CN109950639B - Metal ion battery and preparation method thereof - Google Patents

Metal ion battery and preparation method thereof Download PDF

Info

Publication number
CN109950639B
CN109950639B CN201910127517.XA CN201910127517A CN109950639B CN 109950639 B CN109950639 B CN 109950639B CN 201910127517 A CN201910127517 A CN 201910127517A CN 109950639 B CN109950639 B CN 109950639B
Authority
CN
China
Prior art keywords
fiber
zinc
ion battery
negative electrode
battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910127517.XA
Other languages
Chinese (zh)
Other versions
CN109950639A (en
Inventor
王凯
马衍伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Electrical Engineering of CAS
Original Assignee
Institute of Electrical Engineering of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Electrical Engineering of CAS filed Critical Institute of Electrical Engineering of CAS
Priority to CN201910127517.XA priority Critical patent/CN109950639B/en
Publication of CN109950639A publication Critical patent/CN109950639A/en
Application granted granted Critical
Publication of CN109950639B publication Critical patent/CN109950639B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to the technical field of battery preparation, and particularly relates to a metal ion battery and a preparation method thereof. The battery comprises a substrate, and a positive electrode fiber and a negative electrode fiber wound on the substrate, wherein the positive electrode fiber and the negative electrode fiber are wound with each other, and the positive electrode fiber is a conductive polymer/carbon nano tube composite fiber; the negative electrode fiber is zinc/carbon nanotube composite fiber; and the anode fiber and the cathode fiber are respectively obtained by the gel electrolyte coating step. The battery adopts the structural design that the anode fiber and the cathode fiber are firstly spirally wound and then wound on the substrate, so that the electrochemical performance of the battery and the charge transmission efficiency of the anode and the cathode can be improved, and the battery has low resistance and better rate performance; the positive electrode and the negative electrode of the battery are self-supporting electrodes, and a conductive agent and a binder do not need to be added, so that the inert components in the battery are greatly reduced, and the energy density of the battery is favorably improved.

Description

Metal ion battery and preparation method thereof
Technical Field
The invention belongs to the technical field of battery preparation, and particularly relates to a metal ion battery and a preparation method thereof.
Background
The development of fibrous, woven devices compatible with traditional textile processes is an important approach to achieving flexibility in wearable devices. The fibrous structure can realize the flexibility in the three-dimensional direction, can also weave different fibre function devices into the good fabric of wearable performance through low-cost textile technology like traditional chemical fibre, cotton thread to realize the ideal design target of integrating multiple device on an intelligent clothes.
In chinese patent literature, CN 103904357a discloses a stretchable linear lithium ion battery and a method for manufacturing the same, wherein the method comprises the steps of preparing a carbon nanotube/lithium manganate composite fiber as a positive electrode, preparing a carbon nanotube/lithium titanate composite fiber as a negative electrode, winding the positive and negative electrode fibers in parallel on an elastic rubber, coating a layer of ethylene oxide/succinonitrile/lithium bistrifluoromethylsulfonyl imide gel electrolyte, and finally packaging to obtain the linear lithium ion battery. In the method, positive and negative active materials are firstly dissolved in a solution and then are dripped on the surface of a carbon nano tube, and form composite fibers with the carbon nano tube through physical adsorption, but the composite fibers have weak adsorption force and are easy to fall off in a stretching process, so that capacity retention rate is poor, and the loading capacity of the active materials is uncontrollable and the reproducibility is poor; according to the method, the positive and negative fibers are wound on the elastic rubber in parallel, so that the two fibers are not in contact, the resistance of the battery is increased, the charge transmission efficiency of the positive and negative electrodes is reduced, and the like. In addition, the lithium ion battery is sensitive to oxygen and moisture in the air, and can start to work after being packaged, but the tensile property of the battery is reduced after the packaging layer is added.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to overcome the problems of low charge transmission efficiency of the positive electrode and the negative electrode of the linear battery in the prior art, and the like, so as to provide a fibrous metal ion battery and a preparation method thereof.
Therefore, the invention provides the following technical scheme:
the invention provides a metal ion battery, which comprises a matrix, and a positive electrode fiber and a negative electrode fiber wound on the matrix, wherein the positive electrode fiber and the negative electrode fiber are mutually wound.
The metal ion battery is a zinc ion battery.
The positive electrode fiber is a conductive polymer/carbon nanotube composite fiber, and the mass ratio of the conductive polymer to the carbon nanotube in the conductive polymer/carbon nanotube composite fiber is (6-21): 14;
the diameter of the carbon nanotube fiber is 20-200 μm.
The monomer of the conductive polymer is at least one of aniline, pyrrole and ethylenedioxythiophene.
The negative electrode fiber is a zinc/carbon nanotube composite fiber, and the mass ratio of zinc to the carbon nanotubes in the zinc/carbon nanotube composite fiber is (2-9): 3.
The mass ratio of the anode fibers to the cathode fibers is (1-2) to 2.
The metal ion battery also comprises an electrolyte layer coated on the anode fibers and the cathode fibers, wherein the electrolyte layer is made of acrylamide, polyvinyl alcohol or gelatin;
the matrix is at least one of polyurethane, polydimethylsiloxane and polyurethane elastomer.
The invention also provides a preparation method of the metal ion battery, which comprises the steps of respectively preparing the anode fiber and the cathode fiber, coating electrolyte on the surfaces of the anode fiber and the cathode fiber, winding the coated anode fiber and the coated cathode fiber together, and winding the wound anode fiber and cathode fiber on the substrate to obtain the metal ion battery.
The preparation method of the negative electrode fiber comprises the steps of taking the carbon nano tube as a working electrode, adopting a three-electrode system, taking an aqueous solution containing zinc salt as an electrolyte, and preparing the zinc/carbon nano tube composite fiber by adopting an electrochemical constant potential reduction method.
The preparation method of the anode fiber comprises the steps of placing the carbon nano tube in a solution containing a conductive polymer monomer and a doping agent, and preparing the conductive polymer/carbon nano tube composite fiber at the temperature of-10-25 ℃ by adopting a chemical oxidation or electrochemical oxidation method.
The zinc salt is at least one of zinc sulfate, zinc nitrate and zinc chloride; the concentration of the zinc salt is 0.05-2 mol/L.
The technical scheme of the invention has the following advantages:
1. the invention provides a metal ion battery, which comprises a matrix, and a positive electrode fiber and a negative electrode fiber wound on the matrix, wherein the positive electrode fiber and the negative electrode fiber are wound with each other; wherein, the anode fiber is a conductive polymer/carbon nano tube composite fiber; the negative electrode fiber is zinc/carbon nanotube composite fiber; and the anode fiber and the cathode fiber are respectively obtained by the gel electrolyte coating step. The battery adopts the structural design that the anode fiber and the cathode fiber are firstly spirally wound and then wound on the substrate, so that the electrochemical performance of the battery and the charge transmission efficiency of the anode and the cathode can be improved, and the battery has low resistance and better rate performance; the positive electrode of the battery adopts the conductive polymer/carbon nano tube composite fiber, the negative electrode adopts the zinc/carbon nano tube composite fiber, the zinc/carbon nano tube composite fiber is a self-supporting electrode, and a conductive agent and a binder do not need to be added, so that the inert components in the battery are greatly reduced, and the energy density of the battery is favorably improved.
2. According to the metal ion battery provided by the invention, the structural design that the anode fiber and the cathode fiber are firstly spirally wound and then wound on the substrate is adopted, the stress is mainly concentrated on the substrate, and the anode and the cathode are the spiral fibers and have stretching allowance, so that the battery shows excellent stretching resistance and bending resistance.
3. According to the zinc ion battery provided by the invention, the specific capacity of the battery can reach up to 180mAh/g, the specific capacity retention rate can reach 90% after 5000 times of cyclic charge and discharge, the tensile rate can reach up to 300%, the specific capacity retention rate of the battery can reach up to 95% after continuous stretching or bending for 1000 times, and the energy density of a positive electrode material and a negative electrode material of the battery can reach 205 Wh/kg. Therefore, the zinc battery provided by the invention can work normally under normal conditions or bending and winding conditions, and can be applied to wearable equipment.
4. The metal ion battery provided by the invention adopts the organic electrode material with intrinsic flexibility, namely the conductive polymer, as the positive electrode, compared with MnO2、V2O5The stress generated by the insertion reaction of zinc ions can be effectively buffered by the traditional inorganic zinc ion battery anode material, and the cyclic charge-discharge life of the zinc ion battery is greatly prolonged; in addition, the intrinsic flexibility of the conductive polymer enables the fibrous electrode and the battery to have more excellent mechanical properties of tensile resistance and bending resistance.
According to the metal ion battery provided by the invention, the negative electrode fiber is the zinc/carbon nanotube composite fiber, and the water-based battery is adopted, so that the metal ion battery is stable in air and can stably work without a packaging layer.
5. The preparation method of the metal ion battery comprises the steps of respectively preparing the anode fiber and the cathode fiber, coating electrolyte on the surfaces of the anode fiber and the cathode fiber, winding the coated anode fiber and cathode fiber together, and winding the wound anode fiber and cathode fiber on the substrate to obtain the metal ion battery. The method comprises the steps that the anode fibers and the cathode fibers are wound together and then wound on a substrate to form the ion battery, and the direct winding structural design can improve the electrochemical performance of the battery and the charge transmission efficiency of the anode and the cathode, so that the battery has low resistance and better rate performance; the battery prepared by the preparation method disclosed by the invention has the advantages that the stress is mainly concentrated on the substrate, the positive electrode and the negative electrode are wound on the substrate, the stretching allowance is realized, the phenomenon that the stress damage occurs to the coated current collecting layer and the active layer in the stretching process can be avoided, and the battery shows excellent stretching resistance and bending resistance. The positive electrode fiber and the negative electrode fiber coated with the electrolyte are firstly spirally wound together, so that the relative positions of the positive electrode and the negative electrode are closer, the electrochemical performance of the battery and the charge transmission efficiency of the positive electrode and the negative electrode can be improved, and the battery has low resistance and better rate performance; in addition, the relative position of the positive electrode and the negative electrode is kept unchanged in the stretching process, the structural design can keep the positive electrode and the negative electrode in stable contact, and the stability of charge storage efficiency in the stretching or bending process is ensured.
6. According to the preparation method of the metal ion battery, when the fiber anode and cathode composite fibers are prepared, the in-situ chemical or electrochemical deposition method is adopted to deposit the active materials on the anode carbon nano tube and the cathode carbon nano tube respectively, so that the adhesion force of the active materials on the anode carbon nano tube and the cathode carbon nano tube is good, the active materials are not easy to fall off in the stretching process, and the capacity retention rate is good; and the electrochemical performance and the mechanical tensile property of the battery are obviously improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a process flow diagram for preparing a zinc-ion battery according to example 1 of the present invention;
FIG. 2 is a schematic view showing the intertwining of the positive electrode fibers and the negative electrode fibers of the battery in example 1 of the present invention;
FIG. 3 is a schematic view showing that the positive electrode fibers and the negative electrode fibers are wound around each other and then wound on the substrate in example 1 of the present invention;
fig. 4 is a schematic view showing a stretched state of the battery of fig. 3 in example 1 of the present invention;
FIG. 5 is a scanning electron micrograph of a carbon nanotube fiber prepared in example 1;
FIG. 6 is a scanning electron micrograph of a polyaniline/carbon nanotube fiber prepared after chemical oxidative polymerization in example 1;
FIG. 7 is a scanning electron micrograph of a zinc/carbon nanotube fiber prepared by the electrodeposition method of example 1;
fig. 8 is an optical microscope photograph of a zinc ion battery in example 1 in which the positive electrode fiber and the negative electrode fiber coated with the electrolyte were spirally wound.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a zinc ion battery and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparing the carbon nano tube: fixing a spinnable carbon nanotube array grown by a vapor deposition method (CVD) on a rotatable sample table, continuously pulling out a carbon nanotube film with the width of 12mm from the edge of the array, twisting to form fibers, collecting the fibers on a rotating roller, and spinning the carbon nanotubes into continuous long fibers; wherein the twist angle of the fiber collection is 20 °, the diameter of the carbon nanotube long fiber is 100 μm, as shown in fig. 5;
preparing the conductive polymer/carbon nano tube composite fiber: placing the carbon nano tube long fiber in a sulfuric acid aqueous solution containing aniline monomer, and adding potassium persulfate at 0 ℃ to ensure that aniline is subjected to surface chemical oxidative polymerization on the fiber surface to obtain a conductive polymer/carbon nano tube composite long fiber-shaped electrode, as shown in fig. 6; the mass ratio of the conductive polymer to the carbon nano tube is 1: 1;
preparing the zinc/carbon nanotube composite fiber: adopting a three-electrode system, taking carbon nano tube long fiber as a working electrode, taking a counter electrode as a platinum sheet and a reference electrode as a saturated calomel electrode, and putting 0.2mol/L ZnSO4In the aqueous solution, a constant potential method is adopted, the reduction potential is-0.8V, the reduction time is 10min, and the zinc/carbon nano tube composite long fiber electrode is prepared and obtained, as shown in figure 7; the mass ratio of zinc to the carbon nano tube is 3: 2;
preparing a zinc ion battery: adding Acrylamide (AM) monomer and crosslinking agent N, N' -methylene Bisacrylamide (BIS) into 1mol/L ZnSO4Stirring the mixture in the aqueous solution until the mixture is completely dissolved; the concentration of AM is 3g/mL, and the concentration of BIS is 0.2 mg/mL; then adding initiator potassium persulfate (K)2S2O8) Stirring until the mixture is completely dissolved, wherein the concentration of the mixture is 50 mg/mL; adding the solution into a glass tube with the inner diameter of 120 mu m, and respectively enabling the prepared positive electrode fiber conductive polymer/carbon nano tube and the prepared negative electrode fiber zinc/carbon nano tube to pass through the glass tube, so that the surfaces of the positive electrode fiber and the negative electrode fiber are uniformly and continuously coated with Polyacrylamide (PAAM) hydrogel electrolyte, and the diameters of the coated positive electrode fiber and the coated negative electrode fiber are 120 mu m;
spirally winding the PAAM electrolyte-coated positive electrode fiber and the negative electrode fiber together by using a self-made winding machine (as shown in figures 2 and 8), and then integrally winding the positive electrode fiber and the negative electrode fiber on a polyurethane elastic matrix (as shown in figure 3) to form a fibrous rechargeable zinc-ion battery, wherein the stretched state of the battery is shown in figure 4; the mass ratio of the conductive polymer/carbon nano tube composite long fiber-shaped anode to the zinc/carbon nano tube composite long fiber cathode is 2: 3.
Example 2
The present example provides a zinc ion battery and a method for manufacturing the same, which is different from example 1 only in the material of the substrate, and the substrate in this example is made of polydimethylsiloxane.
Example 3
The present embodiment provides a zinc ion battery and a method for manufacturing the same, which is different from embodiment 1 only in the material of the substrate, and the substrate in this embodiment is made of polyurethane.
Example 4
The embodiment provides a zinc ion battery and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparing the carbon nano tube: fixing a spinnable carbon nanotube array grown by CVD on a rotatable sample table, continuously pulling out a carbon nanotube film with the width of 5mm from the edge of the array, twisting to form fibers, collecting the fibers on a rotating roller, and spinning the carbon nanotubes into continuous long fibers; wherein the twist angle of the fiber collection is 20 degrees, and the diameter of the carbon nano tube long fiber is 20 μm;
preparing the conductive polymer/carbon nano tube composite fiber: placing the carbon nano tube long fiber in a sulfuric acid aqueous solution containing aniline monomers, and adding potassium persulfate at the temperature of 0 ℃ to ensure that aniline is subjected to chemical oxidative polymerization on the surface of the fiber to obtain a conductive polymer/carbon nano tube composite long fiber-shaped electrode, wherein the mass ratio of the conductive polymer to the carbon nano tube is 5: 7;
preparing the zinc/carbon nanotube composite fiber: adopting a three-electrode system, taking carbon nano tube long fiber as a working electrode, taking a counter electrode as a platinum sheet and a reference electrode as a saturated calomel electrode, and putting 0.2mol/L ZnSO4In the aqueous solution, a constant potential method is adopted, the reduction potential is-0.8V, the electrochemical reduction time is 10min, and the zinc/carbon nano tube composite long fiber electrode is prepared, wherein the mass ratio of zinc to the carbon nano tube is 5: 3;
preparing a zinc ion battery: adding Acrylamide (AM) monomer and crosslinking agent N, N' -methylene Bisacrylamide (BIS) into 1mol/L ZnSO4Stirring the mixture in the aqueous solution until the mixture is completely dissolved; the concentration of Acrylamide (AM) monomer is 3g/mL, and BIS is 0.2 mg/mL; then adding initiator potassium persulfate (K)2S2O8) Stirring until completely dissolved, the concentration of which is 50mgmL; adding the solution into a glass tube with the inner diameter of 40 micrometers, and respectively enabling the prepared positive electrode fiber conductive polymer/carbon nano tube and the prepared negative electrode fiber zinc/carbon nano tube to penetrate through the glass tube, so that the surfaces of the positive electrode fiber and the negative electrode fiber are uniformly and continuously coated with PAAM hydrogel electrolyte, and the diameters of the coated positive electrode fiber and the coated negative electrode fiber are 40 micrometers;
spirally winding the positive electrode fiber and the negative electrode fiber coated with the PAAM electrolyte together by adopting a self-made winding machine, and then integrally further winding the positive electrode fiber and the negative electrode fiber on a polyurethane elastic matrix to form a fibrous rechargeable zinc ion battery; the mass ratio of the conductive polymer/carbon nano tube composite long fiber-shaped anode to the zinc/carbon nano tube composite long fiber cathode is 3: 4.
Example 5
The embodiment provides a zinc ion battery and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparing the carbon nano tube: fixing a spinnable carbon nanotube array grown by CVD on a rotatable sample table, continuously pulling out a carbon nanotube film with the width of 20mm from the edge of the array, twisting to form fibers, collecting the fibers on a rotating roller, and spinning the carbon nanotubes into continuous long fibers; wherein the twist angle of the fiber collection is 20 degrees, and the diameter of the carbon nano tube long fiber is 200 μm;
preparing the conductive polymer/carbon nano tube composite fiber: placing the carbon nano tube long fiber in a sulfuric acid aqueous solution containing aniline monomers, and adding potassium persulfate at the temperature of 0 ℃ to ensure that aniline is subjected to chemical oxidative polymerization on the surface of the fiber to obtain a conductive polymer/carbon nano tube composite long fiber-shaped electrode, wherein the mass ratio of the conductive polymer to the carbon nano tube is 1: 1;
preparing the zinc/carbon nanotube composite fiber: adopting a three-electrode system, taking carbon nano tube long fiber as a working electrode, taking a counter electrode as a platinum sheet and a reference electrode as a saturated calomel electrode, and putting 0.2mol/L ZnSO4In the aqueous solution, a constant potential method is adopted, the reduction potential is-0.8V, the electrochemical reduction time is 10min, and the zinc/carbon nano tube composite long fiber electrode is prepared, wherein the mass ratio of zinc to the carbon nano tube is 3: 2;
preparing a zinc ion battery: adding Acrylamide (AM) monomer and crosslinking agent N, N' -methylene Bisacrylamide (BIS) into 1mol/L ZnSO4Stirring the mixture in the aqueous solution until the mixture is completely dissolved; the concentration of Acrylamide (AM) monomer is 3g/mL, and BIS is 0.2 mg/mL; then adding initiator potassium persulfate (K)2S2O8) Stirring until the mixture is completely dissolved, wherein the concentration of the mixture is 50 mg/mL; adding the solution into a glass tube with the inner diameter of 220 mu m, and respectively enabling the prepared positive electrode fiber conductive polymer/carbon nano tube and the prepared negative electrode fiber zinc/carbon nano tube to penetrate through the glass tube, so that PAAM hydrogel electrolyte is uniformly and continuously coated on the surfaces of the positive electrode fiber and the negative electrode fiber, and the fiber diameters of the coated positive electrode fiber and the coated negative electrode fiber are 220 mu m;
spirally winding the positive electrode fiber and the negative electrode fiber coated with the PAAM electrolyte together by adopting a self-made winding machine, and then integrally further winding the positive electrode fiber and the negative electrode fiber on a polyurethane elastic matrix to form a fibrous rechargeable zinc ion battery; wherein the mass ratio of the conductive polymer/carbon nano tube composite long fiber-shaped anode to the zinc/carbon nano tube composite long fiber cathode is 2: 3.
Example 6
This example provides a zinc ion battery and a method for preparing the same, which are different from example 1 only in that, unlike the conductive polymer monomer, aniline is replaced with pyrrole in the step of preparing the conductive polymer/carbon nanotube composite fiber.
Example 7
This example provides a zinc ion battery and a method for preparing the same, which are different from example 1 only in that, unlike the conductive polymer monomer, aniline is replaced with ethylenedioxythiophene in the step of preparing the conductive polymer/carbon nanotube composite fiber.
Example 8
The embodiment provides a zinc ion battery and a preparation method thereof, and the difference from the embodiment 1 is only that the preparation method for preparing the conductive polymer/carbon nanotube composite fiber is different, and specifically the preparation method comprises the steps of adopting a three-electrode system, taking carbon nanotube long fibers as a working electrode, taking a counter electrode as a platinum sheet and a reference electrode as a saturated calomel electrode, putting the carbon nanotube long fibers into a sulfuric acid aqueous solution containing aniline monomers, and performing constant-potential electrochemical oxidation polymerization at the temperature of 0 ℃ for 10min at a potential of 1V to obtain the conductive polymer/carbon nanotube composite long fiber-shaped electrode.
Example 9
This example provides a zinc ion battery and a method for preparing the same, which is different from example 1 only in that the reaction temperature in the step of the conductive polymer/carbon nanotube composite fiber is different, and the temperature of the chemical oxidation reaction of the conductive polymer in this example is-10 ℃.
Example 10
This example provides a zinc ion battery and a method for preparing the same, which is different from example 1 only in that the reaction temperature in the step of the conductive polymer/carbon nanotube composite fiber is different, and the temperature of the chemical oxidation reaction of the conductive polymer in this example is 25 ℃.
Example 11
This example provides a zinc ion battery and a method for manufacturing the same, which is different from example 1 only in that, in the step of depositing zinc metal on the zinc/carbon nanotube composite fiber, the zinc salt is Zn (NO)3)2。
Example 12
This example provides a zinc ion battery and a method for manufacturing the same, which is different from example 1 only in that, in the step of depositing zinc metal on the zinc/carbon nanotube composite fiber, the zinc salt is ZnCl2。
Example 13
This example provides a zinc ion battery and a method for preparing the same, which is different from example 1 only in that the electrolyte for depositing zinc metal in the step of zinc/carbon nanotube composite fiber is 2mol/L ZnSO4An aqueous solution.
Example 14
This example provides a zinc ion battery and a method for preparing the same, which is different from example 1 only in that the electrolyte for depositing zinc metal in the step of zinc/carbon nanotube composite fiber is 0.05mol/L ZnSO4An aqueous solution.
Example 15
The present embodiment provides a zinc ion battery and a method for manufacturing the same, which are different from those of embodiment 1 in terms of a mass ratio of conductive polymer/carbon nanotube composite fibers, a mass ratio of zinc/carbon nanotube composite fibers, and a mass ratio of conductive polymer/carbon nanotube composite fibers to zinc/carbon nanotube composite fibers;
in this embodiment, the mass ratio of the conductive polymer to the carbon nanotube composite fiber in the conductive polymer/carbon nanotube composite fiber is 3: 7; the mass ratio of zinc to the carbon nanotube composite fibers in the zinc/carbon nanotube composite fibers is 2: 3; the mass ratio of the conductive polymer/carbon nanotube composite fiber to the zinc/carbon nanotube composite fiber is 1: 1.1.
Example 16
The present embodiment provides a zinc ion battery and a method for manufacturing the same, which are different from those of embodiment 1 in terms of a mass ratio of conductive polymer/carbon nanotube composite fibers, a mass ratio of zinc/carbon nanotube composite fibers, and a mass ratio of conductive polymer/carbon nanotube composite fibers to zinc/carbon nanotube composite fibers;
in this embodiment, the mass ratio of the conductive polymer to the carbon nanotube composite fiber in the conductive polymer/carbon nanotube composite fiber is 3: 2; the mass ratio of zinc to the carbon nanotube composite fibers in the zinc/carbon nanotube composite fibers is 3: 1; the mass ratio of the conductive polymer/carbon nanotube composite fiber to the zinc/carbon nanotube composite fiber is 1: 2.
Example 17
The present embodiment provides a zinc ion battery and a method for manufacturing the same, which are different from those of embodiment 1 in terms of a mass ratio of conductive polymer/carbon nanotube composite fibers, a mass ratio of zinc/carbon nanotube composite fibers, and a mass ratio of conductive polymer/carbon nanotube composite fibers to zinc/carbon nanotube composite fibers;
in this embodiment, the mass ratio of the conductive polymer to the carbon nanotube composite fiber in the conductive polymer/carbon nanotube composite fiber is 2: 3; the mass ratio of zinc to the carbon nanotube composite fibers in the zinc/carbon nanotube composite fibers is 2: 1; the mass ratio of the conductive polymer/carbon nanotube composite fiber to the zinc/carbon nanotube composite fiber is 1: 1.5.
Example 18
This example provides a zinc-ion battery and a method for preparing the same, which are different from example 1 in that the twist angle of twisting is 30 ° in the step of preparing carbon nanotubes.
Example 19
This example provides a zinc-ion battery and a method for preparing the same, which are different from example 1 in that, in the step of preparing carbon nanotubes, the twist angle of twisting is 10 °.
Example 20
This example provides a zinc ion battery and a method for preparing the same, which is different from example 1 in that, in the step of preparing the zinc ion battery, a gel electrolyte is polyvinyl alcohol; the method specifically comprises the following steps: first, 1g of polyvinyl alcohol (PVA) was dissolved in 10mL of a solution containing 1mol L-1Zinc sulfate (ZnSO)4) In an aqueous solution of (3) (0.1g mL)-1) Heating to 80 ℃ under electromagnetic stirring, and keeping for 0.5 hour until the solution becomes clear to obtain ZnSO4-a PVA gel electrolyte.
Example 21
The present embodiment provides a zinc ion battery and a method for manufacturing the same, which is different from embodiment 1 in that in the step of manufacturing the zinc ion battery, a gel electrolyte is gelatin, and the specific manufacturing method is as follows: first 1.5g of gelatin was dissolved in 15mL of a solution containing 1mol L-1Sodium sulfate (Na)2SO4) In an aqueous solution of (3) (0.1g mL)-1) Heating to 80 ℃ under electromagnetic stirring, and keeping for 0.5 hour until the solution becomes clear to obtain ZnSO4-gelatin gel electrolyte.
Comparative example 1
This comparative example provides a zinc-ion battery and a method for manufacturing the same, which is different from example 1 in that, in the step of manufacturing the zinc-ion battery, a positive electrode coated with a PAAM electrolyte and a negative electrode are wound in parallel on a polyurethane elastic substrate without contacting each other, forming a fibrous rechargeable zinc-ion battery.
Test examples
The test example provides performance tests and test results of the zinc ion batteries obtained in examples 1 to 21 and comparative example 1, and the specific results are shown in table 1:
the specific capacity testing method comprises the following steps: connecting two electrode ends of the prepared battery to a VMP3Multichannel Potentiostats (Bio-logic, France) tester, charging from 0.3V to 1.6V by a constant current charging and discharging method, namely, under the charging and discharging current with the current density of 0.5A g-1, then discharging to 0.3V under the same current, and recording the discharging time, thereby obtaining the specific capacity by calculation;
the method for testing the retention rate of specific capacity of 5000 times of cyclic charge and discharge comprises the following steps: the method for testing the retention rate of the specific capacity of 5000 times of cyclic charge and discharge is similar to the method for testing the specific capacity, only 5000 times of charge and discharge are continuously tested, and then the specific capacity of 5000 th charge and discharge is divided by the specific capacity of the first charge and discharge to obtain the retention rate of the specific capacity of the cyclic charge and discharge, which is represented by R;
the energy density test method comprises the following steps: based on the obtained specific capacity, calculating by using a formula E ═ UdC/m; wherein, U is the charging and discharging voltage range, C is the specific capacity, and m is the total mass of the positive and negative active materials;
the tensile rate test method comprises the following steps: clamping two ends of the fiber battery by using a displacement table, then gradually stretching the battery to a certain length, and calculating the ratio of the stretched length to the initial length;
after continuous stretching for 1000 times, the specific capacity retention rate test method comprises the following steps: stretching from an initial length to a certain length, and then rebounding to the initial length for one cycle; the specific capacity of the battery before and after stretching is tested, and then the specific capacity measured after 1000 stretching cycles is divided by the initial specific capacity before stretching to obtain the capacity retention rate after stretching, which is expressed by S.
Table 1 results of performance test of zinc ion batteries obtained in examples 1 to 21 and comparative example 1
Figure BDA0001974120200000131
Figure BDA0001974120200000141
Table 1, in example 1, compared with comparative example 1, the specific capacity of the zinc ion battery obtained in example 1 is significantly higher than that of the battery in comparative example 1, which shows that the structural design of the present invention that the positive and negative fibers are spirally wound and then wound on the substrate is helpful to improve the electrochemical performance of the battery and the charge transfer efficiency of the positive and negative electrodes; the retention rate of specific capacity of the battery obtained in example 1 after 5000 times of cyclic charge and discharge is higher than that of comparative example 1, which shows that the service life of the battery is longer; the elongation of the battery obtained in example 1 is superior to that of comparative example 1, indicating that the battery provided by the present invention is excellent in tensile resistance and bending resistance. The specific capacity retention rate and the energy densities of the positive electrode fiber and the negative electrode fiber of the battery obtained in example 1 after the battery is continuously drawn for 1000 times are all superior to those of comparative example 1.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (9)

1. A metal ion battery comprises a matrix, and a positive electrode fiber and a negative electrode fiber wound on the matrix, and is characterized in that the positive electrode fiber and the negative electrode fiber are mutually wound;
the metal ion battery is a zinc ion battery;
the anode fiber is a conductive polymer/carbon nano tube composite fiber; the negative electrode fiber is a zinc/carbon nanotube composite fiber.
2. The metal-ion battery of claim 1, wherein the mass ratio of conductive polymer to carbon nanotubes in the conductive polymer/carbon nanotube composite fiber is (6-21): 14;
the diameter of the carbon nanotube fiber is 20-200 μm.
3. The metal-ion battery of claim 2, wherein the monomer of the conductive polymer is at least one of aniline, pyrrole, and ethylenedioxythiophene.
4. The metal-ion battery of claim 2 or 3, wherein the mass ratio of zinc to carbon nanotubes in the zinc/carbon nanotube composite fiber is (2-9): 3.
5. The metal-ion battery of any of claims 1-3, wherein the mass ratio of the positive fibers to the negative fibers is (1-2): 2.
6. The metal-ion battery of any one of claims 1-3, further comprising an electrolyte layer coated on the positive and negative electrode fibers, the electrolyte layer being made of acrylamide, polyvinyl alcohol, or gelatin;
the matrix is at least one of polyurethane, polydimethylsiloxane and polyurethane elastomer.
7. A method for preparing a metal ion battery according to any one of claims 1 to 6, wherein the positive electrode fiber and the negative electrode fiber are prepared separately, an electrolyte is coated on the surfaces of the positive electrode fiber and the negative electrode fiber, the coated positive electrode fiber and the coated negative electrode fiber are wound together, and then the wound body is wound to obtain the metal ion battery.
8. The preparation method of the negative electrode fiber according to claim 7, wherein the negative electrode fiber is prepared by using a carbon nanotube as a working electrode, a three-electrode system, an aqueous solution containing zinc salt as an electrolyte, and an electrochemical constant potential reduction method to obtain the zinc/carbon nanotube composite fiber;
the zinc salt is at least one of zinc sulfate, zinc nitrate and zinc chloride; the concentration of the zinc salt is 0.05-2 mol/L.
9. The preparation method of claim 7 or 8, wherein the positive electrode fiber is prepared by placing the carbon nanotubes in a solution containing a conductive polymer monomer and a dopant, and preparing the conductive polymer/carbon nanotube composite fiber by a chemical oxidation or electrochemical oxidation method at-10 to 25 ℃.
CN201910127517.XA 2019-02-20 2019-02-20 Metal ion battery and preparation method thereof Active CN109950639B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910127517.XA CN109950639B (en) 2019-02-20 2019-02-20 Metal ion battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910127517.XA CN109950639B (en) 2019-02-20 2019-02-20 Metal ion battery and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109950639A CN109950639A (en) 2019-06-28
CN109950639B true CN109950639B (en) 2021-03-19

Family

ID=67006859

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910127517.XA Active CN109950639B (en) 2019-02-20 2019-02-20 Metal ion battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109950639B (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110729518B (en) * 2019-09-08 2022-12-20 复旦大学 Manganese dioxide/graphene-based water-based zinc ion battery and preparation method thereof
CN110911632A (en) * 2019-12-02 2020-03-24 中国工程物理研究院化工材料研究所 Preparation method of zinc ion electrode material capable of being woven and sewn and zinc ion battery
CN112952077A (en) * 2019-12-10 2021-06-11 湖北工业大学 Flexible zinc ion battery and preparation method thereof
CN112993217A (en) * 2019-12-13 2021-06-18 中国科学院大连化学物理研究所 Preparation method of organic-inorganic hybrid material based on vanadium pentoxide and application of organic-inorganic hybrid material in zinc ion battery
CN112072125A (en) * 2020-08-20 2020-12-11 浙江工业大学 Preparation method and application of cobalt diselenide/carbon-based flexible electrode material with interface enhancement structure
CN112563443B (en) * 2020-11-20 2022-08-12 扬州大学 Flexible battery electrode and manufacturing process thereof
CN112563586B (en) * 2020-12-27 2022-02-22 西南大学 Method for improving performance of zinc-iodine battery based on halogen bond effect
CN113540390B (en) * 2021-06-29 2022-04-01 哈尔滨工业大学 Preparation method and application of dynamic interface coating of metal zinc cathode of zinc ion battery
CN115249848A (en) * 2021-09-15 2022-10-28 青岛大学 Ultra-tensile fiber-based water-based zinc ion battery and preparation method thereof
CN117059914B (en) * 2023-07-12 2024-06-14 苏州大学 High-low temperature resistant integrated zinc ion fiber battery and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101728581A (en) * 2008-10-14 2010-06-09 Nec东金株式会社 Lithium ion battery

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103700798A (en) * 2013-12-16 2014-04-02 北京大学 Fiber chemical energy storage power supply and preparation method thereof
CN103904357B (en) * 2014-03-09 2016-03-02 宁国市龙晟柔性储能材料科技有限公司 A kind of stretchable wire lithium ion battery and preparation method thereof
CN104282444A (en) * 2014-09-07 2015-01-14 复旦大学 Stretchable line-shaped super capacitor with carbon nano tube/polyaniline composite materials as counter electrodes and manufacturing method of stretchable line-shaped super capacitor
CN104392845B (en) * 2014-10-17 2017-03-29 复旦大学 A kind of stretchable linear supercapacitor and preparation method of lithium ion battery
CN104617336B (en) * 2015-02-12 2017-04-19 中国工程物理研究院化工材料研究所 Linear flexible lithium ion battery and preparation method thereof
CN106960979A (en) * 2016-01-08 2017-07-18 三星电子株式会社 Fiber shape electric energy acquisition and storage device and its manufacture method
CN106935916A (en) * 2017-03-01 2017-07-07 东莞市联洲知识产权运营管理有限公司 A kind of preparation method of high-performance zinc Polyaniline Secondary Battery
CN108666617A (en) * 2017-04-01 2018-10-16 哈尔滨工业大学（威海） A kind of zinc/Polyaniline Secondary Battery based on organic system electrolyte
CN108400392B (en) * 2018-01-29 2020-08-14 东华理工大学 Chargeable flexible zinc ion battery and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101728581A (en) * 2008-10-14 2010-06-09 Nec东金株式会社 Lithium ion battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
High-Performance Cable-Type Flexible Rechargeable Zn Battery Based on MnO2@CNT FiberMicroelectrode;Wang, Kai等;《ACS APPLIED MATERIALS & INTERFACES》;20180725;第10卷(第29期);第24573-24582页 *
新型纤维状能源器件的发展和思考;张智涛等;《高分子学报》;20161031(第10期);第1284-1296页 *

Also Published As

Publication number Publication date
CN109950639A (en) 2019-06-28

Similar Documents

Publication Publication Date Title
CN109950639B (en) Metal ion battery and preparation method thereof
CN110323074B (en) Asymmetric all-solid-state fibrous flexible supercapacitor and preparation method thereof
CN104617336B (en) Linear flexible lithium ion battery and preparation method thereof
CN108364797B (en) Preparation method of carbon nanotube fabric electrode and yarn electrode and application of electrode
CN110048174B (en) Gel battery electrolyte membrane and preparation method and application thereof
CN109994322B (en) Battery type super capacitor and application thereof
Dong et al. Matching electrode lengths enables the practical use of asymmetric fiber supercapacitors with a high energy density
CN113036096B (en) Water system zinc-manganese battery fiber with double-function protective layer and preparation method thereof
CN107611434A (en) A kind of preparation method and applications of flexible self-supporting porous carbon nanofiber electrode
CN111769278B (en) Water system rechargeable zinc ion battery based on aromatic organic matter positive electrode material and application thereof
US10727003B2 (en) Cord-yarn structured supercapacitor
CN109390559A (en) A kind of preparation of flexible electrode and flexible energy storage device based on the electrode
CN103700798A (en) Fiber chemical energy storage power supply and preparation method thereof
CN110010373B (en) Electrode zinc embedding treatment method and application thereof in preparation of battery type super capacitor
CN109920955A (en) A kind of cementite compound Nano carbon fiber film and preparation method thereof applied to lithium-sulfur cell interlayer
CN109301182A (en) Static Spinning cobalt/N doping porous carbon nano-composite fiber and its preparation and application
CN110690495B (en) Composite gel polymer solid electrolyte, preparation method thereof and sodium ion battery
JP7298872B2 (en) SEPARATOR, SEPARATOR MANUFACTURING METHOD AND LITHIUM ION BATTERY
CN112635762A (en) Lithium ion battery cathode material, preparation method and application thereof, and lithium ion battery
KR20180127092A (en) lithium secondary battery
CN112216518B (en) Flexible zinc ion hybrid capacitor and preparation method and application thereof
CN115458338B (en) Yarn-shaped super capacitor and preparation method thereof
CN112164828A (en) Fibrous flexible aluminum ion battery and preparation method thereof
KR20220047070A (en) Lithium-sulfur battery cathode using fabric material, lithium-sulfur battery including the same, and manufacturing method thereof
CN109449008B (en) Preparation method and application of self-supporting hollow core-shell structure electrode material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant