanofiber is 1; adding 5mL of the CNT solution into the solution, and uniformly mixing and stirring to obtain a mixed solution;
injecting the mixed solution into the fiber coagulating bath through a sample injector to form fibers;
and step four, naturally airing the fiber after cleaning, and airing after soaking the fiber in the lithium chloride solution to obtain the composite electrogenesis fiber.
Further, the first step comprises preparing 3wt% sodium alginate solution, 15mg/mL graphene oxide solution, 5mg/mL CNT solution, 3mol/L lithium chloride solution and 10wt% CaCl 2 Is a fiber coagulation bath.
Further, the preparation of the sodium alginate solution comprises the following steps of weighing a certain amount of deionized water in a beaker, weighing the dried sodium alginate powder after purification, adding the powder into the beaker while stirring, magnetically stirring for 4 hours at room temperature to fully swell sodium alginate, and continuously stirring in a water bath at 50 ℃ for 0.5 hour to fully dissolve the sodium alginate to obtain a uniform and stable sodium alginate solution.
Further, the preparation of the lithium chloride aqueous solution comprises the following steps of adding 12.7g of lithium chloride and 100ml of water into a container, and vigorously stirring at room temperature for 2-3min to obtain a lithium chloride aqueous solution with a concentration of 3 mol/L.
Further, the preparation of the graphene oxide solution comprises the steps of preparing graphene oxide powder and preparing the graphene oxide solution by using the graphene oxide powder;
the preparation of graphene oxide powder comprises the following steps:
A1. 2.5g of graphite and 12.5g of potassium permanganate are weighed and 500mL of 5wt% sulfuric acid is prepared;
A2. adding graphite into sulfuric acid, and fully stirring; adding potassium permanganate into the mixture of graphite and sulfuric acid in batches every 2 minutes in an ice bath at 10 ℃, heating the mixture to 40 ℃ and keeping the temperature for 1 hour, manually stirring the mixture every 10 minutes for 1 hour to uniformly distribute the mixture, standing for 3.5 hours and overnight;
A3. after removal of the supernatant, 300 ml of deionized water and 20 ml of 35% hydrogen peroxide solution were slowly added, the solution turned from tan to golden yellow;
A4. loading the prepared graphene oxide solution into a centrifuge tube, and centrifuging at 4000rmp for about 25 minutes to completely separate the supernatant from the thick reagent;
A5. taking out, pouring out supernatant, and washing with water until the system is neutral to obtain graphene oxide; drying the solution to remove water to obtain graphene oxide powder;
the preparation of the graphene oxide solution from the graphene oxide powder comprises the following steps:
and taking a certain amount of graphene oxide powder, adding deionized water, and intermittently dispersing for 30 minutes by adopting an ultrasonic dispersing instrument to prepare a 15mg/mL graphene oxide solution.
Further, the preparation of the CNT solution comprises the following steps of taking a certain amount of graphitized carboxylated multi-wall carbon nano tube powder, adding deionized water, and intermittently dispersing for 15 minutes by adopting an ultrasonic dispersing instrument to prepare the CNT solution with the concentration of 5 mg/mL.
Further, the preparation of the fiber coagulation bath comprises the following steps of weighing a certain amount of anhydrous calcium chloride, and adding the anhydrous calcium chloride into the fiber coagulation bath according to the volume ratio of 1:1, stirring the mixed solution of deionized water and absolute ethyl alcohol until the mixed solution is fully dissolved, and preparing CaCl with the mass fraction of 10 percent 2 Coagulating bath solution.
Further, in the third step, cleaning the fibers includes cleaning with absolute ethyl alcohol and deionized water in sequence; after the fiber is washed, it is soaked in lithium chloride solution, then collected with polytetrafluoroethylene rod and naturally dried.
Further, the cellulose is 1% cellulose nanofiber prepared by a TEMPO oxidation method; the injector and the needle are an injector and a needle with the inner diameter of 0.648 mm.
The invention also discloses a sodium alginate-based composite electrogenesis fiber, which comprises the electrogenesis fiber prepared by any one of the methods.
Compared with the prior art, the invention has the beneficial effects that:
1. sodium alginate is taken as a matrix, graphene oxide and Carbon Nano Tubes (CNT) are carried to prepare fibers, and after the fibers are treated by a lithium chloride solution, the water absorption performance of the fibers in the air is improved, moisture in the air can be absorbed to become wet and ionize a large number of hydrogen ions, and along with the movement of water molecules along the fibers, the hydrogen ions are gathered to one section of the fibers, so that voltage is generated; the materials used for preparing the fiber belong to materials which can be purchased or prepared in a laboratory, the preparation cost is low, the preparation method is simple and convenient, and the preparation period is short.
2. The fiber taking sodium alginate as a matrix has better toughness, torsion resistance and tensile strength, has strong plasticity, and can be woven into different shapes for application
3. The graphitized carboxylated multi-wall carbon nano-tube and cellulose nano-fiber are added to strengthen and stabilize the generated voltage. None of these added chemical components is corrosive, making the fiber more skin friendly.
Drawings
FIG. 1 shows voltages of sodium alginate solution, graphene oxide solution, and cellulose nanofiber with a content of 5:1:1 under different humidity conditions in a first embodiment of the present invention;
FIG. 2 shows voltages of sodium alginate solution, graphene oxide solution, and cellulose nanofiber with a content of 5:1:2 under different humidity conditions in a second embodiment of the present invention;
FIG. 3 shows voltages of sodium alginate solution, graphene oxide solution, and cellulose nanofiber with a content of 5:1:3 at different humidity in a third embodiment of the present invention
Fig. 4 shows the electricity generation voltage of the sodium alginate solution, the graphene oxide solution and the cellulose nanofiber with the content of 5:1:2 in the air in the fourth embodiment of the present invention.
Detailed Description
In order to enhance the understanding of the present invention, the present invention will be further described in detail with reference to the drawings, which are provided for the purpose of illustrating the present invention only and are not to be construed as limiting the scope of the present invention.
The preparation method of the sodium alginate-based composite electrogenesis fiber comprises the following steps,
1. preparing sodium alginate solution with mass fraction of 3 percent: weighing a certain amount of deionized water in a beaker, weighing the dried sodium alginate powder after purification, adding the sodium alginate powder into the beaker while stirring, magnetically stirring for 4 hours at room temperature to fully swell sodium alginate, and then continuously stirring in a water bath at 50 ℃ for 0.5 hour to fully dissolve the sodium alginate to obtain a uniform and stable sodium alginate solution.
2. Preparing graphene oxide powder: 2.5g of graphite and 12.5g of potassium permanganate are weighed and 500mL of 5wt% sulfuric acid is prepared;
graphite was added to sulfuric acid and stirred well. Potassium permanganate was added to the graphite and sulfuric acid mixture in portions at 2 minute intervals in an ice bath at 10 c, the mixture was heated to 40 c for 1 hour, and after 1 hour, the mixture was evenly distributed by manually stirring 1 time at 10 minute intervals for 3.5 hours and allowed to stand overnight. After removal of the supernatant, 300 ml of deionized water and 20 ml of 35% hydrogen peroxide solution were slowly added, and the solution turned from tan to golden yellow. The prepared graphene oxide solution is filled into a centrifuge tube and centrifuged at 4000rmp for about 25 minutes, so that the supernatant is completely separated from the thick reagent. Taking out, pouring out supernatant, and washing with water until the system is neutral, thus obtaining the graphene oxide. And drying the solution to remove water to obtain graphene oxide powder.
3. Preparing a coagulation bath solution: weighing a certain amount of anhydrous calcium chloride, and adding the anhydrous calcium chloride into the mixture according to the volume ratio of 1:1, stirring the mixed solution of deionized water and absolute ethyl alcohol until the mixed solution is fully dissolved, and preparing CaCl with the mass fraction of 10 percent 2 Coagulating bath solution.
4. Wet spinning to prepare fiber: injecting the mixed solution into a rotary coagulating bath by a sample injector matched with a needle head with a certain diameter (inner diameter is 0.648 mm), wherein the rotating disc speed is 2.5r/min, immersing the fiber in the coagulating bath for 5min, sequentially washing the fiber by ethanol and deionized water to remove residual salt, collecting the fiber by a polytetrafluoroethylene rod, and drying the fiber at room temperature to obtain the sodium alginate-graphene oxide fiber. The fiber is completely soaked in 3mol/L lithium chloride solution, kept at room temperature for 1h, collected by a polytetrafluoroethylene rod, and finally dried at room temperature to obtain the composite electrogenesis fiber.
5. And (3) performing an electrical production test: and (3) connecting the electricity-generating fiber with a voltmeter by using a copper wire, placing the fiber in a constant humidity measuring device for online measurement to generate voltage, and finding out the fiber solution proportion with highest electricity-generating efficiency by a comparison test.
6. Preparing a composite solution: taking a certain amount of graphene oxide powder, adding deionized water, intermittently dispersing for 30 minutes by adopting an ultrasonic dispersing instrument to prepare a 15mg/mL graphene oxide solution, and taking the volume ratio of 5:1:1, mixing and stirring the sodium alginate solution, the graphene oxide solution and the cellulose nanofiber for 2 hours, adding 5mL of 5mg/mL of the CNT solution after ultrasonic dispersion, continuously stirring for 0.5 hour in a constant-temperature water bath at 50 ℃ to prepare the uniformly dispersed sodium alginate-graphene oxide solution, and sealing for later use.
The same method is provided with a volume ratio of 5:1: 2. 5:1: the mixed solution of 3 was used for the comparative test.
Example 1
A preparation method of a sodium alginate-based composite electrogenesis fiber comprises the following steps:
(1) Preparing 3wt% sodium alginate solution, 15mg/mL graphene oxide solution, 5mg/mL CNT solution, 3mol/L lithium chloride solution, 10wt% CaCl 2 Is used for the fiber coagulation bath;
(2) Taking the sodium alginate solution, the graphene oxide solution and the cellulose prepared in the step (1) according to a weight ratio of 5:1:1, uniformly mixing and stirring the mixture in a volume ratio, and adding 5mL of CNT solution to obtain a mixed solution;
(3) Taking the mixed solution in the step (2), and injecting the mixed solution into a coagulating bath through a sample injector and a needle to form fibers;
(4) And (3) cleaning the fiber in the step (3) by adopting absolute ethyl alcohol and deionized water, naturally airing, soaking the fiber in a lithium chloride solution for 1h, collecting the fiber by using a polytetrafluoroethylene rod, naturally airing, and connecting wires at two ends of the fiber to obtain the composite electrogenesis fiber.
Placing the prepared sodium alginate fiber in a constant humidity measuring device, respectively controlling humidity to be 50%, 80% and 90%, measuring electricity generation voltages of fibers with different components, and drawing to obtain a graph 1;
analysis of the voltage profile can yield: as the air humidity increases, the voltage generated by the fibers increases.
Example 2
A preparation method of a sodium alginate-based composite electrogenesis fiber comprises the following steps:
(1) Preparing 3wt% sodium alginate solution, 15mg/mL graphene oxide solution, 5mg/mL CNT solution, 3mol/L lithium chloride solution, 10wt% CaCl 2 Is used for the fiber coagulation bath;
(2) Taking the sodium alginate solution, the graphene oxide solution and the cellulose prepared in the step (1) according to a weight ratio of 5:1: mixing and stirring uniformly in a volume ratio of 2, and adding 5mL of CNT solution to obtain a mixed solution;
(3) Taking the mixed solution in the step (2), and injecting the mixed solution into a coagulating bath through a sample injector and a needle to form fibers;
(4) And (3) cleaning the fiber in the step (3) by adopting absolute ethyl alcohol and deionized water, naturally airing, soaking the fiber in a lithium chloride solution for 1h, collecting the fiber by using a polytetrafluoroethylene rod, naturally airing, and connecting wires at two ends of the fiber to obtain the composite electrogenesis fiber.
Placing the prepared sodium alginate fiber in a constant humidity measuring device, respectively controlling humidity to be 50%, 80% and 90%, measuring electricity generation voltages of fibers with different components, and drawing to obtain a graph 2;
analysis of the voltage profile can yield: as the air humidity increases, the voltage generated by the fibers increases; as the added cellulose increases, the voltage produced by the fibers increases.
Example 3
A preparation method of a sodium alginate-based composite electrogenesis fiber comprises the following steps:
(1) Preparing 3wt% sodium alginate solution, 15mg/mL graphene oxide solution, 5mg/mL CNT solution, 3mol/L lithium chloride solution, 10wt% CaCl 2 Is used for the fiber coagulation bath;
(2) Taking the sodium alginate solution, the graphene oxide solution and the cellulose prepared in the step (1) according to a weight ratio of 5:1:3 volume ratio, uniformly mixing and stirring, and adding 5mL of CNT solution to obtain a mixed solution;
(3) Taking the mixed solution in the step (2), and injecting the mixed solution into a coagulating bath through a sample injector and a needle to form fibers;
(4) And (3) cleaning the fiber in the step (3) by adopting absolute ethyl alcohol and deionized water, naturally airing, soaking the fiber in a lithium chloride solution for 1h, collecting the fiber by using a polytetrafluoroethylene rod, naturally airing, and connecting wires at two ends of the fiber to obtain the composite electrogenesis fiber.
Placing the prepared sodium alginate fiber in a constant humidity measuring device, respectively controlling humidity to be 50%, 80% and 90%, measuring the electricity generation voltages of the fibers with different components, and drawing to obtain a graph 3;
analysis of the voltage profile can yield: as the air humidity increases, the voltage generated by the fibers increases; as the cellulose addition increases, the voltage generated by the fibers increases, but after the cellulose content reaches a certain value, the voltage no longer increases with the increase of the cellulose content.
Example 4
A preparation method of a sodium alginate-based composite electrogenesis fiber comprises the following steps:
(1) Preparing 3wt% sodium alginate solution, 15mg/mL graphene oxide solution, 5mg/mL CNT solution, 3mol/L lithium chloride solution, 10wt% CaCl 2 Is used for the fiber coagulation bath;
(2) Taking the sodium alginate solution, the graphene oxide solution and the cellulose prepared in the step (1) according to a weight ratio of 5:1: mixing and stirring uniformly in a volume ratio of 2, and adding 5mL of CNT solution to obtain a mixed solution;
(3) Taking the mixed solution in the step (2), and injecting the mixed solution into a coagulating bath through a sample injector and a needle to form fibers;
(4) And (3) cleaning the fiber in the step (3) by adopting absolute ethyl alcohol and deionized water, naturally airing, soaking the fiber in a lithium chloride solution for 1h, collecting the fiber by using a polytetrafluoroethylene rod, naturally airing, and connecting wires at two ends of the fiber to obtain the composite electrogenesis fiber.
The fiber prepared as described above was placed in an air environment to measure a real-time voltage, and a voltage curve shown in fig. 4 was obtained, which revealed that the generated voltage was varied with the fluctuation of air humidity over a long period of time, and was maintained at 0.1V or more in most cases.
As can be seen from the four embodiments above,
1. the sodium alginate composite fiber prepared by the method can generate electricity for a long time under the air humidity;
2. as the air humidity increases, the voltage generated by the fibers increases;
3. as the cellulose addition increases, the voltage generated by the fibers increases, but after the cellulose content reaches a certain value, the voltage no longer increases with the increase of the cellulose content.
4. The composite electrogenesis fiber prepared by the invention can be kept above 0.1V under most conditions.
The foregoing detailed description will set forth only for the purposes of illustrating the general principles and features of the invention, and is not meant to limit the scope of the invention in any way, but rather should be construed in view of the appended claims.
Claims (10)
1. A preparation method of a sodium alginate-based composite electrogenesis fiber is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing 2-4wt% sodium alginate solution, 10-20mg/mL graphene oxide solution, 2-8mg/mLCNT solution, 2-4mol/L lithium chloride solution and 5-15wt% CaCl 2 Is used for the fiber coagulating bath;
step two, taking the sodium alginate solution and the graphene oxide solution prepared in the step one, and taking cellulose nanofibers, and uniformly mixing the cellulose nanofibers according to the proportion of 55-70% of sodium alginate solution, 10-15% of graphene oxide solution and 15-33% of cellulose nanofibers; wherein the sum of the percentages of the sodium alginate solution, the graphene oxide solution and the cellulose nanofiber is 1; adding 5mL of the CNT solution into the solution, and uniformly mixing and stirring to obtain a mixed solution;
injecting the mixed solution into the fiber coagulating bath through a sample injector to form fibers;
and step four, naturally airing the fiber after cleaning, and airing after soaking the fiber in the lithium chloride solution to obtain the composite electrogenesis fiber.
2. The method for preparing the sodium alginate-based composite electrogenesis fiber according to claim 1, wherein the method comprises the following steps: the first step comprises preparing 3wt% sodium alginate solution, 15mg/mL graphene oxide solution, 5mg/mL CNT solution, 3mol/L lithium chloride solution and 10wt% CaCl 2 Is a fiber coagulation bath.
3. The method for preparing the sodium alginate-based composite electrogenesis fiber according to claim 1, wherein the method comprises the following steps: the preparation of the sodium alginate solution comprises the following steps of weighing a certain amount of deionized water in a beaker, weighing the dried sodium alginate powder after purification, adding the powder into the beaker while stirring, magnetically stirring for 4 hours at room temperature to fully swell sodium alginate, and then continuously stirring in a water bath at 50 ℃ for 0.5 hour to fully dissolve the sodium alginate to obtain a uniform and stable sodium alginate solution.
4. The method for preparing the sodium alginate-based composite electrogenesis fiber according to claim 1, wherein the method comprises the following steps: the preparation of the lithium chloride solution comprises the following steps of adding 12.7g lithium chloride and 100ml water into a container, and vigorously stirring for 2-3min at room temperature to obtain a lithium chloride aqueous solution with the concentration of 3 mol/L.
5. The method for preparing the sodium alginate-based composite electrogenesis fiber according to claim 1, wherein the method comprises the following steps: the preparation of the graphene oxide solution comprises the steps of preparing graphene oxide powder and preparing the graphene oxide solution by using the graphene oxide powder;
the preparation of graphene oxide powder comprises the following steps:
A1. weighing 2.5g graphite and 12.5g potassium permanganate, and preparing 500ml5wt% sulfuric acid;
A2. adding graphite into sulfuric acid, and fully stirring; adding potassium permanganate into the mixture of graphite and sulfuric acid in batches every 2 minutes in an ice bath at 10 ℃, heating the mixture to 40 ℃ and keeping the temperature for 1 hour, manually stirring the mixture every 10 minutes for 1 hour to uniformly distribute the mixture, standing for 3.5 hours and overnight;
A3. after removal of the supernatant, 300 ml of deionized water and 20 ml of 35% hydrogen peroxide solution were slowly added, the solution turned from tan to golden yellow;
A4. loading the prepared graphene oxide solution into a centrifuge tube, and centrifuging at 4000rmp for 25 minutes to completely separate the supernatant from the thick reagent;
A5. taking out, pouring out supernatant, and washing with water until the system is neutral to obtain graphene oxide; drying the solution to remove water to obtain graphene oxide powder;
the preparation of the graphene oxide solution from the graphene oxide powder comprises the following steps:
and (3) taking a certain amount of graphene oxide powder, adding deionized water, and intermittently dispersing for 30 minutes by adopting an ultrasonic dispersing instrument to prepare 15mg/mL graphene oxide solution.
6. The method for preparing the sodium alginate-based composite electrogenesis fiber according to claim 1, wherein the method comprises the following steps: the preparation of the CNT solution comprises the following steps of taking a certain amount of graphitized carboxylated multiwall carbon nanotube powder, adding deionized water, and intermittently dispersing for 15 minutes by adopting an ultrasonic dispersing instrument to prepare the CNT solution of 5 mg/mL.
7. The method for preparing the sodium alginate-based composite electrogenesis fiber according to claim 1, wherein the method comprises the following steps: the preparation of the fiber coagulation bath comprises the following steps of weighing a certain amount of anhydrous calcium chloride, and adding the anhydrous calcium chloride into the fiber coagulation bath according to the volume ratio of 1:1, stirring the mixed solution of deionized water and absolute ethyl alcohol until the mixed solution is fully dissolved, and preparing CaCl with the mass fraction of 10 percent 2 Coagulating bath solution.
8. The method for preparing the sodium alginate-based composite electrogenesis fiber according to claim 1, wherein the method comprises the following steps: in the third step, cleaning the fiber comprises cleaning by adopting absolute ethyl alcohol and deionized water in sequence; after the fiber is washed, it is soaked in lithium chloride solution, then collected with polytetrafluoroethylene rod and naturally dried.
9. The method for preparing the sodium alginate-based composite electrogenesis fiber according to claim 8, wherein the method comprises the following steps: the cellulose is 1% cellulose nano-fiber prepared by a TEMPO oxidation method, and the injector and the needle are an injector and a needle with an inner diameter of 0.648 mm.
10. The utility model provides a compound electrogenesis fibre based on sodium alginate which characterized in that: an electrogenic fiber produced by the method of any of claims 1-9.
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