CN109065368A - The flexible super capacitor and preparation method thereof of the heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide based on carbon cloth load - Google Patents
The flexible super capacitor and preparation method thereof of the heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide based on carbon cloth load Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of NiS-MoS based on carbon cloth load2The flexible super capacitor and preparation method thereof of heterogeneous nano-chip arrays structure belongs to new energy materials and its device preparation technical field.The NiS-MoS that the flexible super capacitor uses the carbon cloth of the high-purity directly grown on three-dimensional carbon cloth, high density, high orientation to load2Heterogeneous nano-chip arrays structure is anode material, and the carbon cloth of active carbon cladding is cathode material, and PVA/KOH gel is respectively diaphragm and electrolyte, and common assembling obtains.Anode purity is high, density is big, pattern is neat, and the stringent controllable, equipment of growth conditions and simple process, low in cost, capacitance is high, stable charge/discharge is good；The cathode material excellent conductivity, double layer capacity capacity are big；Capacitor preparation process is simple, it is economic and environment-friendly, without post-processing.Supercapacitor proposed by the present invention is light-weight, capacity is big, cycle charge discharge electrical stability is good, while having good flexibility, can be used for the power supply unit of wearable electronic device.
Description
Technical field
The present invention relates to a kind of flexible supers of heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide based on carbon cloth load
Capacitor and preparation method thereof belongs to new energy materials and its device preparation technical field.
Background technique
Supercapacitor be that a kind of own wt is light, charging rate is fast, long service life, power density are high and use at
The general name of this low energy storage device.Since this concept of supercapacitor comes out, research is concerned.According to its energy storage
The difference of mechanism, supercapacitor can be divided into two major classes: i.e. double layer capacity type capacitor and fake capacitance type capacitor.Wherein,
Double layer capacity type capacitor mainly leans on the adsorption-desorption process of electrode surface to store and discharge electric energy, its main feature is that charge and discharge
Electric speed is fast, and power density is high, good cycling stability, but specific capacitance is smaller.And fake capacitance type capacitor mainly leans on electricity
The oxidation-reduction reaction of Rapid reversible stores and discharges electric energy on the material surface of pole, its main feature is that specific capacitance is big, it is usually double
The several times of layer capacitance type capacitor；But just because of wherein there is oxidation-reduction reaction process, causes its electrode unstable, fill
Discharge cycle performance is relatively poor.Therefore, at present the research hotspot in the field first is that, by double layer capacity type and fake capacitance type
Electrode material combines, and integrates the advantage of the two, prepares the supercapacitor that capacity is big, performance is stable.
In numerous known fake capacitance type capacitor electrode materials, nickel based compound such as nickel oxide, nickel hydroxide, vulcanization
Nickel etc., it is wide since nickel element has multiple oxidation states, and material oxidation-reduction activities with higher itself
In the general research and application applied to supercapacitor.Wherein, vulcanize nickel material, including NiS, Ni3S2、NiS2And Ni3S4
Deng, compared to traditional nickel oxide and nickel hydroxide electrode material, theory fake capacitance value with higher, while having higher
Electric conductivity, therefore be potential high-performance super capacitor electrode material.However, the stability due to sulfide is poor, in oxygen
Phenomena such as phase transformation, decomposition, deformation are easy to happen in change-reduction process causes pure nickel sulfide as electrode material in charge and discharge
Capacitive property decline quickly, is unable to satisfy the requirement of multiple cycle charge-discharge in journey.Therefore, by nickel sulfide and other bilayers
Capacitive Material cladding is the effective way for improving nickel sulfide based capacitor electrode material.For example, molybdenum sulfide (MoS2) material,
It is a kind of typical two-dimentional transient metal sulfide, there is lamellar structure, interlayer is combined by weaker Van der Waals force, is had
Conducive to the insertion and abjection of ion (molecule), while electronics can effectively be adsorbed in the surface of its lamella, therefore MoS2Have
Good double layer capacity performance；Moreover, being by stronger Covalent bonding together, therefore MoS in its layer2Also there is stronger mechanicalness
Can, lamellar structure is able to maintain during charge and discharge cycles and is not destroyed, and there is excellent cyclical stability.Thus, by sulphur
Change nickel and MoS2It is mutually compound, by the capacitive property that can promote composite material and utilize MoS2Excellent mechanical stability, most
Integral capacitor performance (W.H.Luo, et al., One- based on nickel sulfide-vulcanization molybdenum composite material supercapacitor are promoted eventually
step extended strategy for the ionic liquid assisted synthesis of Ni3S4-
MoS2heterojunction electrodes for supercapacitors.Journal of Materials
Chemistry A,2017,5,11278)。
However, the performance of electrode material for super capacitor and the pattern of its active material are closely related, how to design and make
The active site for stablizing, fully exposing active material for the microstructure of large specific surface area and stable appearance out, is the neck
The difficult point of domain research.For example, MoS2How the active site of lamellar structure steadily sufficiently exposes at the edge of its nanometer sheet
Its active site is its research hotspot.Moreover, compared to the MoS of other patterns2With vulcanization nickel composite material, two-dimensional sheet is heterogeneous
Structure has many advantages, is more advantageous to and plays MoS2With the respective performance characteristics of nickel sulfide because two-dimensional sheet structure has
Large specific surface area, this is conducive to the shuttle and diffusion of reactive material therebetween, can be from kinetically quickening electrochemical reaction
It carries out；Meanwhile sheet Heterogeneous Composite can effectively expose MoS2Edge active site, and make MoS2Original lamella knot
Structure can obtain intact holding, effectively play its every excellent characteristics.But there is presently no about NiS-MoS2It is heterogeneous to receive
The report of rice piece.
On the other hand, electrode material is configured to three-dimensional multistage tower structure, supercapacitor can be promoted from every side
Performance: (1) active material is directly grown in three-dimensional conductive substrates, load will be made in unit geometric area (volume) more
More effective active materials sufficiently exposes active site, can effectively promote the specific capacitance performance of supercapacitor；(2) three
The conductive network of dimension can promote the electric conductivity of electrode material entirety, to promote the charge-discharge velocity of capacitor and improve power
Density；(3) conducting matrix grain of high mechanical strength reunion of the active material in charge and discharge process can be effectively avoided, decompose and
Deformation etc., to promote the cyclical stability of capacitor；(4) conductive substrates (and collector of capacitor) are used directly for
The assembling of capacitor, it is more convenient to operate, cheap.Currently, be mainly metal material using more three-dimensional conductive substrate,
Such as nickel foam, foam copper and stainless (steel) wire etc., they have certain chemical activity, therefore inorganic active material can be with
It is directly and efficiently grown in metallic conduction substrate.However, utilizing carbon material (such as carbon of high conductivity compared with metal material
Fiber, carbon cloth, carbon paper etc.) as collector there is lot of advantages, for example (,) it is their light-weight, stable chemical performances, environmental-friendly
Etc., it is more suitable for various assembling flexible super capacitors.However, just due to its good chemical inertness, carbon material with
Compatibility between various inorganic material is poor, is difficult directly effectively in its surface growth activity substance.Therefore, develop one kind
Effective method grows nickel sulfide and MoS with high activity directly in carbon-based conductive substrate2Heterogeneous nanometer sheet composite Nano
Material, and it is directly used in the assembling of supercapacitor, it is of great significance.
Therefore, the present invention propose using directly grown on three-dimensional carbon cloth high-purity, high density, high orientation NiS-
MoS2Heterogeneous nano-chip arrays structure is set as anode material, the carbon cloth of active carbon cladding as cathode material on this basis
Meter develops a flexible super capacitor.This composite material of the present invention is by three-dimensional carbon cloth and its table
The NiS-MoS of the array-like of face uniform load2Heterogeneous nanometer sheet is constituted.A kind of three-dimensional of multistage is built in this composite material
Tower structure, using carbon fiber as conducting matrix grain, in the NiS-MoS of its surface uniform load array-like2Heterogeneous nanometer sheet.Its
In, MoS2It is uniformly wrapped on the surface of NiS nanometer sheet, forms a large amount of heterogeneous interface.It is anti-that this structure is conducive to electrochemistry
The shuttle and diffusion for answering substance, from kinetically promoting electrochemical reaction speed；Meanwhile biggish specific surface area helps to fill
Divide exposure NiS and MoS2Active site, improve reactivity；In addition, its tower structure can also effectively avoid NiS and MoS2
Reunion, the structure and pattern of nano-chip arrays are helped to maintain, to improve the stability of this composite material.And
And this NiS-MoS of the present invention2Heterogeneous nano-chip arrays structure anode material purity is high, density is big, pattern is whole
Together, capacitance is high (mainly fake capacitance), and the carbon cloth cathode material excellent conductivity of active carbon cladding, double layer capacity capacity are big.
Therefore, this flexible super capacitor proposed by the present invention has the advantages that (1) condenser capacity is big, in 25mW/cm3
Power density under its energy density be 2.87mWh/cm3, or even in 200mW/cm3High power density output under, the capacitor
Energy density still be up to 0.52mWh/cm3；(2) the material the Nomenclature Composition and Structure of Complexes stability of device is good, the charge and discharge of capacitor
It has good stability；(3) device quality is light, has good flexibility, convenient for integrated assembly, is expected to as wearable electronic device
Power supply unit.Further, since this NiS-MoS of the present invention2Heterogeneous nano-chip arrays structure anode material, synthesis life
Elongate member is stringent controllable, equipment and simple process, at low cost；And in the present invention, cathode material, electrolyte gel, gel every
The preparation of film and capacitor package and assembling process are simple, are not necessarily to post-processing；Therefore, flexible super is prepared with the method for the present invention
The composition, structure and performance of capacitor, Preparation equipment and simple process, prepared device is stablized, and product yield is high, at low cost
Honest and clean, production process clean and environmental protection.
Summary of the invention
It is an object of the present invention to propose a kind of NiS-MoS based on carbon cloth load2Heterogeneous nano-chip arrays structure
Flexible super capacitor.In the flexible super capacitor, using it is a kind of directly grown on three-dimensional carbon cloth it is high-purity
Degree, high density, high orientation NiS-MoS2Heterogeneous nano-chip arrays structure is made as anode material, the carbon cloth of active carbon cladding
For cathode material, polyvinyl alcohol/potassium hydroxide (PVA/KOH) electrolyte gel makees electrolyte and diaphragm respectively, common assembling system
It is made high performance flexible super capacitor.This anode composite material of the present invention be by three-dimensional carbon cloth with
The NiS-MoS of the array-like of its surface uniform load2Heterogeneous nanometer sheet is constituted.Be built in this composite material it is a kind of multistage
Three-dimensional box rack and panel construction, using carbon fiber as conducting matrix grain, in the NiS-MoS of its surface uniform load array-like2Heterogeneous nanometer
Piece.Wherein, MoS2It is uniformly wrapped on the surface of NiS nanometer sheet, forms a large amount of heterogeneous interface.This structure is conducive to electrification
The shuttle and diffusion for learning reactive material, from kinetically promoting electrochemical reaction speed；Meanwhile biggish specific surface area helps
In abundant exposure NiS and MoS2Active site, improve reactivity；In addition, its tower structure can also effectively avoid NiS and
MoS2Reunion, the structure and pattern of nano-chip arrays are helped to maintain, to improve the stability of this composite material.
Moreover, this NiS-MoS of the present invention2Heterogeneous nano-chip arrays structure anode material purity is high, density is big, pattern is whole
Together, capacitance is high (mainly fake capacitance), and the carbon cloth cathode material excellent conductivity of active carbon cladding, double layer capacity capacity are big.
Therefore, this flexible super capacitor proposed by the present invention, capacitance is big, stable charge/discharge is good, is a kind of with a variety of
The high-performance energy storage device of application prospect；Device quality is light, flexible, convenient for integrated assembly, is expected to be used as wearable electronic device
The power supply unit of part.
The second object of the present invention is to provide this NiS-MoS based on carbon cloth load2Heterogeneous nano-chip arrays structure
Flexible super capacitor preparation method.Due to this NiS-MoS of the present invention2Heterogeneous nano-chip arrays structure sun
Pole material, synthesis growth conditions is stringent controllable, equipment and simple process, at low cost；And in the present invention, cathode material, electrolysis
Matter gel, the preparation of gelatin membrane and capacitor package and assembling process are simple, are not necessarily to post-processing；Therefore, with present invention side
Method prepares flexible super capacitor, Preparation equipment and simple process, and the composition, structure and performance of prepared device is stablized, produced
Product high income, low in cost, production process clean and environmental protection.
In order to reach above-mentioned target, the NiS-MoS proposed by the present invention based on carbon cloth load2Heterogeneous nano-chip arrays structure
Flexible super capacitor, which is characterized in that the flexible super capacitor using directly grown on three-dimensional carbon cloth it is high-purity
Degree, high density, high orientation NiS-MoS2Heterogeneous nano-chip arrays structure is made as anode material, the carbon cloth of active carbon cladding
For cathode material；The NiS-MoS2The capacitance of heterogeneous nano-chip arrays structure anode material is high, stable charge/discharge is good, institute
State active carbon cladding carbon cloth cathode material excellent conductivity, double layer capacity capacity it is big, cooperation PVA/KOH gel respectively as every
Film and electrolyte, common assembling obtain high-performance super capacitor flexible.
NiS-MoS provided by the invention based on carbon cloth load2The flexible super capacitor of heterogeneous nano-chip arrays structure
Preparation method, which is characterized in that the NiS-MoS that the capacitor is loaded by carbon cloth2Heterogeneous nano-chip arrays structure anode,
The carbon cloth cathode of PVA/KOH electrolyte gel diaphragm and active carbon cladding, the group " from bottom to top " in PVA/KOH electrolyte gel
It fills.
NiS-MoS proposed by the present invention based on carbon cloth load2The flexible super capacitor of heterogeneous nano-chip arrays structure
Preparation method, include the following steps and content:
(1) cleaning of carbon cloth: carbon cloth uses acetone, 1-2mol/L aqueous hydrochloric acid solution and deionized water in advance, and successively ultrasound is clear
It washes 0.5-1 hours, and dried at 60 DEG C, saves backup.
(2) preparation of anode material: by the pure nickel acetate of commercially available analysis, ammonium molybdate, thiocarbamide and lauryl sodium sulfate powder
It puts into beaker, adding deionized water and being sufficiently stirred mixes it uniformly, and controlling acetic acid nickel concentration in mixed solution is 0.03-
0.05mol/L, the concentration of ammonium molybdate are 0.001-0.005mol/L, and the concentration of thiocarbamide is 0.05-0.08mol/L, dodecyl
Sodium sulfate concentration is 0.15-0.25mol/L；The sodium hydrate aqueous solution of 0.5-1.0mol/L is recycled to adjust reactant mixing molten
The pH value of liquid is between 5.8-7.0；After the reactant mixed solution for filling 50%-80% in a high pressure reaction kettle, it is dipped vertically into
Clean carbon cloth seals reaction kettle；Then reaction kettle is moved in electric furnace, and the rate of 5-20 DEG C/min is heated to 160-200
DEG C and keep the temperature 8-12 hours.After naturally cooling to room temperature, reaction kettle is opened；Carbon cloth is taken out from reaction kettle, and uses deionized water
With alcohol alternately rinsing 3-5 times；Then the NiS-MoS loaded to get the carbon cloth is dried at 60 DEG C2Heterogeneous nano-chip arrays
Structure anode material.At room temperature, it is saved backup in drying box.
(3) activation of carbon cloth: in electrochemical workstation three-electrode system, using clean carbon cloth as working electrode, platinum
Piece is used as to electrode, calomel electrode as reference electrode, the concentrated sulfuric acid/concentrated nitric acid mixed liquor of volume ratio 1:1 as electrolyte,
It is reacted 10 minutes under the voltage of 3V；Then carbon cloth is removed, after being cleaned up with deionized water, is dried at 60 DEG C, saved standby
With.
(4) preparation of cathode material: in beaker, 7:2:1 in mass ratio weighs active carbon, conductive black respectively and gathers inclined
Vinyl fluoride, then in hybrid solid powder and solvent 100mg:(1-1.5mL) ratio be added N-Methyl pyrrolidone make solvent,
Ultrasonic vibration is uniformly mixed it to get active carbon mixed liquor is arrived after stirring；Then this active carbon mixing drop is being activated
Carbon cloth upper and lower surface, the dry 2-4 hour carbon cloth cathode materials coated to get the active carbon at 120 DEG C.In room temperature
Under, it is saved backup in drying box.
(5) preparation of electrolyte gel: in deionized water by PVA dispersion, stirring 1-2 hours at 80-95 DEG C, until
PVA is completely dissolved as transparent gel-form；Then lasting to stir lower cooled to room temperature, then it is slowly added dropwise 0.2-0.5g/mL's
KOH aqueous solution, it is stirring while adding, until being mixed thoroughly to get the PVA/KOH electrolyte gel.At room temperature, it seals up for safekeeping
It is spare.
(6) preparation of gelatin membrane: a small amount of PVA/KOH gel is added dropwise on the glass sheet, keeps gel uniform on the glass sheet
Drawout spontaneously dries 6-10 hours to get the PVA/KOH gelatin membrane.At room temperature, it seals up for safekeeping spare.
(7) assembling of capacitor: assembled by the way of " from bottom to top ".It is first added dropwise in glass mold a small amount of
PVA/KOH electrolyte gel, then spreads cathode material；It is smooth after a small amount of PVA/KOH gel is added dropwise on cathode material again
The upper prefabricated PVA/KOH gelatin membrane of ground covering, and a small amount of PVA/KOH gel is added dropwise；Then after being further continued for superposition anode material,
A small amount of PVA/KOH gel is added dropwise again.Finally, drying at room temperature 8-12 hours.
(8) encapsulation of capacitor: obtained device is sealed and outer packing, the flexible super capacitor is obtained.
In the above preparation method, carbon cloth acetone, 1-2mol/L aqueous hydrochloric acid solution and deionization in the step (1)
Water is successively cleaned by ultrasonic 0.5-1 hours, and dries at 60 DEG C.
In the above preparation method, nickel acetate, ammonium molybdate, thiocarbamide and lauryl sodium sulfate are in the step (2)
The commercially available pure powder reagent of analysis.
In the above preparation method, acetic acid nickel concentration is 0.03- in reactant mixed solution in the step (2)
0.05mol/L, the concentration of ammonium molybdate are 0.001-0.005mol/L, and the concentration of thiocarbamide is 0.05-0.08mol/L, dodecyl
Sodium sulfate concentration is 0.15-0.25mol/L.
In the above preparation method, it is water-soluble that sodium hydroxide used in reactant mixed solution pH value is adjusted in the step (2)
Liquid concentration is 0.5-1.0mol/L, and reactant mixed solution pH value is 5.8-7.0 after adjusting.
In the above preparation method, heating schedule is reacted in the step (2) are as follows: be heated to the rate of 5-20 DEG C/min
160-200 DEG C and 8-12 hours are kept the temperature, then naturally cools to room temperature.
In the above preparation method, the activation of carbon cloth is completed by electrochemical oxidation method in the step (3), wherein electricity
The concentrated sulfuric acid/concentrated nitric acid mixed liquor that liquid is volume ratio 1:1 is solved, and is dried at 60 DEG C after the completion of cleaning.
In the above preparation method, in the step (4) active carbon mixed liquor preparation process are as follows: 7:2:1 in mass ratio
Active carbon, conductive black and Kynoar powder are weighed respectively, then by hybrid solid powder and solvent 100mg:(1-
Ratio 1.5mL) is added N-Methyl pyrrolidone and makees solvent, and ultrasonic vibration is uniformly mixed after stirring.
In the above preparation method, the load capacity of the active carbon coated on carbon cloth in the step (4) is 15-20mg/
cm2。
In the above preparation method, PVA used and KOH is ommercially available AR in the step (5).
In the above preparation method, the concentration of PVA clear gel is 0.1-0.15g/mL, preparation in the step (5)
Condition are as follows: stirred 1-2 hours at 80-95 DEG C.
In the above preparation method, KOH concentration of aqueous solution is 0.2-0.5g/mL in the step (5).
In the above preparation method, the PVA solution of PVA/KOH gel and the volume of KOH solution are prepared in the step (5)
Than for 1:(0.2-0.25).
In the above preparation method, in the step (5) it is all stirring be magnetic agitation, mixing speed be 100-200 turn/
Point, to guarantee not generate bubble.
In the above preparation method, PVA/KOH gelatin membrane spontaneously dries 6-10 hours in the step (6), final to produce
Product are sealed up for safekeeping spare at room temperature.
In the above preparation method, in the step (6) PVA/KOH gelatin membrane finished product with a thickness of 0.1-0.2mm, ruler
It is very little identical as the area of anode and cathode material.
In the above preparation method, the work of anode and cathode material is controlled in the step (7) in whole process
It is identical with area.
In the above preparation method, PVA/KOH gelatin membrane is clipped between cathode and anode material in the step (7),
And each interlayer of cathode, diaphragm, anode is coated with PVA/KOH gel, and thickness is about after controlling every layer of PVA/KOH gel drying
0.10-0.12mm, electrode integral thickness are 0.8-1.2mm.
In the above preparation method, sample assembly finishes in the step (7), dries at room temperature 8-12 hours.
In the above preparation method, housing material is soft insulating material in the step (8).
In the above preparation method, in the step (8) in the encapsulation of capacitor it is noted that sealing, keep gel moisture
It is not lost further.
Present invention is characterized in that the NiS-MoS based on carbon cloth load2The flexibility of heterogeneous nano-chip arrays structure is super
Grade capacitor uses the NiS-MoS of carbon cloth load2Heterogeneous nano-chip arrays structure is as anode material, the carbon cloth of active carbon cladding
As cathode, and this NiS-MoS of the present invention2Heterogeneous nano-chip arrays structure anode material purity is high, density
Greatly, pattern is neat, capacitance is high (mainly fake capacitance), and the carbon cloth of active carbon cladding is as cathode material excellent conductivity, double
Layer capacitance capacity is big.
Therefore, this flexible super capacitor proposed by the present invention has the advantages that (1) condenser capacity is big,
25mW/cm3Power density under its energy density be 2.87mWh/cm3, or even in 200mW/cm3High power density output under,
The energy density of the capacitor is still up to 0.52mWh/cm3；(2) the material the Nomenclature Composition and Structure of Complexes stability of device is good, capacitor
Stable charge/discharge it is good；(3) device quality is light, has good flexibility, convenient for integrated assembly, is expected to be used as wearable electricity
The power supply unit of sub- device.
In addition, the preparation method of flexible super capacitor provided by the invention, has the advantages that used by (1)
NiS-MoS2Heterogeneous nano-chip arrays structure anode material, the stringent controllable, equipment of synthesis growth conditions and simple process, cost
It is low；Cathode material, electrolyte gel used by (2), the preparation of gelatin membrane and capacitor package and assembling process be simple,
Without post-processing；(3) flexible super capacitor, Preparation equipment and simple process, prepared device are prepared with the method for the present invention
Composition, structure and performance stablize, product yield is high, low in cost, production process clean and environmental protection.
Detailed description of the invention
Fig. 1 is the NiS-MoS of the load of carbon cloth obtained by the embodiment of the present invention 12The optics of heterogeneous nano-chip arrays structure
Photo
Fig. 2 is the NiS-MoS of the load of carbon cloth obtained by the embodiment of the present invention 12The microcell of heterogeneous nano-chip arrays structure
Stereoscan photograph
Fig. 3 is the NiS-MoS based on carbon cloth load obtained by the embodiment of the present invention 12Heterogeneous nano-chip arrays structure
The structural schematic diagram of flexible super capacitor
Fig. 4 is the NiS-MoS based on carbon cloth load obtained by the embodiment of the present invention 12Heterogeneous nano-chip arrays structure
The energy and power density curve of flexible super capacitor
Specific embodiment
Below with reference to embodiment, technical scheme is described further.
NiS-MoS proposed by the present invention based on carbon cloth load2The flexible super capacitor of heterogeneous nano-chip arrays structure,
It is characterized in that, the flexible super capacitor uses high-purity, the high density, high orientation directly grown on three-dimensional carbon cloth
NiS-MoS2Heterogeneous nano-chip arrays structure is as anode material, and the carbon cloth of active carbon cladding is as cathode material；It is described
NiS-MoS2The capacitance of heterogeneous nano-chip arrays structure anode material is high, stable charge/discharge is good, the active carbon cladding
Carbon cloth cathode material excellent conductivity, double layer capacity capacity are big, and cooperation PVA/KOH gel is respectively as diaphragm and electrolyte, altogether
High-performance super capacitor flexible is obtained with assembling.
NiS-MoS provided by the invention based on carbon cloth load2The flexible super capacitor of heterogeneous nano-chip arrays structure
Preparation method, which is characterized in that the NiS-MoS that the capacitor is loaded by carbon cloth2Heterogeneous nano-chip arrays structure anode,
The carbon cloth cathode of PVA/KOH electrolyte gel diaphragm and active carbon cladding, the group " from bottom to top " in PVA/KOH electrolyte gel
It fills.
NiS-MoS proposed by the present invention based on carbon cloth load2The flexible super capacitor of heterogeneous nano-chip arrays structure
Preparation method, included the following steps with this and content:
(1) cleaning of carbon cloth: carbon cloth uses acetone, 1-2mol/L aqueous hydrochloric acid solution and deionized water in advance, and successively ultrasound is clear
It washes 0.5-1 hours, and dried at 60 DEG C, saves backup.
(2) preparation of anode material: by the pure nickel acetate of commercially available analysis, ammonium molybdate, thiocarbamide and lauryl sodium sulfate powder
It puts into beaker, adding deionized water and being sufficiently stirred mixes it uniformly, and controlling acetic acid nickel concentration in mixed solution is 0.03-
0.05mol/L, the concentration of ammonium molybdate are 0.001-0.005mol/L, and the concentration of thiocarbamide is 0.05-0.08mol/L, dodecyl
Sodium sulfate concentration is 0.15-0.25mol/L；The sodium hydrate aqueous solution of 0.5-1.0mol/L is recycled to adjust reactant mixing molten
The pH value of liquid is between 5.8-7.0；After the reactant mixed solution for filling 50%-80% in a high pressure reaction kettle, it is dipped vertically into
Clean carbon cloth seals reaction kettle；Then reaction kettle is moved in electric furnace, and the rate of 5-20 DEG C/min is heated to 160-200
DEG C and keep the temperature 8-12 hours.After naturally cooling to room temperature, reaction kettle is opened；Carbon cloth is taken out from reaction kettle, and uses deionized water
With alcohol alternately rinsing 3-5 times；Then the NiS-MoS loaded to get the carbon cloth is dried at 60 DEG C2Heterogeneous nano-chip arrays
Structure anode material.At room temperature, it is saved backup in drying box.
(3) activation of carbon cloth: in electrochemical workstation three-electrode system, using clean carbon cloth as working electrode, platinum
Piece is used as to electrode, calomel electrode as reference electrode, the concentrated sulfuric acid/concentrated nitric acid mixed liquor of volume ratio 1:1 as electrolyte,
It is reacted 10 minutes under the voltage of 3V；Then carbon cloth is removed, after being cleaned up with deionized water, is dried at 60 DEG C, saved standby
With.
(4) preparation of cathode material: in beaker, 7:2:1 in mass ratio weighs active carbon, conductive black respectively and gathers inclined
Vinyl fluoride, then in hybrid solid powder and solvent 100mg:(1-1.5mL) ratio be added N-Methyl pyrrolidone make solvent,
Ultrasonic vibration is uniformly mixed it to get active carbon mixed liquor is arrived after stirring；Then this active carbon mixing drop is being activated
Carbon cloth upper and lower surface, the dry 2-4 hour carbon cloth cathode materials coated to get the active carbon at 120 DEG C.Control carbon cloth
The load capacity of the active carbon of upper cladding is 15-20mg/cm2；Last gained cathode material saves in drying box standby at room temperature
With.
(5) preparation of electrolyte gel: in deionized water by PVA dispersion, stirring 1-2 hours at 80-95 DEG C, until
PVA is completely dissolved, and obtains the transparent gel-form object that concentration is 0.1-0.15g/mL；Then room is naturally cooled under lasting stirring
Temperature, then the KOH aqueous solution of 0.2-0.5g/mL is slowly added dropwise, it is stirring while adding, until being mixed thoroughly to get the PVA/
KOH gel.When preparing PVA/KOH electrolyte gel, the volume ratio for controlling PVA solution and KOH solution is 1:(0.2-0.25), and
It is 100-200 revs/min that whole process, which controls magnetic stirring speed, avoids generating bubble；Last gained PVA/KOH electrolyte gel
It seals up for safekeeping at room temperature spare.
(6) preparation of gelatin membrane: a small amount of PVA/KOH gel is added dropwise on the glass sheet, keeps gel uniform on the glass sheet
Drawout spontaneously dries 6-10 hours to get the PVA/KOH gelatin membrane.Control gelatin membrane finished product with a thickness of 0.1-
0.2mm；Last gained PVA/KOH gelatin membrane is sealed up for safekeeping spare at room temperature.
(7) assembling of capacitor: assembled by the way of " from bottom to top ".It is first added dropwise in glass mold a small amount of
PVA/KOH electrolyte gel, then spreads cathode material；It is smooth after a small amount of PVA/KOH gel is added dropwise on cathode material again
The upper prefabricated PVA/KOH gelatin membrane of ground covering, and a small amount of PVA/KOH gel is added dropwise；Then after being further continued for superposition anode material,
A small amount of PVA/KOH gel is added dropwise again；Finally, drying at room temperature 8-12 hours.Anode and cathode material are controlled in whole process
Active area it is identical, and each interlayer of cathode, diaphragm, anode is coated with PVA/KOH gel, and it is solidifying to control every layer of PVA/KOH
Thickness is about 0.10-0.12mm after glue is dry, and electrode integral thickness is 0.8-1.2mm.
(8) encapsulation of capacitor: obtained device is sealed and carries out outer packing with and with insulation soft material, obtains institute
State flexible super capacitor.
The NiS-MoS of obtained carbon cloth load2Heterogeneous nano-chip arrays structure sample, visually appear to be ater and
A shaggy piece of cloth (see Fig. 1).It is different depending on the application, it is suitably cut, the supercapacitor assembled, in appearance
It can be button-shaped, square-shaped, belt etc., light weight, capacity have greatly good flexibility.
In short, can be prepared with this technology containing the high performance NiS-MoS based on carbon cloth load2Heterogeneous nano-chip arrays
The flexible super capacitor of structure.
Embodiment 1: the preparation step of the present embodiment supercapacitor is successively as follows:
(1) with acetone, 1mol/L aqueous hydrochloric acid solution and deionized water that the carbon cloth of two pieces of 2 × 4cm is successively ultrasonic in advance
Cleaning 1 hour, and dried at 60 DEG C, it saves backup.
(2) in 100mL beaker, 0.224g nickel acetate, 0.074g ammonium molybdate, 0.137g thiocarbamide and 1.73g are sequentially added
Then 30mL deionized water is added in lauryl sodium sulfate, be stirred well to solution clarification；Appropriate 0.5mol/L is slowly added dropwise again
The pH value of reactant mixed solution is adjusted to 6.2 by sodium hydrate aqueous solution；Then mixed solution is all transferred to 40mL high pressure
In hydrothermal reaction kettle, one block of clean carbon cloth in step (1) is dipped vertically into solution, seals reaction kettle；It is then placed in electric furnace
In with the speed of 5 DEG C/min be heated to 180 DEG C and react 9 hours.After naturally cooling to room temperature, reaction kettle is opened, carbon cloth is taken
It is alternately rinsed each 5 times with deionized water and alcohol, is finally dried at 60 DEG C to get the NiS-MoS loaded to required carbon cloth out2
Heterogeneous nano-chip arrays structure anode material.At room temperature, it is saved backup in drying box.
(3) in electrochemical workstation three-electrode system, the dense sulphur of dose volume ratio 1:1 in three electrode reaction containers
Acid-concentrated nitric acid mixed liquor 40mL, using another block of clean carbon cloth in step (1) as working electrode, immersion area is 4cm2；Platinum
Piece and calomel electrode are respectively as to electrode and reference electrode；Reaction 10 minutes is carried out under the voltage of 3V；Then carbon cloth is taken
Under, after cleaning carbon cloth 3 times with deionized water, dries, save backup at 60 DEG C.
(4) in 5mL test tube, 70mg active carbon, 20mg conductive black and 10mg Kynoar is added, is then added
1.4mL N-Methyl pyrrolidone is stirred rear ultrasonic vibration and obtains within 30 minutes uniform activity charcoal mixed liquor；By step (3)
The carbon cloth of activation is cut to 1 × 3cm2Size, in 1 × 2cm2Area on double-faced uniform coat each 0.4mL mixed liquor；At 120 DEG C
Lower drying 4 hours, obtains required cathode material.It is saved backup in drying box at room temperature.
(5) in round bottom three-necked bottle, 2g PVA is added, adds 20mL deionized water, magnetic force stirs in 90 DEG C of oil bath pans
It mixes 1.5 hours, 120 revs/min of whole-process control revolving speed, obtains transparent gel liquid；It is taken out from oil bath pan, gel is shifted
Into beaker, continuing magnetic force stirring is cooled to room temperature, spare.
(6) the aqueous solution 5mL for preparing the KOH of 0.4g/mL, is slowly added dropwise into prepared by step (5) prepared after being cooled to room temperature
It in PVA gel, is stirred in drop, until 5mL solution is all added dropwise；Then it persistently stirs 20 minutes, whole-process control revolving speed
120 revs/min, obtain required PVA/KOH electrolyte gel.It seals up for safekeeping at room temperature spare.
(7) one piece of glass slide is taken, is dried after cleaning, the prepared PVA/KOH electrolyte gel of a dropping step (6), tiling
Keep each section thickness uniform, be dried at room temperature for 8 hours, controls with a thickness of 0.15mm, obtain required PVA/KOH gelatin membrane.
It seals up for safekeeping at room temperature spare.
(8) in a rectangular glass mold, a small amount of PVA/KOH electrolyte gel is first added dropwise, then by cathode material
It lies on gel, guarantees the part (1 × 2cm for being coated with active carbon2) infiltrated completely by gel；Diaphragm is cut to 1 × 2cm2Greatly
It is small, it is smooth to be covered on cathode material；Then a small amount of PVA/KOH gel is added dropwise again；Positive electrode is cut to 1 × 3cm2Greatly
It is small, take 1 × 2cm of one end2Partial stack on diaphragm, guarantee that cathode, anode and diaphragm are aligned, active area is 1 ×
2cm2；A small amount of PVA/KOH gel is finally added dropwise again, guarantees that electrode is coated by gel completely；And it is dry to control every layer of PVA/KOH gel
Thickness is about 0.11mm after dry, and electrode integral thickness is 1mm；It dries at room temperature 10 hours.
(9) it by after sample drying obtained by step (8), first cuts and removes extra gel, then wrap up the plastics of one layer of insulation
Film, then one layer of soft insulating shell of outsourcing, cathode, anode both ends external wire are to get arriving the flexible super capacitor.
Prepared anode material is the array-like NiS-MoS of the high-purity of carbon cloth load, high orientation2Heterogeneous nanometer sheet
(see Fig. 2)；Obtained flexible super capacitor (see Fig. 3), whole long 4cm, wide 1cm, total weight is about 0.5g, is had good
Flexibility, and be hardly damaged；The capacitor has excellent energy-storage property (see Fig. 4) under the test voltage window of 0-1.6V:
In 25mW/cm3Power density under its energy density be 2.87mWh/cm3, or even in 200mW/cm3High power density output
Under, the energy density of the capacitor is still up to 0.52mWh/cm3；Compared to similar flexible super capacitor, its capacitive property is mentioned
30-50% is risen, and preparation method is economic and environment-friendly.
Claims (7)
1. the NiS-MoS based on carbon cloth load2The flexible super capacitor of heterogeneous nano-chip arrays structure, which is characterized in that described
Flexible super capacitor use directly grown on three-dimensional carbon cloth high-purity, high density, high orientation NiS-MoS2It is heterogeneous
Nano-chip arrays structure is as anode material, and the carbon cloth of active carbon cladding is as cathode material；The NiS-MoS2Heterogeneous nanometer
The capacitance of chip arrays structure anode material is high, stable charge/discharge is good, and the carbon cloth cathode material of the active carbon cladding is conductive
Property it is excellent, double layer capacity capacity is big, respectively as diaphragm and electrolyte, common assembling obtains flexible cooperation PVA/KOH gel
High-performance super capacitor.
2. the NiS-MoS described in accordance with the claim 1 based on carbon cloth load2The flexible super electricity of heterogeneous nano-chip arrays structure
The preparation method of container, which is characterized in that the NiS-MoS that the capacitor is loaded by carbon cloth2Heterogeneous nano-chip arrays structure sun
Pole, PVA/KOH electrolyte gel diaphragm and active carbon cladding carbon cloth cathode, " from lower in PVA/KOH electrolyte gel
On " assemble, successively the following steps are included:
(1) cleaning of carbon cloth: carbon cloth uses acetone, 1-2mol/L aqueous hydrochloric acid solution and deionized water to be successively cleaned by ultrasonic in advance
0.5-1 hours, and dried at 60 DEG C, it saves backup；
(2) preparation of anode material: the pure nickel acetate of commercially available analysis, ammonium molybdate, thiocarbamide and lauryl sodium sulfate powder are put into
In beaker, adding deionized water and being sufficiently stirred mixes it uniformly, and controlling acetic acid nickel concentration in mixed solution is 0.03-
0.05mol/L, the concentration of ammonium molybdate are 0.001-0.005mol/L, and the concentration of thiocarbamide is 0.05-0.08mol/L, dodecyl
Sodium sulfate concentration is 0.15-0.25mol/L；The sodium hydrate aqueous solution of 0.5-1.0mol/L is recycled to adjust reactant mixing molten
The pH value of liquid is between 5.8-7.0；After the reactant mixed solution for filling 50%-80% in a high pressure reaction kettle, it is dipped vertically into
Clean carbon cloth seals reaction kettle；Then reaction kettle is moved in electric furnace, and the rate of 5-20 DEG C/min is heated to 160-200
DEG C and keep the temperature 8-12 hours；After naturally cooling to room temperature, reaction kettle is opened；Carbon cloth is taken out from reaction kettle, and uses deionized water
With alcohol alternately rinsing 3-5 times；Then the NiS-MoS loaded to get the carbon cloth is dried at 60 DEG C2Heterogeneous nano-chip arrays
Structure anode material；At room temperature, it is saved backup in drying box；
(3) activation of carbon cloth: in electrochemical workstation three-electrode system, using clean carbon cloth as working electrode, platinized platinum is made
For to electrode, calomel electrode is as reference electrode, and the concentrated sulfuric acid/concentrated nitric acid mixed liquor of volume ratio 1:1 is as electrolyte, 3V's
It is reacted 10 minutes under voltage；Then carbon cloth is removed, after being cleaned up with deionized water, dries, save backup at 60 DEG C；
(4) preparation of cathode material: in beaker, 7:2:1 in mass ratio weighs active carbon, conductive black and polyvinylidene fluoride respectively
Alkene, then in hybrid solid powder and solvent 100mg:(1-1.5mL) ratio be added N-Methyl pyrrolidone make solvent, stir
Ultrasonic vibration is uniformly mixed it to get active carbon mixed liquor is arrived afterwards；Then by this active carbon mixing drop activation carbon
Cloth upper and lower surface, the dry 2-4 hours carbon cloth cathode materials to get active carbon cladding at 120 DEG C；It is wrapped on control carbon cloth
The load capacity of the active carbon covered is 15-20mg/cm2；Last gained cathode material saves backup in drying box at room temperature；
(5) it the preparation of electrolyte gel: in deionized water by PVA dispersion, is stirred 1-2 hours at 80-95 DEG C, until PVA
It is completely dissolved, obtains the transparent gel-form object that concentration is 0.1-0.15g/mL；Then the lower cooled to room temperature of lasting stirring, then
The KOH aqueous solution of 0.2-0.5g/mL is slowly added dropwise, it is stirring while adding, until being mixed thoroughly solidifying to get the PVA/KOH
Glue；When preparing PVA/KOH electrolyte gel, the volume ratio for controlling PVA solution and KOH solution is 1:(0.2-0.25), and it is entire
Process control magnetic stirring speed is 100-200 revs/min, avoids generating bubble；Last gained PVA/KOH electrolyte gel is in room
It is sealed up for safekeeping under temperature spare；
(6) preparation of gelatin membrane: a small amount of PVA/KOH gel is added dropwise on the glass sheet, sprawls gel uniformly on the glass sheet
It opens, spontaneously dries 6-10 hours to get the PVA/KOH gelatin membrane；Control gelatin membrane finished product with a thickness of 0.1-
0.2mm；Last gained PVA/KOH gelatin membrane is sealed up for safekeeping spare at room temperature；
(7) by the way of " from bottom to top ", a small amount of PVA/KOH electrolyte first the assembling of capacitor: is added dropwise in glass mold
Then gel spreads cathode material；After a small amount of PVA/KOH gel is added dropwise on cathode material again, entirely covering is upper prefabricated
PVA/KOH gelatin membrane, and a small amount of PVA/KOH gel is added dropwise；Then it after being further continued for superposition anode material, then is added dropwise a small amount of
PVA/KOH gel；Finally, drying at room temperature 8-12 hours；Moreover, controlling the effect of anode and cathode material in whole process
Area is identical, and each interlayer of cathode, diaphragm, anode is coated with PVA/KOH gel, and controls every layer of PVA/KOH gel drying
Thickness is about 0.10-0.12mm afterwards, and electrode integral thickness is 0.8-1.2mm；
(8) encapsulation of capacitor: obtained device is sealed and carries out outer packing with and with insulation soft material, is obtained described soft
Property supercapacitor.
3. preparation method according to claim 2, which is characterized in that the activation of carbon cloth passes through electrification in the step (3)
It learns method for oxidation to complete, wherein electrolyte is the concentrated sulfuric acid/concentrated nitric acid mixed liquor of volume ratio 1:1, and at 60 DEG C after the completion of cleaning
Lower drying.
4. preparation method according to claim 2, which is characterized in that the preparation of active carbon mixed liquor in the step (4)
Technique are as follows: 7:2:1 in mass ratio weighs active carbon, conductive black and Kynoar powder respectively, then presses hybrid solid powder
The ratio of end and solvent 100mg:(1-1.5mL) are added N-Methyl pyrrolidone and make solvent, and ultrasonic vibration is uniformly mixed after stirring；
The carbon cloth cathode material of active carbon cladding be by active carbon mixing drop activation carbon cloth upper and lower surface, at 120 DEG C
It forms within dry 2-4 hours, the load capacity of the active carbon wherein coated on carbon cloth is 15-20mg/cm2。
5. preparation method according to claim 2, which is characterized in that the preparation work of electrolyte gel in the step (5)
Skill are as follows: in deionized water by PVA dispersion, stirred 1-2 hours at 80-95 DEG C, until PVA is completely dissolved, obtaining concentration is
The transparent gel-form object of 0.1-0.15g/mL；Then lasting to stir lower cooled to room temperature, then 0.2-0.5g/mL is slowly added dropwise
KOH aqueous solution, it is stirring while adding, until be mixed thoroughly to get the PVA/KOH gel；In preparation PVA/KOH electrolysis
When matter gel, the volume ratio for controlling PVA solution and KOH solution is 1:(0.2-0.25)；And whole process controls magnetic agitation
Speed is 100-200 revs/min.
6. preparation method according to claim 2, which is characterized in that the preparation process of gelatin membrane in the step (6)
Are as follows: a small amount of PVA/KOH gel is added dropwise on the glass sheet, makes gel uniform drawout on the glass sheet, spontaneously dries 6-10 hours,
Up to the PVA/KOH gelatin membrane；Wherein, control gelatin membrane finished product with a thickness of 0.1-0.2mm, and last gained PVA/
KOH gelatin membrane is sealed up for safekeeping at room temperature.
7. preparation method according to claim 2, which is characterized in that the packaging technology of capacitor in the step (7) are as follows:
By the way of " from bottom to top ", a small amount of PVA/KOH electrolyte gel is first added dropwise in glass mold, then spreads cathode material
Material；After a small amount of PVA/KOH gel is added dropwise on cathode material again, the upper prefabricated PVA/KOH gelatin membrane of entirely covering, and
A small amount of PVA/KOH gel is added dropwise；Then after being further continued for superposition anode material, then a small amount of PVA/KOH gel is added dropwise；Finally, in room
It is dried under temperature 8-12 hours；Moreover, in whole process control anode it is identical as the active area of cathode material, and cathode, diaphragm,
Each interlayer of anode is coated with PVA/KOH gel, and thickness is about 0.10-0.12mm after controlling every layer of PVA/KOH gel drying,
Electrode integral thickness is 0.8-1.2mm.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109455774A (en) * | 2018-12-27 | 2019-03-12 | 西安交通大学 | A kind of Ni-Fe-OH/MoS2/Ni3S2Composite nano plate/carbon cloth, preparation method and application |
| CN110233065A (en) * | 2019-05-09 | 2019-09-13 | 哈尔滨工业大学 | The preparation method of complex carbon material flexible super capacitance electrode |
| CN110444821A (en) * | 2019-08-01 | 2019-11-12 | 武汉理工大学 | The preparation method of flexible miniature alkaline zinc cell based on three-diemsnional electrode |
| CN110629250A (en) * | 2019-10-14 | 2019-12-31 | 东北大学秦皇岛分校 | Preparation method of Ag-supported quasi-three-dimensional structure embedded flexible electrode material |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101989499A (en) * | 2009-07-29 | 2011-03-23 | 美国纳米股份有限公司 | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
| CN105655140A (en) * | 2016-03-07 | 2016-06-08 | 浙江理工大学 | Preparation method of flaky molybdenum disulfide/nickel sulfide-graphene composite |
-
2018
- 2018-09-04 CN CN201811025876.6A patent/CN109065368B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101989499A (en) * | 2009-07-29 | 2011-03-23 | 美国纳米股份有限公司 | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
| CN105655140A (en) * | 2016-03-07 | 2016-06-08 | 浙江理工大学 | Preparation method of flaky molybdenum disulfide/nickel sulfide-graphene composite |
Non-Patent Citations (2)
| Title |
|---|
| JAYARAMAN BALAMURUGAN,ET AL.: ""Hierarchical Ni-Mo-S and Ni-Fe-S Nanosheets with Ultrahigh Energy Density for Flexible All Solid-State Supercapacitors"", 《ADV. FUNCT. MATER.》 * |
| 陶家友: ""基于锰、钼氧化物及其复合纳米材料的储能器件研究"", 《中国博士学位论文全文数据库 工程科技Ⅱ辑》 * |
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