CN110444822A - A kind of preparation method of the quasi- solid-state Zinc ion battery of integration - Google Patents
A kind of preparation method of the quasi- solid-state Zinc ion battery of integration Download PDFInfo
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
A kind of preparation method of the quasi- solid-state Zinc ion battery of integration, it is related to battery technology field, the present invention is matrix using hydrogel, inside anode and negative electrode material the insertion gel-in-matrix of Zinc ion battery, the integral structure for realizing battery, the problems such as avoiding conventional batteries anode, the layering assembling bring interface of diaphragm and cathode, compatibility and short circuit.Gel electrolyte of the present invention using hydrogel as Zinc ion battery, the flexible zinc load of centre embedding electrodeposition process preparation, is aggregated in gel electrolyte surface as anode for polymer material in-situ chemical later.The interface impedance that the quasi- solid-state Zinc ion battery of the customized integration of shape can be effectively reduced inside battery is obtained, electrolyte ion is promoted quickly to transmit in electrode interior.More positive electrode load areas can be provided for battery above all through this design, and then greatly improve the energy density of battery.The present invention is applied to field of batteries.
Description
Technical field
The present invention relates to Zinc ion battery fields, and in particular to a kind of preparation side of the quasi- solid-state Zinc ion battery of integration
Method.
Background technique
With the fast development of wearable portable electronic device, motivate researcher to the continuous of flexible energy storage device
Research.Because lithium ion battery there are lithium sources it is limited, electrolyte is inflammable, manufacturing cost is expensive the disadvantages of, various high safeties, low cost
Novel battery system furtherd investigate, with reach replace lithium ion battery purpose.Wherein, the chargeable zinc of water system from
Sub- battery is as a kind of emerging battery system, since its nontoxic and pollution-free property and environment friendly, extremely low manufacturing cost etc. are excellent
Point, it is considered to be most hopeful the next-generation energy storage system instead of lithium ion battery.Related water system is chargeable since 2016
Zinc ion battery research it is more and more deep, wherein also relating to various wearable flexible Zinc ion batteries and fiber shape
Zinc ion battery.But the exploitation and design of novel stabilising positive electrode are had focused largely on to the research of Zinc ion battery at present,
The assembling of Zinc ion battery still uses traditional anode, the layer-stepping combination of diaphragm and cathode.The side of this assembled battery
Formula can make all there is interfacial contact internal resistance between anode and diaphragm and cathode and diaphragm, influence the chemical property of battery.In addition,
For being easy after needing the wearable energy storage system of various deformation, battery pole piece and diaphragm layering to be assembled in multiple bending deformation
It is mobile in inside battery that pole piece occurs, and then generates battery short circuit phenomenon.
Although Zinc ion battery using the zinc metal of high capacity as negative electrode material, the reason for the positive electrode developed at present
It is all more much lower than the capacity of zinc load by capacity, cause the capacity of the Zinc ion battery obtained using traditional assembling mode lower.
The area load amount for increasing positive electrode can effectively improve the capacity and energy of Zinc ion battery, but with common mixing paste-painting
The pole piece mode for preparing of cloth goes to increase pole piece thickness, will lead to positive electrode and falls off in charge and discharge process, electrolyte profit
It is wet insufficient, substantially reduce the utilization rate of positive electrode.Therefore, a kind of integrated zinc with high positive load area is prepared
Ion battery is of great significance to the development of wearable energy storage device.
Summary of the invention
The present invention is intended to provide a kind of quasi- solid-state Zinc ion battery of high-energy integration, using gel electrolyte can casting mold
The cathode embedding of Zinc ion battery wherein, is recycled in-situ chemical polymerization to be supported on the anode of Zinc ion battery by characteristic
The outer surface of gel electrolyte efficiently avoids the interfacial contact impedance between battery component, and greatly improves just
The problem of load area of pole, it is hereby achieved that the quasi- solid-state zinc ion of the integration of high area specific energy and high energy density per unit volume
Battery.
The quasi- solid-state Zinc ion battery of a kind of integration of the invention, the preparation of the Zinc ion battery is electrolysed with hydrogel
Matter is matrix, and the cathode of battery is embedded among gel electrolyte matrix, and gel electrolyte outer surface polymerize one layer of polymeric
For the anode of battery.
A kind of preparation method of the quasi- solid-state Zinc ion battery of integration of the invention, it is followed the steps below:
One, the preparation of zinc load: choosing zinc sulfate and Klorvess Liquid is electroplate liquid, with carbon cloth, carbon paper, graphene paper or
Carbon fiber is working electrode, and metallic zinc is that electrode and reference electrode are electroplated on a flexible substrate using above-mentioned electroplate liquid, is obtained
The flexible zinc load of zinc nanometer sheet cladding；
Two, aquogel polymer monomer, initiator and crosslinking agent the initiation of gel electrolyte: are dissolved in zinc salt electrolyte
In, being stirred at room temperature causes aquogel polymer monomer sufficiently, obtains the hydrosol；
Three, the flexible embedding of zinc load and the crosslinking of gel electrolyte: flexible zinc load prepared by step 1 is put into step
In rapid two obtained aqueous solution, be subsequently placed in vacuum oven and be de-gassed, be placed in mold, make in an oven
Flexible zinc load is embedded among the matrix of gel electrolyte by gel electrolyte crosslinking casting mold simultaneously；
Four, positive in-situ chemical polymerization: in aqueous solution by the dispersion of positive polymer monomer, solution A is obtained；By oxidant
Dispersion in aqueous solution, obtains solution B；The volume ratio of solution A and solution B is 1:1, by the solidifying of embedding cathode prepared by step 3
Glue electrolyte matrix is placed in solution A, and solution B is added dropwise in solution A later, is polymerize under the conditions of 0~5 DEG C by stirring
Reaction, in gel electrolyte surface in situ chemical polymerization polymers as cathode materials, the i.e. quasi- solid-state Zinc ion battery of integratorization；
The hydrogel is polyacrylamide, polyacrylic acid and polyvinyl alcohol and one such or several mixture.
The present invention include it is following the utility model has the advantages that
1. the Zinc ion battery of acquisition will using a kind of preparation method of the quasi- solid-state Zinc ion battery of integration of the invention
Positive electrode and negative electrode material are embedded in gel electrolyte intrinsic silicon, and diaphragm needed for not needing conventional batteries preparation avoids
Interface between electrode and diaphragm, and then avoid Zinc ion battery and cause short circuit problem during repeated deformation, and
Reduce the contact impedance between interface.
2. using a kind of preparation method of the quasi- solid-state Zinc ion battery of integration of the invention, the Zinc ion battery knot of acquisition
Structure makes battery obtain more positive electrode loads as axle center, polymer anode similar to coaxial configuration, zinc load as outer layer
Area, to improve the area specific energy and energy density per unit volume of Zinc ion battery.
3. the quasi- solid-state Zinc ion battery of a kind of integration of the invention, electrode material pertains only to electro-deposition during the preparation process
It polymerize two kinds of steps with in-situ chemical, eliminating one in traditional pole piece preparation process is the cumbersome process of class, and life is greatly saved
Produce cost and production time.
4. the quasi- solid-state Zinc ion battery of a kind of integration of the invention, is assembled using gel electrolyte instead of common batteries
Diaphragm in the process saves the production cost of membrane portions.In addition gel electrolyte is instead of liquid electrolyte, in battery
Portion does not have liquid flowing, and there is no the leakage problems of battery.
5. the quasi- solid-state Zinc ion battery of a kind of integration of the invention has extraordinary flexibility, may be implemented repeatedly repeatedly
Bending knots and winding, is widely used space in flexible portable field of electronic device.
6. the quasi- solid-state Zinc ion battery of a kind of integration of the invention, is not related to any Large expensive during the preparation process
Instrument is very suitable to the large-scale commercial production of Zinc ion battery.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the quasi- solid-state Zinc ion battery of integrated flexible；
Fig. 2 is the structural schematic diagram of the quasi- solid-state Zinc ion battery of linear integration；
Fig. 3 is the photo of the quasi- solid-state Zinc ion battery of planar rectangular integration of 1 method of example preparation；
Fig. 4 is the photo of the quasi- solid-state Zinc ion battery of linear integration of 2 method of example preparation.
Specific embodiment
Specific embodiment 1: a kind of quasi- solid-state Zinc ion battery of integration, the preparation of the Zinc ion battery be with
Hydrogel electrolyte is matrix, and the cathode of battery is embedded among gel electrolyte matrix, the polymerization of gel electrolyte outer surface
One layer of polymeric is the anode of battery.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: the hydrogel is polypropylene
Amide, polyacrylic acid and polyvinyl alcohol and one such or several mixture.It is other same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first embodiment in that: the electrolyte be zinc sulfate,
Zinc chloride or trifluoromethayl sulfonic acid zinc.It is other same as the specific embodiment one.
Specific embodiment 4: the present embodiment is different from the first embodiment in that: the cathode of the battery be
The flexible cathode or zinc metal that electrodepositing zinc obtains on carbon cloth, carbon paper, graphene paper or carbon fiber.Other and specific implementation
Mode one is identical.
Specific embodiment 5: the present embodiment is different from the first embodiment in that: the battery just extremely gathers
Aniline, poly-dopamine or quinones polymer.It is other same as the specific embodiment one.
Specific embodiment 6: a kind of preparation method of the quasi- solid-state Zinc ion battery of integration of present embodiment, it is
It follows the steps below:
One, the preparation of zinc load: choosing zinc sulfate and Klorvess Liquid is electroplate liquid, with carbon cloth, carbon paper, graphene paper or
Carbon fiber is working electrode, and metallic zinc is that electrode and reference electrode are electroplated on a flexible substrate using above-mentioned electroplate liquid, is obtained
The flexible zinc load of zinc nanometer sheet cladding；
Two, aquogel polymer monomer, initiator and crosslinking agent the initiation of gel electrolyte: are dissolved in zinc salt electrolyte
In, being stirred at room temperature causes hydrogel sufficiently, obtains the hydrosol；
Three, the flexible embedding of zinc load and the crosslinking of gel electrolyte: flexible zinc load prepared by step 1 is put into step
In rapid two obtained aqueous solution, be subsequently placed in vacuum oven and be de-gassed, be placed in mold, make in an oven
Flexible zinc load is embedded among the matrix of gel electrolyte by gel electrolyte crosslinking casting mold simultaneously；
Four, the dispersion of positive polymer monomer positive in-situ chemical polymerization: is obtained into solution A in aqueous solution；By oxidant
Dispersion in aqueous solution, obtains solution B；The volume ratio of solution A and solution B is 1:1, by the solidifying of embedding cathode prepared by step 3
Glue electrolyte matrix is placed in solution A, and solution B is added dropwise in solution A later, is polymerize under the conditions of 0~5 DEG C by stirring
Reaction, in gel electrolyte surface in situ chemical polymerization polymers as cathode materials, the i.e. quasi- solid-state Zinc ion battery of integratorization；
The hydrogel is polyacrylamide, polyacrylic acid and polyvinyl alcohol and one such or several mixture.
Specific embodiment 7: present embodiment is unlike specific embodiment six: the integration that will be prepared
Quasi- solid-state Zinc ion battery is packaged: the electroplated substrates of flexible zinc load are the collector of battery cathode, separately take positive collection
The battery surface of Fluid inclusions step 4 preparation realizes that consolidation encapsulates the quasi- solid-state Zinc ion battery of integration using heat-shrink tube.Its
It is identical as specific embodiment six.
Specific embodiment 8: present embodiment is unlike specific embodiment six: the anode polymer monomer
For polyaniline, poly-dopamine or quinones polymer, and the concentration of positive polymer monomer is 0.0125~0.125mLmL-1.Its
It is identical as specific embodiment six.
Specific embodiment 9: present embodiment is unlike specific embodiment six: zinc sulfate and chlorine in electroplate liquid
The concentration for changing potassium is 1molL-1.It is other identical as specific embodiment six.
Specific embodiment 10: present embodiment is unlike specific embodiment six:
If just extremely polyaniline, oxidant described in step 4 are ammonium persulfate or potassium peroxydisulfate；
If just extremely poly-dopamine, oxidant described in step 4 are in sodium metaperiodate, hydrogen peroxide or air
Oxygen；
If just extremely quinones polymer, oxidant described in step 4 are iodine, potassium metaperiodate or sodium metaperiodate.
If oxidant is ammonium persulfate, the concentration of oxidant is 0.0458~0.458gmL-1.Other and specific implementation
Mode six is identical.
Specific embodiment 11: present embodiment is unlike specific embodiment six: initiator is ammonium persulfate
Or potassium peroxydisulfate.It is other identical as specific embodiment six.
Specific embodiment 12: present embodiment is unlike specific embodiment six: crosslinking agent N, N- methylene
Base bisacrylamide or glutaraldehyde.It is other identical as specific embodiment six.
The content of present invention is not limited only to the content of the respective embodiments described above, the group of one of them or several specific embodiments
The purpose of invention also may be implemented in contract sample.
It is elaborated according to example and Detailed description of the invention to the present invention:
Embodiment 1
A kind of preparation method of the quasi- solid-state Zinc ion battery of integration of the present embodiment, follows the steps below:
(1) carbon cloth of 1cm × 4cm alcohol is taken to be cleaned by ultrasonic clean, drying.Prepare 1molL-1ZnSO4And 1mol
L-1The mixed solution 50mL of KCl is used as zinc-plated electroplate liquid.Using the carbon cloth cleaned up as working electrode, metallic zinc be to electrode and
Reference electrode, with 1mAcm in electroplate liquid-2Electric current on carbon cloth constant current it is zinc-plated for 24 hours, obtain zinc-plated carbon cloth, spend
Ionized water is dried for standby after rinsing surface.
(2) 4g acrylamide monomer, 0.15g potassium peroxydisulfate initiator are taken, 0.006g N, N- methylene-bisacrylamide is handed over
Connection agent is dissolved in 20mL deionized water, and a hour is stirred at room temperature.
(3) the zinc-plated carbon cloth for taking step (1) to prepare is put in the solution of step (2), is placed in a vacuum drying oven later de-
Gas 30 seconds.Zinc-plated carbon cloth and solution are put in the mold of planar rectangular later, are placed in 50 DEG C of baking ovens casting mold 4 hours.
(4) take 1.0mL aniline monomer in 40mL 1molL-1Hydrochloric acid solution in, separately take 3.67g ammonium persulfate to be dissolved in
40mL 1mol·L-1Hydrochloric acid solution in.The gel electrolyte matrix that cathode is embedded prepared by step (3) is placed in aniline list
In the hydrochloric acid solution of body, half an hour is stirred, the hydrochloric acid solution of ammonium persulfate is added dropwise in the hydrochloric acid solution of aniline monomer later
It is reacted 6 hours under the conditions of 0-5 DEG C, in gel electrolyte surface in situ chemical polymerization polyaniline, uses deionized water after having reacted
Clean up gel surface.
(5) gel for the insertion positive and negative anodes for taking step (4) to be prepared, cuts the polyaniline gel of gel surrounding, leaves
The polyaniline of rectangular top surface and lower surface makees anode, cuts the gel of 0.5cm long on carbon cloth as negative current collector, postposition
In 1molL-1In chlorination zinc electrolyte, electrolyte is fully absorbed.
(6) it takes and cuts battery upper surface and lower surface work that suitable plus plate current-collecting body carbon cloth is covered on step (5) preparation
For the collector of anode, the quasi- solid-state Zinc ion battery consolidation of integration is encapsulated using heat-shrink tube, flexible flat square is prepared
The quasi- solid-state Zinc ion battery of shape integration.
Fig. 3 is the photo of the quasi- solid-state Zinc ion battery of planar rectangular integration of 1 method of example preparation.It is obtained by this method
The area specific energy of the Zinc ion battery obtained can reach 0.3mWh/cm-2To 1.0mWh/cm-2In range, area power is close
Degree can reach 0.1mW/cm-2To 0.6mW/cm-2In range.
Embodiment 2
(1) the carbon cloth fiber alcohol of 3cm long is taken to be cleaned by ultrasonic clean, drying.Prepare 1molL-1ZnSO4And 1mol
L-1The mixed solution 50mL of KCl is used as zinc-plated electroplate liquid.Using the carbon cloth cleaned up as working electrode, metallic zinc be to electrode and
Reference electrode, with 1mAcm in electroplate liquid-2Electric current on carbon cloth the zinc-plated 12h of constant current, obtain zinc-plated carbon cloth fiber,
It is dried for standby after rinsing surface with deionized water.
(2) 4g acrylamide monomer, 0.15g potassium peroxydisulfate initiator are taken, 0.006g N, N- methylene-bisacrylamide is handed over
Connection agent is dissolved in 20mL deionized water, and a hour is stirred at room temperature.
(3) the zinc-plated carbon cloth for taking step (1) to prepare is put in the solution of step (2), is placed in a vacuum drying oven later de-
Gas 30 seconds.Zinc-plated carbon cloth and solution are put in linear mold, are placed in 50 DEG C of baking ovens casting mold 4 hours later.
(4) take 1.5mL aniline monomer in 40mL 1molL-1Hydrochloric acid solution in, separately take 5.5g ammonium persulfate to be dissolved in
40mL 1mol·L-1Hydrochloric acid solution in., the gel electrolyte matrix that cathode is embedded prepared by step (3) is placed in aniline
In the hydrochloric acid solution of monomer, half an hour is stirred, the hydrochloric acid solution of ammonium persulfate is added dropwise to the hydrochloric acid solution of aniline monomer later
In reacted 6 hours under the conditions of 0-5 DEG C, in gel electrolyte surface in situ chemical polymerization polyaniline, use deionization after having reacted
Water cleans up gel surface.
(5) gel for taking the insertion anode and cathode that step (4) is prepared cuts coagulating for 0.5cm long on carbon cloth fiber
Glue be used as negative current collector, be placed on 1molL-1In chlorination zinc electrolyte, electrolyte is fully absorbed.
(6) the suitable plus plate current-collecting body carbon cloth of cutting is taken to be wrapped in collection of the battery surface of step (5) preparation as anode
Fluid is encapsulated the quasi- solid-state Zinc ion battery consolidation of integration using heat-shrink tube, be prepared the linear quasi- solid zinc of integration from
Sub- battery.
Fig. 4 is the photo of the quasi- solid-state Zinc ion battery of linear integration of 2 method of example preparation.It is obtained by this method
The length specific energy of Zinc ion battery can reach 0.03mWh/cm-1To 0.10mWh/cm-1In range, length power density
It can reach 0.05mW/cm-1To 0.9mW/cm-1In range.
Embodiment 3
(1) graphene paper of 5cm × 5cm is taken.Prepare 1molL-1ZnSO4And 1molL-1The mixed solution 50mL of KCl
As zinc-plated electroplate liquid.Using the carbon cloth cleaned up as working electrode, metallic zinc is to electrode, and saturated calomel electrode is reference electricity
Pole, with 2mAcm in electroplate liquid-2Electric current in graphene paper the zinc-plated 48h of constant current, obtain zinc-plated graphene paper, use
Deionized water is dried for standby after rinsing surface.
(2) 4g acrylamide monomer, 0.15g potassium peroxydisulfate initiator are taken, 0.006g N, N- methylene-bisacrylamide is handed over
Connection agent is dissolved in 20mL deionized water, and a hour is stirred at room temperature.
(3) the zinc-plated carbon cloth for going to step (1) to prepare is put in the solution of step (2), is placed in a vacuum drying oven later de-
Gas 30 seconds.Zinc-plated carbon cloth and solution are put in the mold of plane square later, are placed in 50 DEG C of baking ovens casting mold 4 hours.
(4) take 1.5mL aniline monomer in 40mL 1molL-1Hydrochloric acid solution in, separately take 5.5g ammonium persulfate to be dissolved in
40mL 1mol·L-1Hydrochloric acid solution in., the gel electrolyte matrix that cathode is embedded prepared by step (3) is placed in aniline
In the hydrochloric acid solution of monomer, half an hour is stirred, the hydrochloric acid solution of ammonium persulfate is added dropwise to the hydrochloric acid solution of aniline monomer later
In reacted 6 hours under the conditions of 0-5 DEG C, in gel electrolyte surface in situ chemical polymerization polyaniline, use deionization after having reacted
Water cleans up gel surface.
(5) gel of the insertion anode and cathode that take step (4) to be prepared, cuts the polyaniline gel of gel surrounding,
The polyaniline for leaving square shape upper and lower surfaces makees anode, cuts the gel of 0.5cm × 0.5cm area in graphene paper
As negative current collector, be placed on 1molL-1In chlorination zinc electrolyte, electrolyte is fully absorbed.
(6) take cut suitable plus plate current-collecting body graphene paper be covered on step (5) preparation battery upper surface make and under
Surface is the collector of anode, encapsulates the quasi- solid-state Zinc ion battery consolidation of integration using heat-shrink tube, plane is being prepared just
The rectangular quasi- solid-state Zinc ion battery of integration.
Claims (10)
1. a kind of quasi- solid-state Zinc ion battery of integration, which is characterized in that the preparation of the Zinc ion battery is with hydrogel electricity
Xie Zhiwei matrix, the cathode of battery are embedded among gel electrolyte matrix, and gel electrolyte outer surface polymerize a layers of polymer
Object is the anode of battery.
2. the quasi- solid-state Zinc ion battery of a kind of integration according to claim 1, it is characterised in that the hydrogel is poly-
Acrylamide, polyacrylic acid and polyvinyl alcohol and one such or several mixture.
3. the quasi- solid-state Zinc ion battery of a kind of integration according to claim 1, it is characterised in that the electrolyte is sulphur
Sour zinc, zinc chloride or trifluoromethayl sulfonic acid zinc.
4. the quasi- solid-state Zinc ion battery of a kind of integration according to claim 1, it is characterised in that the cathode of the battery
It is the flexible cathode or zinc metal that electrodepositing zinc obtains on carbon cloth, carbon paper, graphene paper or carbon fiber.
5. the quasi- solid-state Zinc ion battery of a kind of integration according to claim 1, it is characterised in that the anode of the battery
For polyaniline or poly-dopamine；Or quinones polymer.
6. a kind of preparation method of the quasi- solid-state Zinc ion battery of integration, which is characterized in that it is followed the steps below:
One, the preparation of zinc load: choosing zinc sulfate and Klorvess Liquid is electroplate liquid, with carbon cloth, carbon paper, graphene paper or carbon fiber
Dimension is working electrode, and metallic zinc is that electrode and reference electrode are electroplated on a flexible substrate using above-mentioned electroplate liquid, obtains zinc and receives
The flexible zinc load of rice piece cladding；
Two, the initiation of gel electrolyte: aquogel polymer monomer, initiator and crosslinking agent are dissolved in zinc salt electrolyte, In
Stirring causes aquogel polymer monomer sufficiently at room temperature, obtains the hydrosol；
Three, the flexible embedding of zinc load and the crosslinking of gel electrolyte: flexible zinc load prepared by step 1 is put into step 2
In obtained aqueous solution, be subsequently placed in vacuum oven and be de-gassed, be placed in mold, make gel in an oven
Flexible zinc load is embedded among the matrix of gel electrolyte by electrolyte crosslinking casting mold simultaneously；
Four, positive in-situ chemical polymerization: in aqueous solution by the dispersion of positive polymer monomer, solution A is obtained；By disperse oxidant
In aqueous solution, solution B is obtained；The volume ratio of solution A and solution B is 1:1, and the gel electricity of cathode will be embedded prepared by step 3
Solution matter matrix is placed in solution A, stirs, solution B is added dropwise in solution A later, carries out polymerization reaction under the conditions of 0~5 DEG C,
In gel electrolyte surface in situ chemical polymerization polymers as cathode materials, the i.e. quasi- solid-state Zinc ion battery of integratorization；It is described
Hydrogel is polyacrylamide, polyacrylic acid and polyvinyl alcohol and one such or several mixture.
7. a kind of preparation method of the quasi- solid-state Zinc ion battery of integration according to claim 6, which is characterized in that will make
The standby obtained quasi- solid-state Zinc ion battery of integration is packaged: the electroplated substrates of flexible zinc load are the afflux of battery cathode
Body separately takes the battery surface of plus plate current-collecting body package step 4 preparation, realizes that consolidation encapsulates the quasi- solid-state of integration using heat-shrink tube
Zinc ion battery.
8. a kind of preparation method of the quasi- solid-state Zinc ion battery of integration according to claim 6, which is characterized in that described
Positive polymer monomer is polyaniline, poly-dopamine or quinones polymer.
9. a kind of preparation method of the quasi- solid-state Zinc ion battery of integration according to claim 6, which is characterized in that plating
The concentration of zinc sulfate and potassium chloride is 1molL in liquid-1。
10. a kind of preparation method of the quasi- solid-state Zinc ion battery of integration according to claim 6, which is characterized in that
If just extremely polyaniline, oxidant described in step 4 are ammonium persulfate or potassium peroxydisulfate；
If just extremely poly-dopamine, oxidant described in step 4 are the oxygen in sodium metaperiodate, hydrogen peroxide or air；
If just extremely quinones polymer, oxidant described in step 4 are iodine, potassium metaperiodate or sodium metaperiodate.
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