CN116013701A - Yarn-shaped super capacitor and two-electrode one-step electrodeposition preparation method thereof - Google Patents
Yarn-shaped super capacitor and two-electrode one-step electrodeposition preparation method thereof Download PDFInfo
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 11
- 238000004804 winding Methods 0.000 claims description 10
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 8
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- 238000002347 injection Methods 0.000 claims description 5
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- 239000011701 zinc Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
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- 239000000758 substrate Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
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- 238000011065 in-situ storage Methods 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 2
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- 229910001956 copper hydroxide Inorganic materials 0.000 claims 1
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 70
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Images
Classifications
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- 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
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention belongs to the technical field of energy storage devices, and particularly relates to a yarn-shaped super capacitor and a two-electrode one-step electrodeposition preparation method thereof. Firstly, using conductive carbon wires as a base material, electrostatically spinning TPU nanofibers on the surface of the conductive carbon wires, electrodepositing manganese dioxide on the surfaces of the conductive carbon wires by a timing current method, and finally pouring electrolyte and packaging a pipe orifice to obtain an integrated linear yarn-shaped supercapacitor; the preparation method can be applied to the field of flexible and wearable energy storage devices in an expanding way. The method has the advantages of simple process, convenient operation and universal materials, can easily realize serial connection and parallel connection while endowing the device with linearity, flexibility and plaiting property, and endows the energy storage device with excellent inheritance and expansibility.
Description
Technical Field
The invention belongs to the technical field of energy storage devices, and particularly relates to a yarn-shaped super capacitor and a two-electrode one-step electrodeposition preparation method thereof.
Background
With the rapid development of electronic devices, the development of electrochemical energy storage devices tends to be miniaturized, intelligent and personalized, while flexible or wearable electronic products are leading to the trend of next-generation consumer electronic products, super Capacitors (SCs) are receiving a great deal of attention as energy storage devices due to excellent characteristics of high power density, long cycle life, high rate performance, rapid charge and discharge and the like, and due to the remarkable application potential in the aspects of flexible or wearable electronic products, wearable super capacitors are rapidly developing. Compared with the traditional two-dimensional film super capacitor or fabric super capacitor, super capacitors with one-dimensional structure (fiber/yarn super capacitors) are considered to be more promising types because of the characteristics of light weight, portability and braiding, and can meet the power supply requirement of multifunctional equipment in a wearable electronic system in the future.
The commercial conductive carbon wire has the advantages of high conductivity, light weight, high modulus, high specific surface area and the like, is a good current collector material for preparing the fiber super capacitor, and has high specific surface area which can provide more sites for electrochemical deposition, but the hydrophobicity of the commercial conductive carbon wire can influence the electrodeposition process and needs further hydrophilic treatment; electrode materials are one of the key factors determining the electrochemical performance of supercapacitors, so the choice of electrode materials with excellent performance is a necessary condition for the study of supercapacitors. The electrode materials for the super capacitor at present mainly comprise carbon materials, transition metal oxides, conductive polymers and the like, and manganese dioxide is a transition metal oxide which is widely focused in the materials, and has the advantages of abundant resources, low price, environmental friendliness and the like, so that the manganese dioxide becomes an ideal electrode material.
The electrochemical deposition method can obtain the nano-sized electrode material under simple conditions, and the electrode material prepared by the method not only can change the surface area of an electrode and increase the reaction activity, but also can obviously improve the service life of the material; compared with a three-electrode deposition mode, the size of the electrolytic cell can be greatly reduced by using a two-electrode deposition mode, and electrodeposition can be performed in a micro-environment.
The nanofiber prepared by the electrostatic spinning has high orientation, high porosity and insulativity, so that the nanofiber prepared on the surface of the electrode fiber by the electrostatic spinning can play a good role in a diaphragm, and meanwhile, the high porosity of the nanofiber can provide more channels for ion transmission; further, we find that after electrostatic spinning on the surface of the current collector, the nanofiber does not affect the electrodeposition process, and meanwhile, manganese dioxide generated by electrodeposition is difficult to peel off in a large area due to the protection of the nanofiber, so that a brand new idea is provided for the application of the electrostatic spinning technology in the yarn-shaped super capacitor.
Disclosure of Invention
The invention aims to provide a preparation method of a yarn-shaped super capacitor, which has the advantages of simple process, convenient operation and common materials, and can easily realize serial connection and parallel connection while endowing the device with linearity, flexibility and plaiting property, and endow the energy storage device with excellent inheritance and expansibility.
The technical scheme adopted for solving the technical problems is as follows:
a method of making a yarn-like supercapacitor, the method comprising the steps of:
(1) Preparation of spinning solution for electrostatic spinning:
dissolving Thermoplastic Polyurethane (TPU) in an N-N dimethylformamide solvent, wherein the mass fraction of the thermoplastic polyurethane is 15-25%, and stirring at room temperature for more than 12 hours to obtain a thermoplastic polyurethane spinning solution;
(2) Hydrophilic treatment of conductive carbon wires:
placing the conductive carbon wire in 5-10mol/L nitric acid solution in an autoclave with a Teflon lining for hydrothermal treatment, wherein the hydrothermal temperature is 90-150 ℃ and the hydrothermal time is 60-180min;
after the treated conductive carbon wire is washed by ethanol, deep washing is carried out in an autoclave with a Teflon lining under the condition of pH 8-9 to neutralize the acidic condition, the conductive carbon wire is prevented from being excessively corroded, the deep washing temperature is 100-250 ℃, the time is 60-180min, and then the conductive carbon wire is dried in an oven at 70 ℃ for overnight;
(3) Preparing TPU nanofiber/conductive carbon yarn:
taking the conductive carbon yarn obtained in the step (2) as a substrate, and adopting the thermoplastic polyurethane spinning solution obtained in the step (1) to carry out electrostatic spinning to obtain TPU nanofiber/conductive carbon yarn, wherein the weight ratio of the conductive carbon yarn to the TPU nanofiber in the yarn is 5:1-2;
(4) Yarn-shaped super capacitor preparation
Two TPU nanofiber/conductive carbon yarn yarns with the same length of 5-20cm and a zinc wire are parallelly plugged into a PTFE tube, electrolyte containing manganese element is poured into the PTFE tube through a syringe pump, and MnO loaded on the surface of the conductive carbon yarn is synthesized in situ by adopting a chronoamperometric electrodeposition process 2 The voltage of the active material is 1.8-2.5V, and the electrodeposition time is 300-6000s;
and after the reaction is finished, the zinc wires are extracted, electrolyte is supplemented, and the PTFE pipe orifice is sealed by glue, so that the sealed yarn-shaped super capacitor is obtained.
The invention adopts the electrostatic spinning technology to prepare the nanofiber and the chronoamperometric electrodeposition process to prepare the supercapacitor, has simple and convenient method, is easy to continuously prepare, overcomes the defects of poor processability and mechanical property of the nanofiber while endowing the device with linearity and flexibility, and directly uses electrolyte to carry out the electrochemical deposition process in a superfine PTFE tube, thereby further reducing the cost.
Too low a concentration of the spinning solution may cause the spinning solution to be too thin to form a spinning solution, and too high a concentration may cause the solution to have too high a viscosity to cause spinning to be difficult.
Preferably, the thermoplastic polyurethane in step (1) has a molecular weight of 10000 to 50000.
Preferably, the conductive carbon wire in the step (2) has one or more of 1K, 3K, 12K and 24K. The K number refers to the number of commercial conductive carbon wires, belongs to industry general terms, and is preferably the conductive carbon wires with the specification below 12K to control the thickness of the conductive carbon wires, so that the size of the manufactured energy storage device is smaller.
Preferably, the substance providing weak alkaline condition in the step (2) is one or more of urea, sodium carbonate, ferric hydroxide, ferrous hydroxide and cupric hydroxide, and the concentration is 0.01-0.1mol/L.
Preferably, the parameters set in the step (3) of electrospinning are as follows: the included angle between the needle tip and the central axis of the collector is 60 degrees plus or minus 5 degrees, the distance between the needle tip and the collector is 6-8 cm, the injection pump advances the spinning solution at the speed of 0.7-0.8 mL/h, the spinning process uses 12-17KV direct current high voltage power, the rotating speed of the funnel-shaped collector is 80-120rpm, and the speed of the winding device is 0.06-0.08 m/min. The electrostatic spinning device mainly comprises a positive and negative high-voltage power supply, an injection pump, a funnel-shaped collector and a winding device, wherein a schematic diagram is shown in figure 4, polymer is pulled into filaments through high voltage power supply, taylor cones are formed, sprayed nano fibers have positive and negative charges, electrons are contacted and offset with each other at the middle part of the device and deposited on the surface of the funnel-shaped collector to form a film, the film is hooked on the winding device through a core material or a hook, the film is driven to rotate by the collector to finish twisting to form nano fiber yarns or nano fiber core-spun yarns, and the nano fiber yarns are collected on the winding device to meet continuous preparation requirements. Through accurately controlling parameters of electrostatic spinning, spinning solution can be easily drawn and uniformly adsorbed on a funnel-shaped collector and twisted on the surface of the face yarn to form certain twist, so that the surface uniformity is improved, the specific surface area is further improved, and the uniform and complete attachment of liquid metal on the surface is ensured.
Preferably, the electrolyte preparation flow described in the step (4) is as follows: dissolving electrolyte in deionized water at room temperature to prepare electrolyte; the electrolyte is manganese sulfate (MnSO) 4 ) Zinc sulphate (ZnSO) 4 ) Lithium chloride (LiCl), sulfuric acid (H) 2 SO 4 ) Or potassium hydroxide (KOH) or one or more of them, the concentration of manganese sulfate in the electrolyte is 0.1-2mol/L.
Preferably, the PTFE tube in step (4) has a diameter of 0.5 to 10mm.
Preferably, the diameter of the zinc wire in step (4) is 0.3-2mm. The smaller the diameter of the PTFE tube and zinc wire, the smaller the size of the energy storage device that can be made is enough to allow for better application.
Preferably, the voltage of the time-current method in the step (4) is selected to be 2.2V, and the electrodeposition time is 600-1200s. The invention adopts one-step method to electrodeposit manganese dioxide as an active substance to prepare the super capacitor, and the step of a two-electrode timing current method is the technical difficulty and is most important. The standard electrode potential for zinc is-0.76V and for manganese is 1.12V, with the further preferred condition being electrodeposition by chronoamperometry at 2.2V for 900s in order to ensure successful deposition of manganese dioxide while avoiding decomposition of water.
Preferably, the glue in the step (4) is one or more of UV glue, latex, hot melt glue and sealing glue.
The yarn-shaped super capacitor manufactured by the manufacturing method comprises a conductive carbon wire current collector, a nanofiber layer, an active substance, an electrolyte and an encapsulation material.
Firstly, using conductive carbon wires as a base material, electrostatically spinning TPU nanofibers on the surface of the conductive carbon wires, electrodepositing manganese dioxide on the surfaces of the conductive carbon wires by a timing current method, and finally pouring electrolyte and packaging a pipe orifice to obtain an integrated linear yarn-shaped supercapacitor; the preparation method can be applied to the field of flexible and wearable energy storage devices in an expanding way. Compared with the prior art, the method has the following characteristics:
(1) The invention uses the conductive carbon wire as the substrate, can endow the device with good mechanical and physical properties, has good conductivity, and can perfectly fuse the fibrous structure with the traditional clothes;
(2) The invention adopts the electrostatic spinning technology, can overcome the defects of poor processability and mechanical property of the nanofiber, is convenient and quick to continuously prepare, can protect manganese dioxide from large-area stripping, seals the manganese dioxide in the nanofiber, and has good interlayer effect in the system due to the insulativity of the nanofiber;
(3) The invention uses a chronoamperometric electrodeposition manganese dioxide, can take the PTFE tube as an electrodeposition place and electrolyte as an electrolytic cell, reduces the electrodeposition procedures of a complex three-electrode system, and ensures that the process is simpler and more convenient;
the prepared independent or series-parallel yarn-shaped super capacitor has excellent mechanical flexibility and electrochemical performance.
Drawings
FIG. 1 is an SEM image of the pre-hydrothermal conductive carbon wire of supplemental example 1;
FIG. 2 is an SEM image of post-hydrothermal conductive carbon filaments of supplemental example 1;
FIG. 3 is an infrared spectrum analysis chart in supplementary example 1;
FIG. 4 is a schematic view of a self-made electrospinning apparatus in supplementary example 2, in which (1) is a winding apparatus, (2) is a syringe pump, and (3) is a funnel-type collector;
FIG. 5 is a SEM image of the low magnification conductive carbon wire of supplemental example 2;
FIG. 6 is an STM diagram of the TPU/conductive carbon filament of supplemental example 2;
FIG. 7 is a cross-sectional view of the TPU/conductive carbon filament of supplemental example 2;
FIG. 8 is an SEM image of TPU nanofiber/manganese dioxide/conductive carbon filament of supplemental example 3;
FIG. 9 is a mapping graph of TPU nanofiber/manganese dioxide/conductive carbon filament of supplemental example 3, wherein graph a is an SEM graph of TPU nanofiber/manganese dioxide/conductive carbon filament, (b) element C, (C) element O, (d) element Mn, (e) element Zn, (f) element S;
FIG. 10 is an SEM image of manganese dioxide/conductive carbon wires of supplemental example 3;
FIG. 11 is a mapping graph of manganese dioxide/conductive carbon wire in supplemental example 3, wherein graph a is an SEM graph of manganese dioxide/conductive carbon wire, (b) O element, (c) Mn element, and (d) Zn element;
FIG. 12 is an SEM image of a 300s deposited manganese dioxide/conductive carbon wire of supplemental example 4;
FIG. 13 is an SEM image of a 3000s deposited manganese dioxide/conductive carbon wire of supplemental example 4;
FIG. 14 is an SEM image of a 6000s deposited manganese dioxide/conductive carbon wire of supplemental example 4;
FIG. 15 is an EIS spectrum of a yarn-like supercapacitor in example 5;
FIG. 16 is a current-voltage curve of the yarn-like supercapacitor of example 5;
FIG. 17 is a constant current charge-discharge curve of the yarn-like supercapacitor of example 5;
FIG. 18 is a constant current charge-discharge curve of 2 or 3 yarn-like supercapacitors in series in supplemental example 5;
FIG. 19 is a plot of very current charge and discharge for 2, 3 yarn-like supercapacitors in parallel in supplemental example 5;
FIG. 20 is a current-voltage curve of the string-parallel yarn-like supercapacitor of supplemental example 5;
FIG. 21 is a diagram of three yarn-like supercapacitors in series to power a hygrothermograph in supplemental example 5;
FIG. 22 is a graphical representation of the series connection of three yarn-like supercapacitors to illuminate a small bulb in supplemental example 5;
FIG. 23 is a long cycle test curve of the yarn-like supercapacitor of supplemental example 6;
FIG. 24 is a charge-discharge curve of turns 1 to 4 in a long cycle test of the yarn-like supercapacitor of supplemental example 6;
fig. 25 is a charge-discharge curve of 15001 to 15004 th turns in a long-cycle test of the yarn-like supercapacitor in supplementary example 6.
Detailed Description
The technical scheme of the invention is further specifically described by the following specific examples. It should be understood that the practice of the invention is not limited to the following examples, but is intended to be within the scope of the invention in any form and/or modification thereof.
In the present invention, unless otherwise specified, all parts and percentages are by weight, and the equipment, materials, etc. used are commercially available or are conventional in the art. The methods in the following examples are conventional in the art unless otherwise specified.
The invention uses conductive carbon wire as current collector, and obtains good hydrophilicity by hydro-thermal method, builds TPU nanometer fiber with directivity and uniformity on the surface by electrostatic spinning, uses PTFE tube as packaging material and electrochemical deposition reaction place, pours electrolyte in the tube, electro-chemically deposits manganese dioxide active substance on the surface of conductive carbon wire by two-electrode one-step method, and finally packages to prepare yarn-shaped super capacitor. The TPU nanofiber prepared by the electrostatic spinning technology has the advantages of high porosity, insulativity and high mechanical strength, can be used as a reliable diaphragm material in a device, can not influence the electrochemical deposition, provides more application prospects for the nanofiber in the field of supercapacitors, and has the advantages of simple steps and controllable deposition amount.
The invention realizes the excellent performances of mechanical flexibility, electrochemical performance and good series-parallel performance of the yarn-shaped super capacitor by applying the electrostatic spinning technology, carrying out hydrothermal conductive carbon wire, carrying out electrochemical deposition by two electrodes, screening active substances and electrolytes and the like, and provides a new idea for flexible intelligent wearable electronic devices and fabrics.
Example 1
A hydrophilic treatment method of conductive carbon wires comprises the following specific steps:
the commercial 3K conductive carbon wire is used as a raw material, the commercial 3K conductive carbon wire is placed in an autoclave with a Teflon lining, 6mol/L nitric acid is used as a solution, the conductive carbon wire is immersed in the nitric acid, the commercial 3K conductive carbon wire is subjected to hydrothermal treatment at 110 ℃ for 120min, the commercial 3K conductive carbon wire is placed in a urea solution at 0.05mol/L for deep cleaning, the commercial 3K conductive carbon wire is subjected to treatment at 180 ℃ for 120min, the commercial 3K conductive carbon wire is cleaned by ethanol, and the commercial 3K conductive carbon wire is dried overnight in an oven at 70 ℃, and is weighed by an electronic balance, so that the mass of the commercial Teflon lining conductive carbon wire is 180mg/cm.
Supplementary example 1 conductive carbon filament characterization
SEM images before and after the hydrothermal treatment of the conductive carbon filament are shown in the accompanying drawings 1 and 2, the surface of the conductive carbon filament after the hydrothermal treatment is etched more, so that the hydrophilicity is increased, more sites are provided for the deposition of manganese dioxide, and infrared spectrum analysis is shown in the accompanying drawings 3, so that the conductive carbon filament after the hydrothermal treatment is 3436.45cm compared with the conductive carbon filament before the hydrothermal treatment -1 The peak value is obviously increased, which indicates that the overall hydroxyl content of the fiber is obviously increased after the hydrothermal treatment.
Example 2
A preparation method of conductive yarn comprises the following specific steps:
(1) Preparation of spinning solution for electrostatic spinning
10g of TPU is weighed and dissolved in 40ml of DMF solvent, and magnetically stirred for 3 hours at 80 ℃ to form a uniform TPU spinning solution;
(2) Hydrophilic treatment of conductive carbon filaments
As in example 1;
(3) Preparation of conductive yarn
Taking conductive carbon wires as a substrate, adopting the TPU spinning solution prepared in the step (1), and carrying out electrostatic spinning by using self-made electrostatic spinning equipment, wherein the specific preparation method is as shown in a supplementary example 2, so as to prepare TPU nanofiber core spun yarns; supplementary example 2 preparation and characterization of TPU nanofibers/conductive carbon filaments
(1) Electrostatic spinning device constitution and principle: the electrostatic spinning device mainly comprises a positive and negative high-voltage power supply, an injection pump, a funnel-shaped collector and a winding device, wherein a schematic diagram is shown in figure 4, polymer is pulled into filaments through high voltage power supply, taylor cones are formed, sprayed nano fibers have positive and negative charges, electrons are contacted and offset with each other at the middle part of the device and deposited on the surface of the funnel-shaped collector to form a film, the film is hooked on the winding device through a core material or a hook, the film is driven to rotate by the collector to finish twisting to form nano fiber yarns or nano fiber core-spun yarns, and the nano fiber yarns are collected on the winding device to meet continuous preparation requirements.
(2) Electrospinning parameters: the angle between the needle point and the collector is 60 degrees, the distance between the needle point and the collector is 8cm, the injection pump advances the spinning solution at the speed of 0.7mL/h, 16KV direct-current high-voltage electricity is used in the spinning process, the rotating speed of the funnel-shaped collector is 80rpm, and the speed of the winding device is 0.06m/min, so that uniform and continuous nanofiber core spun yarns can be prepared;
(3) The SEM images of the conductive carbon filament, the TPU nanofiber/conductive carbon filament and the sectional views of the TPU nanofiber/nanofiber are shown in fig. 5, 6 and 7, it can be seen that the conductive carbon filament is in a loose state before being coated by the nanofiber, the occupied volume is large, the conductive carbon filament is bundled by the nanofiber after the TPU nanofiber is coated on the surface of the conductive carbon filament by electrostatic spinning, the sectional views can also illustrate the point, and meanwhile, the nanofiber is uniformly oriented on the surface of the conductive carbon filament, has a compact structure, and cannot observe the structure of the internal conductive carbon filament. From the sectional view, it can be seen that the diameter of the conductive carbon filament after being bundled is 530.4 μm, the thickness of the nanofiber is 37.1 μm, the overall diameter is only 603.6 μm, the smaller diameter can enable the overall diameter of the assembled device to be smaller, the miniaturization is easier to meet, and the weight of the TPU nanofiber is 48mg/cm by using an electronic balance for weighing.
Example 3
A preparation method of a yarn-shaped super capacitor comprises the following specific steps:
(1) Preparation of spinning solution for electrostatic spinning
10g of TPU is weighed and dissolved in 40ml of DMF solvent, and magnetically stirred for 3 hours at 80 ℃ to form a uniform TPU spinning solution;
(2) Hydrophilic treatment of conductive carbon filaments
As in example 1;
(3) Preparation of conductive yarn
Same as in example 2;
(4) Yarn-shaped super capacitor preparation
Two TPU nanofiber/conductive carbon yarn yarns with the length of 5cm and a zinc wire are parallelly plugged into a PTFE tube, electrolyte is poured into the PTFE tube through a syringe pump, the electrolyte is electrodeposited for 900s under the condition of 2.2V through a chronoamperometry, the zinc wire is extracted after the reaction is finished, the electrolyte is replenished, and the PTFE tube orifice is sealed by UV glue, so that the sealed yarn-shaped super capacitor is obtained.
The formula of the electrolyte comprises the following steps: 36% of zinc sulfate, 27% of manganese sulfate and the balance of deionized water, wherein the total mass of the electrolyte is 100%.
Supplemental example 3 analysis of morphology of TPU nanofiber/manganese dioxide/conductive carbon filament
Taking out the TPU nanofiber/manganese dioxide/conductive carbon wire after the reaction is finished, soaking in deionized water for ten minutes to remove the influence of zinc sulfate and manganese sulfate in the electrolyte, wherein no granular deposition is observed on the surface of the TPU nanofiber/manganese dioxide/conductive carbon wire as shown in figure 8, which indicates that no manganese dioxide is deposited on the surface of the fiber, and further verifying the inference from a mapping graph as shown in figure 9; after the nanofibers are stripped, a large amount of and uniform manganese dioxide deposition can be observed on the conductive carbon wire, and as shown in fig. 10, the mapping graph can hardly observe the possibility that the sulfur element can further remove manganese sulfate, which not only shows that manganese dioxide can be successfully deposited on the conductive carbon wire, but also shows that manganese dioxide can not be deposited on the surfaces of the nanofibers, and the direct contact of an electrode material and a current collector can ensure the low resistance and high ion mobility of the whole device.
Example 4
A preparation method of a yarn-shaped super capacitor comprises the following specific steps:
(1) Preparation of spinning solution for electrostatic spinning
10g of TPU is weighed and dissolved in 40ml of DMF solvent, and magnetically stirred for 3 hours at 80 ℃ to form a uniform TPU spinning solution;
(2) Hydrophilic treatment of conductive carbon filaments
As in example 1;
(3) Preparation of conductive yarn
Same as in example 2;
(4) Yarn-shaped super capacitor preparation
Two TPU nanofiber/conductive carbon yarn yarns with the length of 5cm and a zinc wire are parallelly plugged into a PTFE tube, electrolyte is poured into the PTFE tube through a syringe pump, 300, 3000 and 6000 seconds are electrodeposited through a chronoamperometry under the condition of 2.2V, the zinc wire is extracted after the reaction is finished, the electrolyte is replenished, and a PTFE tube orifice is sealed by UV glue, so that the sealed yarn-shaped supercapacitor is obtained.
Supplementary example 4 conductive carbon filament morphology analysis
Taking out the TPU nanofiber/manganese dioxide/conductive carbon wire after the reaction is finished, soaking the TPU nanofiber/manganese dioxide/conductive carbon wire in deionized water for ten minutes to remove the influence of zinc sulfate and manganese sulfate in electrolyte, as shown in figures 12-14, the deposition amount of manganese dioxide on the surface of the conductive carbon wire for electrodeposition 300s is small, the capacity of a device is small after the subsequent assembly into a supercapacitor, and more manganese dioxide deposits are formed on the surface of the conductive carbon wire for deposition 3000s and 6000s, so that spherical deposits are formed, the manganese dioxide in the spherical deposits cannot fully play a role to reduce the specific capacity, meanwhile, the distance between the manganese dioxide on the outer layer and the conductive carbon wire current collector is far because of poor conductivity of the manganese dioxide, and the impedance of the device is increased to influence the overall performance, so that the preferable deposition time is 900s is determined.
Example 5
A preparation method of a yarn-shaped super capacitor comprises the following specific steps:
(1) Preparation of spinning solution for electrostatic spinning
10g of TPU is weighed and dissolved in 40ml of DMF solvent, and magnetically stirred for 3 hours at 80 ℃ to form a uniform TPU spinning solution;
(2) Hydrophilic treatment of conductive carbon filaments
As in example 1;
(3) Preparation of conductive yarn
Same as in example 2;
(4) Yarn-shaped super capacitor preparation
Two TPU nanofiber/conductive carbon yarn yarns with the length of 5cm and a zinc wire are parallelly plugged into a PTFE tube, electrolyte is poured into the PTFE tube through a syringe pump, the electrolyte is electrodeposited for 900s under the condition of 2.2V through a chronoamperometry, the zinc wire is extracted after the reaction is finished, the electrolyte is replenished, and the PTFE tube orifice is sealed by UV glue, so that the sealed yarn-shaped super capacitor is obtained.
The formula of the electrolyte comprises the following steps: 36% of zinc sulfate, 27% of manganese sulfate and the balance of deionized water, wherein the total mass of the electrolyte is 100%.
Further characterizing the electrochemical performance of the prepared yarn-like super capacitor, the Nyquist curve is shown in FIG. 15, electrons only move on the current collector due to the very fast time in the high frequency region, the contact resistance between components is tested, the intercept Ri between the high frequency region and the X axis is about 42 omega, which indicates that the yarnThe contact resistance of the super capacitor is very small, and the included angle between the low-frequency area and the X axis is relatively large, which indicates that the super capacitor has good capacitance; the current-voltage curve is shown in FIG. 16, and is 0-0.8V, 10-50mV s -1 The Cyclic Voltammetry (CV) test is carried out at different scanning rates, and no obvious characteristic peak can be seen from the CV curve, which indicates that no oxidation-reduction reaction is generated in the charge-discharge process, only the double-layer reaction is generated, and meanwhile, the CV curve presents a rectangle-like shape, which indicates that the yarn-like capacitor can be subjected to the reversible charge-discharge process; constant current charge and discharge (GCD) as shown in figure 17, constant current charge and discharge test is carried out under the conditions of 0-0.8V and 25-100 mu A, the reversion curve is basically in isosceles triangle shape, the potential of the discharge curve is linear with time, meanwhile, the discharge curve has almost no voltage drop, and meanwhile, exciting is that under the constant current condition of 25 mu A, the charge and discharge time of the yarn-shaped super capacitor can reach surprisingly 1500s, which shows excellent energy storage performance and also provides possibility for long-time energy supply for devices.
Example 6
A preparation method of a yarn-shaped super capacitor comprises the following specific steps:
(1) Preparation of spinning solution for electrostatic spinning
10g of TPU is weighed and dissolved in 40ml of DMF solvent, and magnetically stirred for 3 hours at 80 ℃ to form a uniform TPU spinning solution;
(2) Hydrophilic treatment of conductive carbon filaments
As in example 1;
(3) Preparation of conductive yarn
Same as in example 2;
(4) Yarn-shaped super capacitor preparation
Two TPU nanofiber/conductive carbon yarn yarns with the length of 5cm and a zinc wire are parallelly plugged into a PTFE tube, electrolyte is poured into the PTFE tube through a syringe pump, the electrolyte is electrodeposited for 900s under the condition of 2.2V through a chronoamperometry, the zinc wire is extracted after the reaction is finished, the electrolyte is replenished, and the PTFE tube orifice is sealed by UV glue, so that a sealed yarn-shaped super capacitor is obtained, and the multi-heeled yarn-shaped super capacitor is prepared.
The formula of the electrolyte comprises the following steps: 36% of zinc sulfate, 27% of manganese sulfate and the balance of deionized water, wherein the total mass of the electrolyte is 100%.
Supplementary example 5 series-parallel test of yarn-like super capacitor
Because of the rapid charge and discharge and smaller voltage window of the super capacitor, a single super capacitor is difficult to meet the requirement of supplying energy with long-acting high voltage, so that whether the super capacitor can be simply connected in series and parallel is one of important tests, as shown in figure 18, constant current charge and discharge tests are carried out under the condition of 25 mu A, the charge and discharge time is not obviously changed under the condition of connecting 2 or 3 yarn-shaped super capacitors in series, the voltage can be multiplied, and meanwhile, the voltage drop is not obviously fluctuated; in the condition of connecting 2 or 3 yarn-shaped supercapacitors in parallel, as shown in figure 19, the voltage window does not change obviously, the charge and discharge time can reach 2 or 3 times of that of a single supercapacitor, meanwhile, the supercapacitor can be easily connected in series and in parallel, a CV diagram of the series and parallel connection is shown in figure 20, and the CV curve can further illustrate the excellent series and parallel connection capability of the yarn-shaped supercapacitor; the excellent serial-parallel performance enables the three-yarn super capacitor to become a common energy accumulator in life, when the serial number reaches 3, the voltage window can reach 2.4V, and the rated voltage of a commonly used dry battery is achieved, so that the three-yarn super capacitor can be used for supplying energy to devices, as shown in figures 21 and 22, the three-yarn super capacitor can be used for easily lighting a small bulb after being connected in series, and meanwhile, the three-yarn super capacitor can also be used for supplying energy to common electrical appliances such as a temperature and humidity device and a clock instead of the dry battery.
Example 7
A preparation method of a yarn-shaped super capacitor comprises the following specific steps:
(1) Preparation of spinning solution for electrostatic spinning
10g of TPU is weighed and dissolved in 40ml of DMF solvent, and magnetically stirred for 3 hours at 80 ℃ to form a uniform TPU spinning solution;
(2) Hydrophilic treatment of conductive carbon filaments
As in example 1;
(3) Preparation of conductive yarn
Same as in example 2;
(4) Yarn-shaped super capacitor preparation
Two TPU nanofiber/conductive carbon yarn yarns with the length of 2cm and a zinc wire are parallelly plugged into a PTFE tube, electrolyte is poured into the PTFE tube through a syringe pump, the electrolyte is electrodeposited for 900s under the condition of 2.2V through a chronoamperometry, the zinc wire is extracted after the reaction is finished, the electrolyte is replenished, and the PTFE tube orifice is sealed by UV glue, so that a sealed yarn-shaped super capacitor is obtained, and the multi-heeled yarn-shaped super capacitor is prepared.
The formula of the electrolyte comprises the following steps: 36% of zinc sulfate, 27% of manganese sulfate and the balance of deionized water, wherein the total mass of the electrolyte is 100%.
Further characterizing the electrochemical performance of the yarn-shaped super capacitor, the long-cycle test curve is shown in figures 23-25, at 0.025mA/cm 2 The test of the yarn-shaped super capacitor under the current density of (3) shows that the efficiency of the yarn-shaped super capacitor is not changed after 15000 cycles of charge and discharge, the cycle efficiency is always kept between 98 and 100 percent, the capacity is not obviously reduced, the charge and discharge time of the first cycle is 125s, and the charge and discharge time after 15000 cycles is still kept at about 120s, so that the cycle stability of YSC is good, and the capacity is not obviously changed.
In this specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, so that the same or similar parts between the embodiments are referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The yarn-shaped super capacitor and the two-electrode one-step electrodeposition preparation method thereof provided by the invention are described in detail. The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (10)
1. A method for manufacturing a yarn-like supercapacitor, characterized in that it comprises the steps of:
(1) Preparation of spinning solution for electrostatic spinning:
dissolving Thermoplastic Polyurethane (TPU) in an N-N dimethylformamide solvent, wherein the mass fraction of the thermoplastic polyurethane is 15-25%, and stirring the mixture at room temperature for more than 12 and h to obtain a thermoplastic polyurethane spinning solution;
(2) Hydrophilic treatment of conductive carbon wires:
placing the conductive carbon wire in 5-10mol/L nitric acid solution in an autoclave with a Teflon lining for hydrothermal treatment, wherein the hydrothermal temperature is 90-150 ℃ and the hydrothermal time is 60-180min;
after the treated conductive carbon wire is washed by ethanol, deep washing is carried out in an autoclave with a Teflon lining under the condition of pH 8-9, the temperature of the deep washing is 100-250 ℃ for 60-180min, and then the conductive carbon wire is dried in an oven at 70 ℃ for overnight;
(3) Preparing TPU nanofiber/conductive carbon yarn:
taking the conductive carbon yarn obtained in the step (2) as a substrate, and adopting the thermoplastic polyurethane spinning solution obtained in the step (1) to carry out electrostatic spinning to obtain TPU nanofiber/conductive carbon yarn, wherein the weight ratio of the conductive carbon yarn to the TPU nanofiber in the yarn is 5:1-2;
(4) Yarn-shaped super capacitor preparation
Two TPU nanofiber/conductive carbon yarn yarns with the same length of 5-20 and cm and a zinc wire are parallelly plugged into a PTFE tube, electrolyte containing manganese element is poured into the PTFE tube through a syringe pump, and MnO loaded on the surface of the conductive carbon yarn is synthesized in situ by adopting a chronoamperometric electrodeposition process 2 The active material, the voltage of the timing amperometric method is selected to be 1.8-2.5V, and the electrodeposition time is 300-6000s;
and after the reaction is finished, the zinc wires are extracted, electrolyte is supplemented, and the PTFE pipe orifice is sealed by glue, so that the sealed yarn-shaped super capacitor is obtained.
2. The method of manufacturing according to claim 1, characterized in that: the molecular weight of the thermoplastic polyurethane in the step (1) is 10000-50000.
3. The method of manufacturing according to claim 1, characterized in that: in the step (2), the specification of the conductive carbon wire is one or more of 1K, 3K, 12K and 24K.
4. The method of manufacturing according to claim 1, characterized in that: the substances providing weak base conditions in the step (2) are one or more of urea, sodium carbonate, ferric hydroxide, ferrous hydroxide and copper hydroxide, and the concentration is 0.01-0.1mol/L.
5. The method of manufacturing according to claim 1, characterized in that: parameters set in the step (3) of electrostatic spinning are as follows: the included angle between the needle tip and the central axis of the collector is 60 degrees plus or minus 5 degrees, the distance between the needle tip and the collector is 6-8 cm, the injection pump advances the spinning solution at the speed of 0.7-0.8 mL/h, the direct-current high-voltage power is applied to 12-17KV in the spinning process, the rotating speed of the funnel-shaped collector is 80-120rpm, and the speed of the winding device is 0.06-0.08 m/min.
6. The method of manufacturing according to claim 1, characterized in that: the electrolyte preparation flow in the step (4) is as follows: dissolving electrolyte in deionized water at room temperature to prepare electrolyte; the electrolyte is manganese sulfate (MnSO) 4 ) Zinc sulphate (ZnSO) 4 ) Lithium chloride (LiCl), sulfuric acid (H) 2 SO 4 ) Or potassium hydroxide (KOH) or one or more of them, the concentration of manganese sulfate in the electrolyte is 0.1-2mol/L.
7. The method of manufacturing according to claim 1, characterized in that: the PTFE tube diameter in the step (4) is 0.5-10. 10mm.
8. The method of manufacturing according to claim 1, characterized in that: the diameter of the zinc wire in the step (4) is 0.3-2mm.
9. The method of manufacturing according to claim 1, characterized in that: the voltage of the time amperometry in the step (4) is selected to be 2.2V, and the electrodeposition time is 600-1200s.
10. A yarn-like supercapacitor made by the method of making of claim 1, the energy storage device comprising a conductive carbon filament current collector, a nanofiber layer, an active material, an electrolyte, and an encapsulating material.
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