CN109950639A - One metal ion species battery and preparation method thereof - Google Patents
One metal ion species battery and preparation method thereof Download PDFInfo
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- CN109950639A CN109950639A CN201910127517.XA CN201910127517A CN109950639A CN 109950639 A CN109950639 A CN 109950639A CN 201910127517 A CN201910127517 A CN 201910127517A CN 109950639 A CN109950639 A CN 109950639A
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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
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- 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
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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
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Abstract
The invention belongs to battery preparation technology fields, and in particular to metal ion species battery and preparation method thereof.The battery includes the positive polar fibers and cathode fiber of matrix and winding on it, and the positive polar fibers and cathode fiber are mutually wound, wherein positive polar fibers are conductive polymer/carbon nanotube composite fiber；Cathode fiber is zinc/carbon nano tube composite fibre；Coated gel electrolyte step process obtains respectively for the positive polar fibers and the cathode fiber.The battery can promote the chemical property of battery and the charge transfer efficiency of positive and negative anodes, battery is made to have low resistance and better high rate performance using first the structure being wound in again on matrix after positive polar fibers and cathode fiber elder generation spiral winding is designed；The anode and cathode are self-supporting electrode, do not need addition conductive agent and binder, significantly reduce the inert fraction in battery, are conducive to the energy density for improving battery.
Description
Technical field
The invention belongs to battery preparation technology fields, and in particular to metal ion species battery and preparation method thereof.
Background technique
Developing the threadiness compatible with traditional textile processes to weave device is the important of realization wearable device flexibility
Approach.Fibrous structure can be realized the flexibility on three-dimensional, can also be as traditional chemical fiber, cotton thread, by low
Different fiber function elements is woven into wearable fabric of good performance by the textile technology of cost, to realize a variety of devices
Part is integrated in the ideal design target in an Intelligent garment.
In Chinese patent literature, the stretchable linear lithium ion battery of one kind and its system are disclosed in CN 103904357A
Preparation Method, this method prepare carbon nanotube/LiMn2O4 composite fibre as anode respectively, then prepare carbon nanotube/lithium titanate
Then positive and negative anodes fibers parallel is wrapped on an elastic rubber by composite fibre as cathode, positive and negative two electrode not phase mutual connection
Touching, then one layer of ethylene oxide/succinonitrile/bis trifluoromethyl sulfimide lithium gel-like electrolyte is applied, it finally encapsulates, obtains one kind
Linear lithium ion battery.In the method, anode and cathode active materials are first dissolved in solution, then drop coating is led to carbon nano tube surface
It crosses physisorption and carbon nanotube forms composite fibre, but the adsorption capacity of the composite fibre is not strong, drawing process is easy to fall off,
Cause capacity retention ratio poor, and the load capacity of active material is uncontrollable, reproducibility is bad；This method uses positive and negative anodes fibers parallel
The mode being wrapped on elastic rubber contacts two fibers not, can have the resistance for increasing battery, reduce the charge of positive and negative anodes
The problems such as efficiency of transmission.In addition, lithium ion battery is more sensitive to oxygen, moisture in air, need just start after encapsulating
Work, but can decline plus the tensile property of battery after encapsulated layer.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that linear battery plus-negative plate charge in the prior art is overcome to transmit
The problems such as low efficiency, to provide a kind of fibrous metal ion battery and preparation method thereof.
For this purpose, the present invention provides the following technical scheme that
The present invention provides a metal ion species battery, positive polar fibers and cathode fibre including matrix and winding on it
Dimension, the positive polar fibers and cathode fiber are mutually wound.
The metal ion battery is Zinc ion battery.
The positive polar fibers are conductive polymer/carbon nanotube composite fiber, and the conducting polymer/carbon nanotube is compound
Conducting polymer and the mass ratio of carbon nanotube are (6-21) in fiber: 14；
The carbon nano-tube fibre diameter is 20~200 μm.
The monomer of the conducting polymer is at least one of aniline, pyrroles and ethylenedioxy thiophene.
The cathode fiber is zinc/carbon nano tube composite fibre, zinc and carbon nanometer in the zinc/carbon nano tube composite fibre
The mass ratio of pipe is (2-9): 3.
The mass ratio of the positive polar fibers and cathode fiber is (1-2): 2.
The metal ion battery further includes coated in the electrolyte layer on positive polar fibers and cathode fiber, the electrolysis
Matter layer is made of acrylamide, polyvinyl alcohol or gelatin；
Described matrix is at least one of polyurethanes, dimethyl silicone polymer and polyurethane elastomer.
The present invention also provides a kind of preparation methods of above-mentioned metal ion battery, prepare the positive polar fibers and institute respectively
State cathode fiber, in the positive polar fibers and the cathode fiber surface coated electrolyte, then by after coating positive polar fibers and
Cathode fiber is intertwined, and is then wound on the matrix, and the metal ion battery is obtained.
The preparation method of the cathode fiber is, using carbon nanotube as working electrode, using three-electrode system, to contain
Zinc/carbon nano tube composite fibre is prepared using electrochemistry constant potential restoring method as electrolyte in the aqueous solution of zinc salt.
The preparation method of the positive polar fibers is, carbon nanotube is placed in containing conducting polymer monomer, dopant
In solution, at -10~25 DEG C, conducting polymer/carbon nanometer is prepared using the method for chemical oxidation or electrochemical oxidation
Pipe composite fibre.
The zinc salt is at least one of zinc sulfate, zinc nitrate and zinc chloride；The concentration of the zinc salt be 0.05~
2mol/L。
Technical solution of the present invention has the advantages that
1. metal ion battery provided by the invention, which includes the positive polar fibers and cathode of matrix and winding on it
Fiber, the positive polar fibers and cathode fiber are mutually wound；Wherein, positive polar fibers are the compound fibre of conducting polymer/carbon nanotube
Dimension；Cathode fiber is zinc/carbon nano tube composite fibre；The positive polar fibers and the cathode fiber distinguish coated gel electrolyte
Matter step process obtains.The battery is using the knot being first wound in again on matrix after positive polar fibers and cathode fiber elder generation spiral winding
Structure design, can promote the chemical property of battery and the charge transfer efficiency of positive and negative anodes, and battery is made to have low resistance and more
Good high rate performance；The anode uses conductive polymer/carbon nanotube composite fiber, and cathode is multiple using zinc/carbon nanotube
Condensating fiber is self-supporting electrode, does not need addition conductive agent and binder, significantly reduces the inert fraction in battery, have
Conducive to the energy density for improving battery.
2. metal ion battery provided by the invention, the battery is using first by positive polar fibers and cathode fiber elder generation spiral winding
The structure design being wound in again on matrix afterwards, stress is concentrated mainly on matrix, and anode and cathode itself are helical fibers,
With surplus is stretched, the battery is enable to have shown excellent stretch-proof and resistance to bend(ing).
3. Zinc ion battery provided by the invention, the specific capacity of the battery reaches as high as 180mAh/g, cycle charge-discharge
5000 specific capacity conservation rates up to 90%, extensibility up to 300%, it is continuously elongated or bending 1000 times after, the ratio of battery
Capacity retention ratio highest can be 95%, and the energy density of battery plus-negative plate material is up to 205Wh/kg.Therefore, provided by the invention
Zinc battery normal condition or by bending wind in the case where can work normally, can apply in wearable device.
4. metal ion battery provided by the invention, the battery is this with intrinsic flexible organic using conducting polymer
Electrode material is as anode, compared to MnO2、V2O5Deng the inorganic Zinc ion battery positive electrode of tradition, zinc can be effectively buffered
Ion inserts the stress that embedding reaction generates, and the cycle charge discharge electric life of Zinc ion battery is substantially improved；Furthermore the sheet of conducting polymer
Sign is flexible, so that fibrous electrodes and battery have superior stretch-proof, mechanical property resistant to bending.
Metal ion battery provided by the invention, cathode fiber are zinc/carbon nano tube composite fibre, using water system electricity
Pond, stable in the air, not needing encapsulated layer can steady operation.
5. the preparation method of metal ion battery provided by the invention, including, positive polar fibers and described are prepared respectively
Cathode fiber in the positive polar fibers and the cathode fiber surface coated electrolyte, then by the positive polar fibers after coating and is born
Polar fibers are intertwined, and are then wound on the matrix, and the metal ion battery is obtained.This method by it is described just
Polar fibers and the cathode fiber are first intertwined, and are then wrapped on matrix again and form ion battery, this direct winding
Structure design can be promoted battery chemical property and promoted positive and negative anodes charge transfer efficiency, make battery have low electricity
Resistance and better high rate performance；Stress is concentrated mainly on matrix using battery prepared by preparation method of the invention, anode
It is wound in matrix with cathode, has and stretches surplus, can avoid the current collector layer coated occur in drawing process and active layer is answered
The phenomenon that power is destroyed, enables the battery to have shown excellent stretch-proof and resistance to bend(ing).The positive polar fibers of coated electrolyte and
Cathode fiber is spirally wound together into first, so that the relative position of anode and cathode is more nearly, can promote the electricity of battery
The charge transfer efficiency of chemical property and positive and negative anodes makes battery have low resistance and better high rate performance；In addition, stretching
The relative position of journey anode and cathode remains unchanged, the structure design can keep positive and negative electrode contact stablize, guarantee stretch or
The stability of person's bending process charge storage efficiency.
6. the preparation method of metal ion battery provided by the invention, when preparing fiber anode and cathode composite fibre,
Active material is deposited to respectively in positive and negative electrode carbon nanotube using in situ chemistry or electrochemical deposition method, make its
Adhesive force on anode and cathode carbon nanotube is good, and not easily to fall off in drawing process, capacity retention ratio is preferable；And the electrification of battery
It learns performance and mechanical stretch performance is obviously improved.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the process flow chart that the embodiment of the present invention 1 prepares Zinc ion battery；
Fig. 2 is the positive polar fibers of battery in the embodiment of the present invention 1 and the schematic diagram that cathode fiber is mutually wound；
Fig. 3 is that positive polar fibers and cathode fiber are wrapped in showing on matrix after first mutually winding again in the embodiment of the present invention 1
It is intended to；
Fig. 4 is the schematic diagram of the tensional state of Fig. 3 battery in the embodiment of the present invention 1；
Fig. 5 is the scanning electron microscope (SEM) photograph of the carbon nano-tube fibre prepared in embodiment 1；
Fig. 6 is the stereoscan photograph of the Polymerization of Polyaniline/carbon Nanotube fiber prepared after chemical oxidising polymerisation in embodiment 1；
Fig. 7 is zinc/carbon nano-tube fibre stereoscan photograph that in embodiment 1 prepared by electro-deposition method；
Fig. 8 be in embodiment 1 by after coated electrolyte positive polar fibers and cathode fiber spiral be intertwined composition
The optical microscope photograph of Zinc ion battery.
Specific embodiment
There is provided following embodiments is to preferably further understand the present invention, it is not limited to the best embodiment party
Formula is not construed as limiting the contents of the present invention and protection scope, anyone under the inspiration of the present invention or by the present invention and its
The feature of his prior art is combined and any and identical or similar product of the present invention for obtaining, all falls within of the invention
Within protection scope.
Specific experiment step or condition person are not specified in embodiment, according to the literature in the art described routine experiment
The operation of step or condition can carry out.Reagents or instruments used without specified manufacturer, being can be by commercially available acquisition
Conventional reagent product.
Embodiment 1
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, is specifically included:
Preparation carbon nanotube: it is fixed on and can rotate using the carbon nano pipe array that spins of vapour deposition process (CVD) growth
Sample stage on, from array edges pull straight width be 12mm carbon nano-tube film, form fiber after twisting, be then collected in
On the roller of rotation, carbon nanotube is spun into serialization long fibre；Wherein, the spiral angle that fiber is collected is 20 °, and carbon nanotube is long fine
Tieing up diameter is 100 μm, as shown in Figure 5；
It prepares conductive polymer/carbon nanotube composite fiber: carbon nanotube long fibre is placed in containing aniline monomer
In aqueous sulfuric acid, at 0 DEG C, potassium peroxydisulfate is added, so that aniline obtains conducting polymer in fiber surface chemical oxidising polymerisation
Object/carbon nanotube composite long fiber shape electrode, as shown in Figure 6；Conducting polymer and the mass ratio of carbon nanotube are 1:1；
Prepare zinc/carbon nano tube composite fibre: using three-electrode system, using carbon nanotube long fibre as working electrode,
It is platinized platinum to electrode, reference electrode is saturated calomel electrode, is put into 0.2mol/L ZnSO4In aqueous solution, using constant potential side
Method, reduction potential are -0.8V, recovery time 10min, zinc/carbon nanotube composite long fiber electrode are prepared, such as Fig. 7 institute
Show；Zinc and the mass ratio of carbon nanotube are 3:2；
It prepares Zinc ion battery: acrylamide (AM) monomer and crosslinking agent N, N'- methylene-bisacrylamide (BIS) is added
Enter the ZnSO of 1mol/L4In aqueous solution, stirring is to being completely dissolved；The concentration of AM is 3g/mL, BIS 0.2mg/mL；Then it is added
Initiator potassium persulfate (K2S2O8) stirring is to being completely dissolved, concentration 50mg/mL；It is 120 μm that internal diameter, which is added, in above-mentioned solution
Glass tube in, positive polar fibers conducting polymer/carbon nanotube of preparation and cathode fiber zinc/carbon nanotube are each passed through
Glass tube is stated, so that positive polar fibers and cathode fiber surface uniformly continuous coat polyacrylamide (PAAM) hydrogel electrolyte,
The diameter of positive polar fibers and cathode fiber is 120 μm after coating；
Using homemade wrapping machine, the positive polar fibers for coating PAAM electrolyte and cathode fiber spiral shape are intertwined
(as shown in Figure 2 and Figure 8), then whole to be further would around on a urethane elastomers matrix (as described in Figure 3), shape
At fibrous Rechargeable zinc ion battery, the state that battery stretches is shown in Fig. 4；Conducting polymer/carbon nanotube composite long fiber shape
Anode and zinc/carbon nanotube composite long fiber cathode mass ratio are 2:3.
Embodiment 2
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference with embodiment 1 is only that matrix
Material, the present embodiment matrix use dimethyl silicone polymer.
Embodiment 3
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference with embodiment 1 is only that matrix
Material, the present embodiment matrix use polyurethane.
Embodiment 4
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, is specifically included:
Preparation carbon nanotube: being fixed on rotatable sample stage using the carbon nano pipe array that spins of CVD growth, from
Array edges pull straight the carbon nano-tube film that width is 5mm, and twisting is collected on the roller of rotation after forming fiber, carbon is received
Mitron is spun into serialization long fibre；Wherein, the spiral angle that fiber is collected is 20 °, and carbon nanotube long fibre diameter is 20 μm；
It prepares conductive polymer/carbon nanotube composite fiber: carbon nanotube long fibre is placed in containing aniline monomer
In aqueous sulfuric acid, 0 DEG C at a temperature of, be added potassium peroxydisulfate so that aniline is led in fiber surface chemical oxidising polymerisation
Electric polymer/carbon nanotube composite long fiber shape electrode, wherein conducting polymer and the mass ratio of carbon nanotube are 5:7；
Prepare zinc/carbon nano tube composite fibre: using three-electrode system, using carbon nanotube long fibre as working electrode,
It is platinized platinum to electrode, reference electrode is saturated calomel electrode, is put into 0.2mol/L ZnSO4In aqueous solution, using constant potential side
Method, reduction potential are -0.8V, and the electrochemical reduction time is 10min, and zinc/carbon nanotube composite long fiber electrode is prepared,
In, the mass ratio of zinc and carbon nanotube is 5:3；
It prepares Zinc ion battery: acrylamide (AM) monomer and crosslinking agent N, N'- methylene-bisacrylamide (BIS) is added
Enter the ZnSO of 1mol/L4In aqueous solution, stirring is to being completely dissolved；The concentration of acrylamide (AM) monomer is 3g/mL, and BIS is
0.2mg/mL；Then initiator potassium persulfate (K is added2S2O8) stirring is to being completely dissolved, concentration 50mg/mL；It will be above-mentioned molten
Liquid is added in the glass tube that an internal diameter is 40 microns, and the positive polar fibers conducting polymer/carbon nanotube and cathode of preparation is fine
Dimension zinc/carbon nanotube is each passed through above-mentioned glass tube, so that positive polar fibers and cathode fiber surface uniformly continuous coat PAAM water
Gel electrolyte, positive polar fibers and cathode fibre diameter are 40 μm after coating；
Using homemade wrapping machine, the positive polar fibers for coating PAAM electrolyte and cathode fiber spiral shape are wrapped in one
It rises, it is then whole to be further would around on a urethane elastomers matrix, form fibrous Rechargeable zinc ion battery；
Conducting polymer/carbon nanotube composite long fiber shape anode and zinc/carbon nanotube composite long fiber cathode mass ratio are 3:4.
Embodiment 5
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, is specifically included:
Preparation carbon nanotube: being fixed on rotatable sample stage using the carbon nano pipe array that spins of CVD growth, from
Array edges pull straight the carbon nano-tube film that width is 20mm, and twisting is collected on the roller of rotation after forming fiber, by carbon
Nanotube is spun into serialization long fibre；Wherein, the spiral angle that fiber is collected is 20 °, and carbon nanotube long fibre diameter is 200 μm；
It prepares conductive polymer/carbon nanotube composite fiber: carbon nanotube long fibre is placed in containing aniline monomer
In aqueous sulfuric acid, 0 DEG C at a temperature of, be added potassium peroxydisulfate so that aniline is led in fiber surface chemical oxidising polymerisation
Electric polymer/carbon nanotube composite long fiber shape electrode, wherein conducting polymer and the mass ratio of carbon nanotube are 1:1；
Prepare zinc/carbon nano tube composite fibre: using three-electrode system, using carbon nanotube long fibre as working electrode,
It is platinized platinum to electrode, reference electrode is saturated calomel electrode, is put into 0.2mol/L ZnSO4In aqueous solution, using constant potential side
Method, reduction potential are -0.8V, and the electrochemical reduction time is 10min, and zinc/carbon nanotube composite long fiber electrode is prepared,
In, the mass ratio of zinc and carbon nanotube is 3:2；
It prepares Zinc ion battery: acrylamide (AM) monomer and crosslinking agent N, N'- methylene-bisacrylamide (BIS) is added
Enter the ZnSO of 1mol/L4In aqueous solution, stirring is to being completely dissolved；The concentration of acrylamide (AM) monomer is 3g/mL, and BIS is
0.2mg/mL；Then initiator potassium persulfate (K is added2S2O8) stirring is to being completely dissolved, concentration 50mg/mL；It will be above-mentioned molten
Liquid is added in the glass tube that an internal diameter is 220 μm, by the positive polar fibers conducting polymer/carbon nanotube and cathode fiber of preparation
Zinc/carbon nanotube is each passed through above-mentioned glass tube, so that positive polar fibers and cathode fiber surface uniformly continuous coat PAAM water-setting
Glue electrolyte, the fibre diameter of positive polar fibers and cathode fiber is 220 μm after coating；
Using homemade wrapping machine, the positive polar fibers for coating PAAM electrolyte and cathode fiber spiral shape are wrapped in one
It rises, it is then whole to be further would around on a urethane elastomers matrix, form fibrous Rechargeable zinc ion battery；
Wherein, conducting polymer/carbon nanotube composite long fiber shape anode and zinc/carbon nanotube composite long fiber cathode mass ratio are
2:3。
Embodiment 6
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference with embodiment 1 is only that, conduction is poly-
Monomer adduct is different, and in preparing conductive polymer/carbon nanotube composite fiber step, aniline is replaced with pyrroles.
Embodiment 7
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference with embodiment 1 is only that, conduction is poly-
Monomer adduct is different, and in preparing conductive polymer/carbon nanotube composite fiber step, aniline is replaced with enedioxy thiophene
Pheno.
Embodiment 8
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference with embodiment 1 is only that preparation is led
Electric polymer/carbon nano tube composite fibre preparation method is different, specifically includes, using three-electrode system, carbon nanotube is long
Fiber is platinized platinum to electrode, reference electrode is saturated calomel electrode, is put into the sulfuric acid water containing aniline monomer as working electrode
In solution, 0 DEG C at a temperature of use constant potential electrochemically oxidative polymerization, current potential 1V, the electropolymerization time be 10min, obtain
Conducting polymer/carbon nanotube composite long fiber shape electrode.
Embodiment 9
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference with embodiment 1 is only that, conduction is poly-
It is different to close reaction temperature in object/carbon nano tube composite fibre step, the temperature of the present embodiment conducting polymer chemical oxidation reaction
It is -10 DEG C.
Embodiment 10
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference with embodiment 1 is only that, conduction is poly-
It is different to close reaction temperature in object/carbon nano tube composite fibre step, the temperature of the present embodiment conducting polymer chemical oxidation reaction
It is 25 DEG C.
Embodiment 11
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference with embodiment 1 is only that, zinc/carbon
In nanotube composite fibre step, zinc salt when deposited metal zinc is Zn (NO3)2。
Embodiment 12
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference with embodiment 1 is only that, zinc/carbon
In nanotube composite fibre step, zinc salt when deposited metal zinc is ZnCl2。
Embodiment 13
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference with embodiment 1 is only that, zinc/carbon
In nanotube composite fibre step, electrolyte when deposited metal zinc is 2mol/L ZnSO4Aqueous solution.
Embodiment 14
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference with embodiment 1 is only that, zinc/carbon
In nanotube composite fibre step, electrolyte when deposited metal zinc is 0.05mol/L ZnSO4Aqueous solution.
Embodiment 15
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference from embodiment 1 is that, conducting polymer
Object/carbon nano tube composite fibre mass ratio, zinc/carbon nano tube composite fibre mass ratio, conducting polymer/carbon nanotube are multiple
Condensating fiber is different with zinc/carbon nano tube composite fibre mass ratio；
In the present embodiment, conducting polymer and carbon nano tube composite fibre in conductive polymer/carbon nanotube composite fiber
Mass ratio be 3:7；The mass ratio of zinc and carbon nano tube composite fibre is 2:3 in zinc/carbon nano tube composite fibre；Conducting polymer
Object/carbon nano tube composite fibre and zinc/carbon nano tube composite fibre mass ratio are 1:1.1.
Embodiment 16
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference from embodiment 1 is that, conducting polymer
Object/carbon nano tube composite fibre mass ratio, zinc/carbon nano tube composite fibre mass ratio, conducting polymer/carbon nanotube are multiple
Condensating fiber is different with zinc/carbon nano tube composite fibre mass ratio；
In the present embodiment, conducting polymer and carbon nano tube composite fibre in conductive polymer/carbon nanotube composite fiber
Mass ratio be 3:2；The mass ratio of zinc and carbon nano tube composite fibre is 3:1 in zinc/carbon nano tube composite fibre；Conducting polymer
Object/carbon nano tube composite fibre and zinc/carbon nano tube composite fibre mass ratio are 1:2.
Embodiment 17
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference from embodiment 1 is that, conducting polymer
Object/carbon nano tube composite fibre mass ratio, zinc/carbon nano tube composite fibre mass ratio, conducting polymer/carbon nanotube are multiple
Condensating fiber is different with zinc/carbon nano tube composite fibre mass ratio；
In the present embodiment, conducting polymer and carbon nano tube composite fibre in conductive polymer/carbon nanotube composite fiber
Mass ratio be 2:3；The mass ratio of zinc and carbon nano tube composite fibre is 2:1 in zinc/carbon nano tube composite fibre；Conducting polymer
Object/carbon nano tube composite fibre and zinc/carbon nano tube composite fibre mass ratio are 1:1.5.
Embodiment 18
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference from embodiment 1 is that, preparing carbon
In the step of nanotube, the spiral angle of twisting is 30 °.
Embodiment 19
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference from embodiment 1 is that, preparing carbon
In the step of nanotube, the spiral angle of twisting is 10 °.
Embodiment 20
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference from embodiment 1 is that, preparing zinc
In ion battery step, gel electrolyte is polyvinyl alcohol；Specifically: 1g polyvinyl alcohol (PVA) is dissolved in 10mL first and is contained
1molL-1Zinc sulfate (ZnSO4) aqueous solution in (0.1g mL-1), it is heated to 80 DEG C under electromagnetic agitation, is kept for 0.5 hour, until
Solution becomes to clarify, and obtains ZnSO4- PVA gel electrolyte.
Embodiment 21
A kind of Zinc ion battery and preparation method thereof is present embodiments provided, the difference from embodiment 1 is that, preparing zinc
In ion battery step, gel electrolyte is gelatin, is specifically contained the preparation method is as follows: 1.5g gelatin is dissolved in 15mL first
1molL-1Sodium sulphate (Na2SO4) aqueous solution in (0.1g mL-1), it is heated to 80 DEG C under electromagnetic agitation, is kept for 0.5 hour, directly
Become to clarify to solution, obtains ZnSO4Gelatin gel electrolyte.
Comparative example 1
This comparative example provides a kind of Zinc ion battery and preparation method thereof, the difference from embodiment 1 is that, prepare zinc from
In the step of sub- battery, by the anode for coating PAAM electrolyte, cathode wound in parallel in a urethane elastomers matrix
On, it does not contact with each other, forms fibrous Rechargeable zinc ion battery.
Test example
The performance test for the Zinc ion battery that this test example provides embodiment 1-21 and comparative example 1 obtains and test knot
Fruit, concrete outcome table 1:
Wherein, the test method of specific capacity are as follows: be connected to two electrode tips of the battery of preparation
VMP3Multichannel Potentiostats (Bio-logic company, France) tester, by constant current charge-discharge method,
I.e. in the case where current density is the charging and discharging currents of 0.5A g-1, it is charged to 1.6V from 0.3V, is then discharged again under same electric current
To 0.3V, discharge time is recorded, it is possible thereby to which specific capacity is calculated；
The test method of the conservation rate of 5000 specific capacities of cycle charge-discharge: the holding of 5000 specific capacities of cycle charge-discharge
The test method of rate is similar with specific volume weight testing method, only 5000 charge and discharge of follow-on test, then with the 5000th charge and discharge
The specific capacity of electricity can be obtained the specific capacity conservation rate of cycle charge-discharge, indicated with R divided by the specific capacity of first time charge and discharge；
The test method of energy density: it based on obtained specific capacity, is calculated and is obtained with formula E=∫ UdC/m；Wherein, U fills
Discharge voltage range, C are specific capacities, and m is the gross mass of anode and cathode active materials；
The test method of extensibility: clamping the both ends of fibre cell with displacement platform, then starts gradually to stretch battery and arrive
A certain length calculates the ratio of tensile elongation and initial length；
After continuously elongated 1000 times, the test method of specific capacity conservation rate: it is stretched to a certain length from initial length, then
Springing back to initial length is a circulation；Test stretches the battery specific capacity of front and back, measures after then being recycled with 1000 stretchings
Specific capacity divided by stretch before initial specific capacities be stretch after capacity retention ratio, indicated with S.
The performance test results for the Zinc ion battery that 1 embodiment 1-21 of table and comparative example 1 obtain
Table 1, embodiment 1 are compared with comparative example 1, and the specific capacity for the Zinc ion battery that embodiment 1 obtains is apparently higher than comparison
The specific capacity of battery in example 1 illustrates to be wound on matrix again after the present invention uses anode and cathode fiber elder generation spiral winding
Structure design helps to improve the chemical property of battery and the charge transfer efficiency of positive and negative anodes；The battery that embodiment 1 obtains
The conservation rate of 5000 specific capacities of cycle charge-discharge is higher than comparative example 1, illustrates that the service life of battery of the present invention is longer；Implement
The extensibility for the battery that example 1 obtains is better than comparative example 1, illustrates that the stretch resistance of battery provided by the invention can be with resistance to bend(ing) energy
It is excellent.The energy of specific capacity conservation rate, positive polar fibers and cathode fiber after continuously elongated 1000 times of the battery that embodiment 1 obtains
Density is superior to comparative example 1.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And thus amplify out it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a metal ion species battery, positive polar fibers and cathode fiber including matrix and winding on it, which is characterized in that institute
It states positive polar fibers and cathode fiber is mutually wound.
2. metal ion battery according to claim 1, which is characterized in that the metal ion battery is zinc ion electricity
Pond.
3. metal ion battery according to claim 1 or 2, which is characterized in that the positive polar fibers be conducting polymer/
Carbon nano tube composite fibre, the quality of conducting polymer and carbon nanotube in the conductive polymer/carbon nanotube composite fiber
Than for (6-21): 14；
The carbon nano-tube fibre diameter is 20~200 μm.
4. metal ion battery according to claim 3, which is characterized in that the monomer of the conducting polymer be aniline,
At least one of pyrroles and ethylenedioxy thiophene.
5. according to any metal ion battery of claim 2-4, which is characterized in that the cathode fiber is that zinc/carbon is received
Mitron composite fibre, zinc and the mass ratio of carbon nanotube are (2-9) in the zinc/carbon nano tube composite fibre: 3.
6. -5 any metal ion battery according to claim 1, which is characterized in that the positive polar fibers and cathode fiber
Mass ratio be (1-2): 2.
7. -6 any metal ion battery according to claim 1, which is characterized in that further include be coated in positive polar fibers and
Electrolyte layer on cathode fiber, the electrolyte layer are made of acrylamide, polyvinyl alcohol or gelatin；
Described matrix is at least one of polyurethanes, dimethyl silicone polymer and polyurethane elastomer.
8. a kind of preparation method of metal ion battery as claimed in claim 1 to 7, which is characterized in that prepare respectively described
Positive polar fibers and the cathode fiber, in the positive polar fibers and the cathode fiber surface coated electrolyte, then will be after coating
Positive polar fibers and cathode fiber be intertwined, then wound on the matrix, obtain the metal ion battery.
9. preparation method according to claim 8, which is characterized in that the preparation method of the cathode fiber is to receive carbon
Mitron is as working electrode, using three-electrode system, to contain the aqueous solution of zinc salt as electrolyte, using electrochemistry constant potential
Zinc/carbon nano tube composite fibre is prepared in restoring method；
The zinc salt is at least one of zinc sulfate, zinc nitrate and zinc chloride；The concentration of the zinc salt is 0.05~2mol/L.
10. preparation method according to claim 8 or claim 9, which is characterized in that the preparation method of the positive polar fibers is to incite somebody to action
Carbon nanotube be placed in containing conducting polymer monomer, dopant solution in, at -10~25 DEG C, using chemical oxidation or
Conductive polymer/carbon nanotube composite fiber is prepared in the method for electrochemical oxidation.
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