CN206322594U - A kind of flexible and transparent all-solid-state supercapacitor based on fake capacitance material - Google Patents
A kind of flexible and transparent all-solid-state supercapacitor based on fake capacitance material Download PDFInfo
- Publication number
- CN206322594U CN206322594U CN201621183658.1U CN201621183658U CN206322594U CN 206322594 U CN206322594 U CN 206322594U CN 201621183658 U CN201621183658 U CN 201621183658U CN 206322594 U CN206322594 U CN 206322594U
- Authority
- CN
- China
- Prior art keywords
- feooh
- transparent
- compound
- nano
- flexible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The utility model provides a kind of flexible and transparent all-solid-state supercapacitor based on fake capacitance material, including：Ni(OH)2Anode electrode, the Ni (OH)2Anode electrode includes the first flexible substrate and is compound in the Ni (OH) of first flexible substrate2Nano-chip arrays transparent membrane；The Ni (OH) is compound in described in being compound in2First graphene layer of nano-chip arrays transparent membrane；It is compound in the dielectric substrate of first graphene layer；It is compound in the second graphene layer of the dielectric substrate；The FeOOH negative electrodes of second graphene layer are compound in, the FeOOH negative electrodes include being compound in the FeOOH nano-wire arrays transparent membrane of second graphene layer and are compound in the second flexible substrate of the FeOOH nano-wire arrays transparent membrane；It is coated on the Ni (OH)2The silver paste of anode electrode and FeOOH negative electrodes edge.
Description
Technical field
The utility model belongs to supercapacitor technologies field, and in particular to a kind of flexible and transparent based on fake capacitance material
All-solid-state supercapacitor and preparation method thereof.
Background technology
Flexible energy-storage system is the key of flexible electronic device driving force of new generation.As self-powered transparent liquid crystal is shown
Device and wearable or implantable devices the development of intelligence, transparent electron have attracted the attention of people with its unique glamour.
The appearance of transparent flexible all-solid-state supercapacitor can meet demand of some electronic equipments to special function, particularly energy
Source supplying system security in actual applications and esthetic requirement.However, at present transparent ultracapacitor energy density and
Power density suffers from limitation, and on the other hand the restriction of one side electrode transparency receptor 1 activity material carrying capacity, is commonly used at present
Carbon material theoretical capacity is relatively low.
The energy density of ultracapacitor is determined by its capacity and operating voltage.With the counterfeit of wide operating voltage window
Capacitance energy storage material is the key for improving super capacitor energy density and power density.At present, with the counterfeit electricity of high theoretical capacity
Capacity materials prepare high-efficient transparent electrode it is extremely challenging because these electrodes successful preparations need and meanwhile satisfaction lower three because
Element：(1) material should relatively easily grow (such as ITO and PET), or independently can be grown on substrate on a transparent substrate
Realize transparent；(2) active material must possess efficient surface micro-structure, large area and good electric conductivity, to improve its appearance
Amount；(3) potential window of positive and negative electrode can be maximized, and be complementary to one another, so as to improve operable voltage.
And the electrode of ultracapacitor in the market is difficult to meet above-mentioned condition, obtained super capacitor energy is close
Degree is low and cycle performance is poor, limits the further development of ultracapacitor.
Utility model content
In view of this, the technical problems to be solved in the utility model is to provide a kind of flexibility based on fake capacitance material thoroughly
Bright all-solid-state supercapacitor and preparation method thereof, the flexible and transparent based on fake capacitance material that the utility model is provided is all solid state
Ultracapacitor has higher energy density and good cycle performance.
The utility model provides a kind of flexible and transparent all-solid-state supercapacitor based on fake capacitance material, including：
Ni(OH)2Anode electrode, the Ni (OH)2Anode electrode includes the first flexible substrate and is compound in described first
The Ni (OH) of flexible substrate2Nano-chip arrays transparent membrane；
The Ni (OH) is compound in described in being compound in2First graphene layer of nano-chip arrays transparent membrane；
It is compound in the dielectric substrate of first graphene layer；
It is compound in the second graphene layer of the dielectric substrate；
The FeOOH negative electrodes of second graphene layer are compound in, the FeOOH negative electrodes are described including being compound in
The FeOOH nano-wire arrays transparent membrane of second graphene layer and it is compound in the FeOOH nano-wire arrays transparent membrane
Second flexible substrate；
It is coated on the Ni (OH)2The silver paste of anode electrode and FeOOH negative electrodes edge.
It is preferred that, the flexible substrate is selected from ITO substrates.
It is preferred that, the dielectric substrate is selected from KOH dielectric substrates.
Compared with prior art, the utility model is all solid state super there is provided a kind of flexible and transparent based on fake capacitance material
Capacitor, including：Ni(OH)2Anode electrode, the Ni (OH)2Anode electrode includes the first flexible substrate and is compound in described
The Ni (OH) of first flexible substrate2Nano-chip arrays transparent membrane；The Ni (OH) is compound in described in being compound in2Nano-chip arrays
First graphene layer of transparent membrane；It is compound in the dielectric substrate of first graphene layer；It is compound in the dielectric substrate
Second graphene layer；The FeOOH negative electrodes of second graphene layer are compound in, the FeOOH negative electrodes include compound
In second graphene layer FeOOH nano-wire arrays transparent membrane and to be compound in the FeOOH nano-wire arrays transparent
Second flexible substrate of film；It is coated on the Ni (OH)2The silver paste of anode electrode and FeOOH negative electrodes edge.This practicality
The ultracapacitor of new offer is asymmetrical ultracapacitor, by Ni (OH)2@rGO and FeOOH@rGO are respectively as positive and negative
Electrode assembling is formed.Wherein, Ni (OH)2Amorphous in nano-chip arrays transparent membrane and FeOOH nano-wire array transparent membranes
State structure it is highly irregular, be conducive to the expansion and contraction of volume, promote the infiltration and diffusion of ion.In combination with graphene
With unique physicochemical properties, FeOOH nano wires and Ni (OH) can be used as2The three-dimensional clad of nanometer sheet, so that
The approach of three-dimensional transmission ion/electronics is set up, the energy density and cycle performance of ultracapacitor is improved.
As a result show, the energy density for the ultracapacitor that the utility model is provided is up to 0.67mWh cm-3, (its work
Voltage is 1.8V), the capability retention after 10000 discharge and recharges is 84.6%.
Brief description of the drawings
Fig. 1 is all solid state super for the flexible and transparent based on fake capacitance material that the utility model that the utility model is provided is provided
The structural representation of the cross section of level capacitor；
The preparation stream for the flexible and transparent all-solid-state supercapacitor based on fake capacitance material that Fig. 2 provides for the utility model
Cheng Tu；
Fig. 3 is Ni (OH)2The SEM figures of nano-chip arrays transparent membrane；
Fig. 4 is the SEM figures of FeOOH nano-wire array transparent membranes under low power；
Fig. 5 is graphene coated Ni (OH) under low power2The SEM figures of anode electrode；
Fig. 6 is the SEM figures of graphene coated FeOOH negative electrodes under high power；
Fig. 7 is pure ITO/PET substrates, Ni (OH)2Electrode, FeOOH electrodes and ultracapacitor light transmission rate curve；
Fig. 8 be three electrode tests under FeOOH transparent flexible electrodes electrochemical properties；
Fig. 9 for the transparent ultracapacitor of all-solid-state flexible that the utility model is provided electrochemical property test result.
Embodiment
The utility model provides a kind of flexible and transparent all-solid-state supercapacitor based on fake capacitance material, including：
Ni(OH)2Anode electrode, the Ni (OH)2Anode electrode includes the first flexible substrate and is compound in described first
The Ni (OH) of flexible substrate2Nano-chip arrays transparent membrane；
The Ni (OH) is compound in described in being compound in2First graphene layer of nano-chip arrays transparent membrane；
It is compound in the dielectric substrate of first graphene layer；
It is compound in the second graphene layer of the dielectric substrate；
The FeOOH negative electrodes of second graphene layer are compound in, the FeOOH negative electrodes are described including being compound in
The FeOOH nano-wire arrays transparent membrane of second graphene layer and it is compound in the FeOOH nano-wire arrays transparent membrane
Second flexible substrate；
It is coated on the Ni (OH)2The silver paste of anode electrode and FeOOH negative electrodes edge.
As shown in figure 1, Fig. 1 is saturating for the flexibility based on fake capacitance material that the utility model that the utility model is provided is provided
The structural representation of the cross section of bright all-solid-state supercapacitor.In Fig. 1,1 is Ni (OH)2Nano-chip arrays transparent membrane, 2 are
FeOOH nano-wire arrays transparent membrane, 3 be the first flexible substrate, 4 be the second flexible substrate, 5 be the first graphene layer, 6 be
Two graphene layers, 7 be silver paste, 8 be dielectric substrate.As shown in Figure 1, all solid state super electricity of flexible and transparent that the utility model is provided
Two pieces of electrodes that container is mainly prepared by different materials, and middle all solid state electrolyte are constituted.Two pieces of wherein positive and negative electrodes
Using ITO/PET as substrate, collector is used as using conductive silver paste.
Specifically, the flexible and transparent all-solid-state supercapacitor based on fake capacitance material that the utility model is provided includes Ni
(OH)2Anode electrode, the Ni (OH)2Anode electrode includes the first flexible substrate and is compound in first flexible substrate
Ni(OH)2Nano-chip arrays transparent membrane；
First flexible substrate is conductive film substrate, preferably ITO substrates, more preferably ITO/PET substrates.
The Ni (OH)2Anode electrode also includes the Ni (OH) for being compound in first flexible substrate2Nano-chip arrays are transparent
Film, wherein, the Ni (OH)2In nano-chip arrays transparent membrane, the Ni (OH)2Nano-chip arrays transparent membrane is by vertical
The Ni (OH) of arrangement2Nanometer blade unit is formed.
The ultracapacitor that the utility model is provided, which also includes being compound in, described is compound in the Ni (OH)2Nano-chip arrays
First graphene layer of transparent membrane, wherein, the graphene layer is used as Ni (OH)2Ni (OH) in nano-chip arrays transparent membrane2
The three-dimensional clad of nanometer sheet, make graphene as pack case connect electrode base ITO layer so that set up three-dimensional transmit from
The approach of son/electronics, improves conductance；And electric double layer capacitance contributes to energy storage.And graphene layer can also be effective
Electrolyte caused by all redox reactions of reduction is peeled off and dissolved, and window voltage is improved, so as to improve power
Density and energy density.
The ultracapacitor that the utility model is provided also includes the dielectric substrate for being compound in first graphene layer.This reality
With new not specifically limited to the species for preparing electrolyte solution, well known to a person skilled in the art suitable for
The species of the electrolyte of ultracapacitor, can be that liquid electrolyte can also be solid-state electrolytic solution.In the utility model
In, it is preferred to use solid-state electrolyte layer prepared by KOH alkaline solution.
The ultracapacitor that the utility model is provided also includes the second graphene layer for being compound in the dielectric substrate.
The ultracapacitor that the utility model is provided also includes the FeOOH negative electricities for being compound in second graphene layer
Pole, the FeOOH negative electrodes include the FeOOH nano-wire arrays transparent membrane for being compound in second graphene layer and multiple
Together in the second flexible substrate of the FeOOH nano-wire arrays transparent membrane.
Wherein, the FeOOH negative electrodes include compound transparent with second graphene layer FeOOH nano-wire arrays
Film, the film has microcosmic nanostructured and transparent self-supporting.Wherein, the FeOOH nano-wire arrays transparent membrane is by hanging down
The FeOOH nanowire units of in line row are formed.Amorphous structure crystallization FeOOH has good chemical property, because it is tied
Structure is highly irregular, is conducive to the expansion and contraction of volume, promotes the infiltration and diffusion of ion.Second graphene layer with
FeOOH nano-wire arrays transparent membrane is combined, and the graphene layer is received as FeOOH in FeOOH nano-wire array transparent membranes
The three-dimensional clad of rice noodles, makes graphene connect the ITO layer of electrode base as pack case, thus set up three-dimensional transmission ion/
The approach of electronics, improves conductance；And electric double layer capacitance contributes to energy storage.And graphene layer can also be reduced effectively
Electrolyte caused by all redox reactions is peeled off and dissolved, and window voltage is improved, so as to improve power density
And energy density.
The FeOOH negative electrodes also include the second flexible substrate, and second flexible substrate is conductive film substrate, excellent
Elect ITO substrates, more preferably ITO/PET substrates as.
The ultracapacitor that the utility model is provided also includes being coated on the Ni (OH)2Anode electrode and FeOOH negative poles
The silver paste of electrode edge.
The utility model additionally provides a kind of above-mentioned flexible and transparent all-solid-state supercapacitor based on fake capacitance material
Preparation method, comprises the following steps：
A Ni (OH)) is prepared2Anode electrode：
In confined conditions, nickel source compound and ammoniacal liquor are mixed, obtains mixed solution；
The mixed solution is subjected to heating response, Ni (OH) is obtained2Nano-chip arrays transparent membrane；
By the Ni (OH)2Nano-chip arrays transparent membrane is transferred in the first flexible substrate, obtains Ni (OH)2Positive pole electricity
Pole；
B FeOOH negative electrodes) are prepared：
In confined conditions, the aqueous solution of ammonia and Fe source compound is reacted in gas-liquid interface, is obtained FeOOH and is received
Nanowire arrays transparent membrane；
The FeOOH nano-wire arrays transparent membrane is transferred in the second flexible substrate, FeOOH negative electrodes are obtained；
C the first graphene layer) is compound in the Ni (OH)2The Ni (OH) of anode electrode2Nano-chip arrays transparent membrane
Side, obtains the first laminated film；
Second graphene layer is compound in the FeOOH nano-wire array transparent membranes side of the FeOOH negative electrodes, obtained
Second laminated film；
D) silver paste is respectively coated in behind the edge of first laminated film and the second laminated film, incited somebody to action by electrolyte
First laminated film and the second laminated film are combined, and obtain all solid state super capacitor of flexible and transparent based on fake capacitance material
Device；
Step A) and step B) limited without order.
The flexible and transparent all-solid-state supercapacitor based on fake capacitance material provided below in conjunction with Fig. 2 the utility model
Preparation method illustrate, Fig. 2 is all solid state super electricity of the flexible and transparent based on fake capacitance material that the utility model is provided
The preparation flow figure of container.
The Ni (OH) that the utility model is provided2The preparation method of anode electrode is：
In confined conditions, nickel source compound and ammoniacal liquor are mixed, obtains mixed solution；
The mixed solution is subjected to heating response, Ni (OH) is obtained2Nano-chip arrays transparent membrane；
By the Ni (OH)2Nano-chip arrays transparent membrane is transferred in the first flexible substrate, obtains Ni (OH)2Positive pole electricity
Pole；
After the utility model first mixes nickel source compound and ammoniacal liquor, it is placed under airtight condition, can also be contained to described
The container for putting nickel source compound and ammoniacal liquor is sealed, and mixture is stirred, and the stirring is preferably magnetic agitation, until
Untill obtaining settled solution, stop stirring, obtain mixed solution；
Wherein, the nickel source compound is preferably Nickelous nitrate hexahydrate, and the concentration of the ammoniacal liquor is preferably 25wt%, described
The mass volume ratio of nickel source compound and ammoniacal liquor is preferably (16~20) g：(17~20) ml, more preferably (17~19) g：(18
~19) ml.
Then, heated at constant temperature is carried out to the mixed solution, the temperature of the heating is preferably 60~65 DEG C, more preferably
62~64 DEG C, during being heated, ammonia is escaped from mixed solution, in the gas-liquid interface and nickel source of mixed solution
Compound is reacted, and Ni (OH) is grown in solution surface2Nano-chip arrays transparent membrane.
Then, by the Ni (OH)2Nano-chip arrays transparent membrane is transferred in the first flexible substrate, obtains Ni (OH)2Just
Pole electrode.
Specifically, flexible substrate is utilized into Electrostatic Absorption, the Ni (OH) of gas-liquid intersection2Nano-chip arrays transparent membrane
It is transferred in flexible substrate.
Ni (OH) will be compounded with2The flexible substrate of nano-chip arrays transparent membrane is cleaned up with deionized water, is dried, and is obtained
To the Ni (OH) of the transparent ultracapacitor of all-solid-state flexible2Anode electrode.
The preparation method of FeOOH negative electrodes that the utility model is provided is：
In confined conditions, the aqueous solution of ammonia and Fe source compound is reacted in gas-liquid interface, is obtained FeOOH and is received
Nanowire arrays transparent membrane；
The FeOOH nano-wire arrays transparent membrane is transferred in the second flexible substrate, FeOOH negative electrodes are obtained；
Specifically, in confined conditions, the ammonia and the aqueous solution of Fe source compound that ammoniacal liquor is volatilized are in gas-liquid interface
Reacted, obtained FeOOH nano-wire array transparent membranes；The temperature of the reaction be 20~30 DEG C, preferably 24~26 DEG C,
The time of the reaction is 48~72h, more preferably 60~70h；
The mode that the utility model is reacted the ammonia and Fe source compound is not specifically limited, can also be by
Carried out according to such as mode：
Fe source compound is mixed with water, the aqueous solution of Fe source compound is obtained；
The container for filling the Fe source compound aqueous solution is sealed with the diaphragm seal with some apertures；
After ammoniacal liquor is mixed with water, sealed with the diaphragm seal with some apertures；
The container of the above-mentioned Fe source compound aqueous solution and ammoniacal liquor is placed in same closed container, the ammonia ease in ammoniacal liquor
Entered to after going out by the aperture on diaphragm seal in the container for filling the Fe source compound aqueous solution, in gas-liquid interface, ammonia with
Fe source compound is reacted, and obtains FeOOH nano-wire array transparent membranes.
Wherein, the Fe source compound is preferably ferric sulfate, and the concentration of the ammoniacal liquor is preferably 25wt%.
The FeOOH nano-wire arrays transparent membrane is transferred in the second flexible substrate, FeOOH negative electrodes are obtained.
Specifically, flexible substrate is utilized into Electrostatic Absorption, the FeOOH nano-wire arrays transparent membrane of gas-liquid intersection is turned
Move in flexible substrate.
The flexible substrate for being compounded with FeOOH nano-wire array transparent membranes is cleaned up with deionized water, dries, obtains
The FeOOH anode electrodes of the transparent ultracapacitor of all-solid-state flexible.
The utility model is not limited the preparation order of the anode electrode and negative electrode.
Then, the first graphene layer is compound in the Ni (OH)2The Ni (OH) of anode electrode2Nano-chip arrays thin transparent
Film side, obtains the first laminated film；
Second graphene layer is compound in the FeOOH nano-wire array transparent membranes side of the FeOOH negative electrodes, obtained
Second laminated film；
The utility model is not specifically limited to the preparation method of first graphene layer or the second graphene layer, this
Preparation method known to art personnel.
In the utility model, first graphene layer or the second graphene layer are preferably made as follows
It is standby：
Disperse graphene in 1-METHYLPYRROLIDONE, obtain the dispersion liquid of graphene；
Behind the bottom that the dispersion liquid of the graphene is placed in the container for filling water, then in the surface dropwise addition acetic acid second of water
Ester, through after a period of time, obtaining graphene film.
In the utility model, the utility model is not particularly limited to the source of the graphene, can select physics
The graphene of method synthesis, the graphene that can also be prepared selected from chemical method.
Graphene is carried out sonic oscillation by the utility model first, then, graphene dispersion in 1-METHYLPYRROLIDONE,
Obtain the dispersion liquid of graphene；Wherein, the concentration of the graphene dispersing solution is preferably 0.05wt%.
Then, the dispersion liquid of graphene is placed in behind the bottom for the container for filling water, then acetic acid second is added dropwise on the surface of water
Ester, through after a period of time, obtaining graphene layer.
In the growth course of above-mentioned graphene layer, exhausting preferably is carried out with air exhauster, the purpose is to use up ethyl acetate
Fast volatilization.
After the completion of graphene layer growth, by Ni (OH)2At anode electrode and FeOOH negative electrodes difference never graphene
Put into solution, picked up in the place for having graphene so that graphene film is attached to Ni (OH) respectively2Anode electrode and FeOOH
On negative electrode, the first laminated film and the second laminated film are obtained.
Silver paste is respectively coated in behind the edge of first laminated film and the second laminated film, by electrolyte by institute
State the first laminated film and the second laminated film is compound, obtain all solid state super capacitor of flexible and transparent based on fake capacitance material
Device.
Specifically, silver paste is respectively coated in behind the edge of first laminated film and the second laminated film, dried,
Time is preferably 10~30min.
Then, by electrolyte be respectively coated in the first laminated film the first graphene layer and the second laminated film second
The surface of graphene layer.Wherein, whether observation electrolyte separates in silver paste, if separation, is coated onto electrolyte with glue head dropper
In silver paste.
The utility model is not specifically limited to the species of the electrolyte.
It is preferred that carrying out the preparation of electrolyte as follows：
The aqueous solution of polyvinyl alcohol (PVA) is mixed with the KOH aqueous solution, mixed solution is obtained；
Sodium Polyacrylate is added into the mixed solution, mixes, obtains electrolyte.
Specifically, carrying out heating water bath after PVA is mixed with water, it is stirred while heating, the poly- second clarified
The aqueous solution of enol (PVA)；
Then, it is KOH is soluble in water, the KOH aqueous solution is obtained, the aqueous solution of the KOH is added dropwise to above-mentioned polyethylene
In the aqueous solution of alcohol (PVA), stirred when being added dropwise, the mixed solution clarified；
Finally, to above-mentioned mixed solution and dripping Sodium Polyacrylate (PAAS), settled solution is obtained after stirring, that is, is electrolysed
Liquid.
The first laminated film and the second laminated film that electrolyte is respectively coated are combined, electrolyte is coated with
Side be combined, by the volatilization of solvent, electrolyte is bonded together due to sticky double-layer filmses, bond during, keep away
Exempt to have air into bubble is formed, constitute device, obtain the flexible and transparent all-solid-state supercapacitor based on fake capacitance material.
The ultracapacitor that the utility model is provided is asymmetrical ultracapacitor, by Ni (OH)2@rGO and FeOOH@
RGO assembles respectively as positive and negative electrode.Wherein, Ni (OH)2Nano-chip arrays transparent membrane and FeOOH nano-wire arrays
Amorphous structure is highly irregular in transparent membrane, is conducive to the expansion and contraction of volume, promotes the infiltration and diffusion of ion.
There are unique physicochemical properties in combination with graphene, FeOOH nano wires and Ni (OH) can be used as2The three of nanometer sheet
Clad is tieed up, so as to set up the approach of three-dimensional transmission ion/electronics, the energy density and cyclicity of ultracapacitor is improved
Energy.
As a result show, the energy density for the ultracapacitor that the utility model is provided is up to 0.67mWh cm-3, (its work
Voltage is 1.8V), the capability retention after 10000 discharge and recharges is 84.6%.
For a further understanding of the utility model, with reference to embodiment the utility model is provided based on fake capacitance material
Flexible and transparent all-solid-state supercapacitor of material and preparation method thereof is illustrated, and protection domain of the present utility model is not by following
The limitation of embodiment.
Embodiment 1
Originally the preparation method of the flexible and transparent all-solid-state supercapacitor of example is applied, is comprised the following steps：
(1) 20g nickel nitrate hexahydrate is weighed in culture dish, then is measured in 20mL 25% ammoniacal liquor addition culture dish,
Sealed at once with preservative film, then carried out magnetic agitation, the time is 10min, obtains settled solution, removes preservative film, fast
Speed takes out stirrer, and preservative film good seal is used again.
(2) heater is preheating to 65 DEG C, then the solution being stirred is carried out 65 DEG C of heated at constant temperature, the time is 10min, molten
Liquid surface grows a thin layer of Ni (OH)2, remove preservative film.To Ni (OH)2Nano-chip arrays transparent membrane carries out Electronic Speculum and swept
Face, it is Ni (OH) as a result to see Fig. 3, Fig. 32The SEM figures of nano-chip arrays transparent membrane.By Fig. 3 it can be seen that being distributed in region equal
The Ni (OH) of even arranged regular2Nano-chip arrays.
(3) ITO of the suitable size of clip, when solution is not cooled down also, using Electrostatic Absorption, the Ni of solution surface
(OH)2It is transferred on ITO, then ITO is gently invaded in deionized water cleans up, then slowly take out, dry, preserves
It is good, the Ni (OH) of the transparent ultracapacitor of all-solid-state flexible is thus made2Anode electrode.(4) 20g Fe (SO) are weighed4It is dissolved in Sheng
In the culture dish for having 100mL deionized waters, magnetic agitation 15min obtains settled solution, seals culture dish with preservative film, is used in combination
Fine needle uniformly pricks four apertures on preservative film；2mL concentrated ammonia liquor and 8mL deionized water, mixing are instilled in a small flask
Uniformly, also sealed with preservative film, and an aperture is pricked with fine needle on preservative film；Culture dish and small flask are placed in closed appearance
In device, the two is allowed fully to react at room temperature, until the gas-liquid intersection of culture dish has grown a thin layer of FeOOH nano wires
Array transparent membrane, the time is 2d；Electronic Speculum surface sweeping is carried out to FeOOH nano-wire arrays transparent membrane, it is low as a result to see Fig. 4, Fig. 4
The SEM figures of FeOOH nano-wire array transparent membranes under times, by Fig. 4 it can be seen that the FeOOH nano-wire arrays of arranged regular.
(5) fully after reaction, culture dish is taken out, clip is adapted to the ITO substrates of size, by Electrostatic Absorption, by gas-liquid
The FeOOH of junction is transferred on ITO substrates；ITO is slowly invaded in deionized water again and cleaned up, then is slowly taken out,
Dry, the FeOOH negative electrodes of the transparent ultracapacitor of all-solid-state flexible are thus made.
(6) PVA6g is weighed in plastic bottle, then is measured in 55mL deionized water addition plastic bottle, and then semitight will
Plastic bottle is placed in 75 DEG C of heating water bath pot, while being slowly stirred, mixing speed is 10r/min, until being clarified
Solution, the time is 2h, finally picks up the bubble of plastics bottle surface.
(7) KOH for weighing 6g is dissolved in 5mL deionized water, dropwise plus in plastic bottle, while accelerating mixing speed, is stirred
Speed is mixed for 45r/min, is dripped off after KOH, semitight slows down mixing speed, mixing speed is 10r/min, continues to stir, directly
To settled solution is obtained, the time is 0.5h；
(8) 8 are instilled toward plastic bottle and drips PAAS, continued to stir, until obtaining settled solution, the time is 0.5h, take out plastics
Bottle, is cooled down, in plastic bottle is exactly electrolyte in atmosphere.
(9) the graphene ultrasonic vibration 2h for synthesizing Physical；The deionized water for weighing 20mL is poured into small culture dish, is used
Glue head dropper amount graphene 1mL, instills culture dish bottom；The air exhauster of ventilating kitchen is opened, 3mL acetic acid is measured with glue head dropper
Ethyl ester, drips to culture dish surface；Culture dish is observed, until all graphenes float to solution surface, air exhauster is closed, obtains stone
Black alkene film.
(10) Ni (OH)2Put at anode electrode and FeOOH negative electrodes never graphene in solution, there is graphite
The place of alkene is picked up so that graphene film is attached to Ni (OH)2On anode electrode and FeOOH negative electrodes.To Ni (OH)2Positive pole
Electrode and FeOOH negative electrodes carry out Electronic Speculum surface sweeping, as a result see Fig. 5 and Fig. 6, and Fig. 5 is graphene coated Ni (OH) under low power2Just
The SEM figures of pole electrode.Ni (OH) shown in Fig. 52The graphene film of layer of transparent, card are coated above nano-chip arrays film
It is bright to prepare graphene-Ni (OH)2Three-dimensional composite material；Fig. 6 is graphene coated FeOOH negative electrodes under high power
SEM schemes.It will be appreciated from fig. 6 that the graphene film of the upper cladding layer of transparent of FeOOH nano-wire arrays, it was demonstrated that obtained graphene-
FeOOH three-dimensional composite material.
(11) Ni (OH)2Fine silver paste is coated at the edge of anode electrode and FeOOH negative electrodes, then is dried, the time
For 20min, appropriate electrolyte is then drawn with glue head dropper, drop 3 drips to Ni (OH)2Anode electrode and FeOOH negative electrodes
On, slowly applying uniform, then dry naturally, until electrolyte becomes sticky, the time is 10min, during which, to observe electrolyte and exist
Whether separated in silver paste, if separation, is coated onto electrolyte in silver paste, the silver paste on particularly four angles with glue head dropper.
(12) Ni (OH) of electrolyte will be coated2Electrode and FeOOH electrodes are slowly stained with, it is to avoid had air to enter and formed gas
Bubble, constitutes device, wraps preservative film, waits device sizing.
Light transmission rate test is carried out to the above-mentioned electrode prepared and super capacitor device, as a result sees that Fig. 7, Fig. 7 are
Pure ITO/PET substrates, Ni (OH)2Electrode, FeOOH electrodes and ultracapacitor light transmission rate curve.It can see by figure
The electrode of different materials and the flexible and transparent all-solid-state supercapacitor being prepared into are saturating under different-waveband under ITO/PET substrates
The transparency of light rate, thus provable electrode and device.It may be seen that under the wave band 550nm of visible ray Fe electrodes and Ni
Electrode light transmittance is respectively 75.1%, and 68.7%, and it is 52.3% to be made after device, display prepared electrode material and device
The transparency of part is good.
Electro-chemical test analysis is carried out to the above-mentioned FeOOH negative electrodes prepared, it is three electrodes as a result to see Fig. 8, Fig. 8
The electrochemical properties of FeOOH transparent flexible electrodes under test.Fig. 8 (a) schemes for the CV of pure FeOOH transparent flexible electrodes.Its
Sweep speed is from 0.1V/S to 1V/S, and Fig. 8 shows a pair of redox peaks, but as the increase for sweeping speed becomes unobvious；Fig. 8
(b) scheme with (c) for the CV of the FeOOH transparent flexible electrodes after coated graphite alkene, its redox reaction is analogous to pure
FeOOH, but because electrical conductivity declines, its CV curve shows as current strength enhancing and redox peak position shifts；Together
When from Fig. 8 (c) it can be seen that, although as the increase for sweeping speed, sweep speed from 2V/S to 40V/S, its redox peaks still clearly may be used
See, this show capacitance characteristic good after FeOOH coated graphite alkene；After Fig. 8 (d) is pure FeOOH and coated graphite alkene
FeOOH transparent flexibles electrode cycle 1000 times after capacitance recoverable amount contrast, find after FeOOH coated graphite alkene it
Cyclical stability is by greatly improving；Fig. 8 (d) is the resistance of the FeOOH transparent flexible electrodes after pure FeOOH and coated graphite alkene
Anti- figure, it is seen that the FeOOH internal resistances of coated graphite alkene are reduced, and have more preferable capacitance characteristic.
Embodiment 2
Originally the preparation method of the flexible and transparent all-solid-state supercapacitor of example is applied, is comprised the following steps：
(1) 16g nickel nitrate hexahydrate is weighed in culture dish, then is measured in 17mL 25% ammoniacal liquor addition culture dish,
Sealed at once with preservative film, then carried out magnetic agitation, the time is 10min, obtains settled solution, removes preservative film, fast
Speed takes out stirrer, and preservative film good seal is used again.
(2) heater is preheating to 63 DEG C, then the solution being stirred is carried out 63 DEG C of heated at constant temperature, the time is 10min, molten
Liquid surface grows a thin layer of Ni (OH)2, remove preservative film.
(3) ITO of the suitable size of clip, when solution is not cooled down also, using Electrostatic Absorption, the Ni of solution surface
(OH)2It is transferred on ITO, then ITO is gently invaded in deionized water cleans up, then slowly take out, dry, preserves
It is good, the Ni (OH) of the transparent ultracapacitor of all-solid-state flexible is thus made2Anode electrode.
(4) 22g Fe (SO) are weighed4It is dissolved in the culture dish for filling 100mL deionized waters, magnetic agitation 20min is obtained
Settled solution, seals culture dish, and four apertures are uniformly pricked on preservative film with fine needle with preservative film；Instilled in a small flask
3mL concentrated ammonia liquor and 7mL deionized water, are well mixed, are also sealed with preservative film, and prick one small on preservative film with fine needle
Hole；Culture dish and small flask are placed in closed container, allow the two fully to react at room temperature, until the gas-liquid of culture dish is handed over
Boundary director has gone out a thin layer of FeOOH, and the time is 3d；
(5) fully after reaction, culture dish is taken out, clip is adapted to the ITO substrates of size, by Electrostatic Absorption, by gas-liquid
The FeOOH of junction is transferred on ITO substrates；ITO is slowly invaded in deionized water again and cleaned up, then is slowly taken out,
Dry, the FeOOH negative electrodes of the transparent ultracapacitor of all-solid-state flexible are thus made.
(6) PVA5g is weighed in plastic bottle, then is measured in 50mL deionized water addition plastic bottle, and then semitight will
Plastic bottle is placed in 75 DEG C of heating water bath pot, while being slowly stirred, mixing speed is 8r/min, until it is molten to obtain clarification
Liquid, the time is 2h, finally picks up the bubble of plastics bottle surface.
(7) KOH for weighing 6g is dissolved in 5mL deionized water, dropwise plus in plastic bottle, while accelerating mixing speed, is stirred
Speed is mixed for 45r/min, is dripped off after KOH, semitight slows down mixing speed, mixing speed is 8r/min, continues to stir, directly
To settled solution is obtained, the time is 0.5h；
(8) 7 are instilled toward plastic bottle and drips PAAS, continued to stir, until obtaining settled solution, the time is 0.5h, take out plastics
Bottle, is cooled down, in plastic bottle is exactly electrolyte in atmosphere.
(9) the graphene ultrasonic vibration 2h for synthesizing Physical；The deionized water for weighing 20mL is poured into small culture dish, is used
Glue head dropper amount graphene 1mL, instills culture dish bottom；The air exhauster of ventilating kitchen is opened, 3mL acetic acid is measured with glue head dropper
Ethyl ester, drips to culture dish surface；Culture dish is observed, until all graphenes float to solution surface, air exhauster is closed, obtains stone
Black alkene film.
(10) Ni (OH)2Put at anode electrode and FeOOH negative electrodes never graphene in solution, there is graphite
The place of alkene is picked up so that graphene film is attached to Ni (OH)2On anode electrode and FeOOH negative electrodes.
(11) Ni (OH)2Fine silver paste is coated at the edge of anode electrode and FeOOH negative electrodes, then is dried, the time
For 20min, appropriate electrolyte is then drawn with glue head dropper, drop 8 drips to Ni (OH)2Anode electrode and FeOOH negative electrodes
On, slowly applying uniform, then dry naturally, until electrolyte becomes sticky, the time is 10min, then tilts Ni (OH)2Positive pole
Electrode and FeOOH negative electrodes, the time is 50s, unnecessary electrolyte is dripped on the table, finally dries 1min.
(12) Ni (OH) of electrolyte will be coated2Electrode and FeOOH electrodes are slowly stained with, it is to avoid had air to enter and formed gas
Bubble, constitutes device, wraps preservative film, waits device sizing.
Embodiment 3
Originally the preparation method of the flexible and transparent all-solid-state supercapacitor of example is applied, is comprised the following steps：
(1) 16g nickel nitrate hexahydrate is weighed in culture dish, then is measured in 17mL 25% ammoniacal liquor addition culture dish,
Sealed at once with preservative film, then carried out magnetic agitation, the time is 10min, obtains settled solution, removes preservative film, fast
Speed takes out stirrer, and preservative film good seal is used again.
(2) heater is preheating to 63 DEG C, then the solution being stirred is carried out 63 DEG C of heated at constant temperature, the time is 10min, molten
Liquid surface grows a thin layer of Ni (OH)2, remove preservative film.
(3) ITO of the suitable size of clip, when solution is not cooled down also, using Electrostatic Absorption, the Ni of solution surface
(OH)2It is transferred on ITO, then ITO is gently invaded in deionized water cleans up, then slowly take out, dry, preserves
It is good, the Ni (OH) of the transparent ultracapacitor of all-solid-state flexible is thus made2Anode electrode.
(4) 20g Fe (SO) are weighed4It is dissolved in the culture dish for filling 100mL deionized waters, magnetic agitation 15min is obtained
Settled solution, seals culture dish, and four apertures are uniformly pricked on preservative film with fine needle with preservative film；Instilled in a small flask
2mL concentrated ammonia liquor and 8mL deionized water, are well mixed, are also sealed with preservative film, and prick one small on preservative film with fine needle
Hole；Culture dish and small flask are placed in closed container, allow the two fully to react at room temperature, until the gas-liquid of culture dish is handed over
Boundary director has gone out a thin layer of FeOOH, and the time is 2d；
(5) fully after reaction, culture dish is taken out, clip is adapted to the ITO substrates of size, by Electrostatic Absorption, by gas-liquid
The FeOOH of junction is transferred on ITO substrates；ITO is slowly invaded in deionized water again and cleaned up, then is slowly taken out,
Dry, the FeOOH negative electrodes of the transparent ultracapacitor of all-solid-state flexible are thus made.
(6) PVA7g is weighed in plastic bottle, then is measured in 58mL deionized water addition plastic bottle, and then semitight will
Plastic bottle is placed in 75 DEG C of heating water bath pot, while being slowly stirred, mixing speed is 10r/min, until being clarified
Solution, the time is 2h, finally picks up the bubble of plastics bottle surface.
(7) KOH for weighing 6g is dissolved in 5mL deionized water, dropwise plus in plastic bottle, while accelerating mixing speed, is stirred
Speed is mixed for 45r/min, is dripped off after KOH, semitight slows down mixing speed, mixing speed is 10r/min, continues to stir, directly
To settled solution is obtained, the time is 0.5h；
(8) 7 are instilled toward plastic bottle and drips PAAS, continued to stir, until obtaining settled solution, the time is 0.5h, take out plastics
Bottle, is cooled down, in plastic bottle is exactly electrolyte in atmosphere.
(9) the graphene ultrasonic vibration 2h for synthesizing Physical；The deionized water for weighing 20mL is poured into small culture dish, is used
Glue head dropper amount graphene 1mL, instills culture dish bottom；The air exhauster of ventilating kitchen is opened, 3mL acetic acid is measured with glue head dropper
Ethyl ester, drips to culture dish surface；Culture dish is observed, until all graphenes float to solution surface, air exhauster is closed, obtains stone
Black alkene film.
(10) Ni (OH)2Put at anode electrode and FeOOH negative electrodes never graphene in solution, there is graphite
The place of alkene is picked up so that graphene film is attached to Ni (OH)2On anode electrode and FeOOH negative electrodes.
(11) Ni (OH)2Fine silver paste is coated at the edge of anode electrode and FeOOH negative electrodes, then is dried, the time
For 20min, appropriate electrolyte is then drawn with glue head dropper, drop 3 drips to Ni (OH)2Anode electrode and FeOOH negative electrodes
On, slowly applying uniform, then dry naturally, until electrolyte becomes sticky, the time is 10min, during which, to observe electrolyte and exist
Whether separated in silver paste, if separation, is coated onto electrolyte in silver paste, the silver paste on particularly four angles with glue head dropper.
(12) Ni (OH) of electrolyte will be coated2Electrode and FeOOH electrodes are slowly stained with, it is to avoid had air to enter and formed gas
Bubble, constitutes device, wraps preservative film, waits device sizing.
To the flexible and transparent device electrochemical property test under above-mentioned two electrode.As a result it is the utility model to see Fig. 9, Fig. 9
The electrochemical property test result of the transparent ultracapacitor of all-solid-state flexible of offer.
Fig. 9 (a) is that to sweep speed be that asymmetric type supercapacitor is in the CV figures of different voltage windows under 0.1V/S, and we can be with
See the fake capacitance behavior under different voltage windows.It can be seen that with the increase of voltage window, its redox peaks is more obvious,
Particularly there are apparent redox peaks under 0-1.8V, illustrate that its electric capacity is dominated by faraday's reaction；Fig. 9 (b) is
Charging and discharging curve of the asymmetric type supercapacitor under different current densities, it has under different current densities significantly fills
Discharge platform, further demonstrate redox reaction, this curves with above surveyed CV.Fig. 9 (c) is asymmetric super
Electric capacity recoverable amount of the level capacitor after circulating 10000 times, after 5000 times circulate, capability retention is up to 92.9%, even
After circulation 10000 times, also 84.6% capacity illustrates its superior stable circulation characteristic；Fig. 9 (d) be individual devices and
Two devices of series connection scheme contrast in the 0.1V/S CV swept under speed, and potential window expands to 3.6V after two devices in series, and
Redox peaks still with matching that single ultracapacitor is surveyed, illustrate that it has well as transparent energy storage system
Application prospect.
From above-described embodiment as can be seen that the utility model based on a kind of method of simple possible to FeOOH and Ni (OH)2
The preparation of electrode material, and graphene film is quickly prepared with the method for self assembly, the structure by way of graphene film is coated
Into graphene-oxyhydroxide composite, and analyze chemical property and the conduct of its front and rear electrode of graphene film cladding
The chemical property of electrode material for super capacitor, it is known that the graphene of preparation-oxyhydroxide composite can obtain non-
Normal high specific capacitance and well stability, are a kind of excellent super capacitor materials.The utility model utilizes FeOOH and Ni
(OH)2The electrode and KOH/PVA solid-state electrolytic solutions of preparation, are assembled into asymmetry transparent flexible ultracapacitor.The device exists
There is 52.3% light transmittance under 550nm, its specific capacity is 0.2mA cm in current density-2When may be up to 17.42mF cm-2,
After being circulated by 10000, its capacity can still keep the 84.6% of initial capacity；Meanwhile, the energy density of the device reaches
0.67mWh cm-3.The new high-performance super capacitor based on graphene-oxyhydroxide composite of the utility model can be with
Applied to current consumption electronic product and various flexible and transparent electronic device products.
The above is only preferred embodiment of the present utility model, it is noted that for the common skill of the art
For art personnel, on the premise of the utility model principle is not departed from, some improvements and modifications can also be made, these improve and
Retouching also should be regarded as protection domain of the present utility model.
Claims (3)
1. a kind of flexible and transparent all-solid-state supercapacitor based on fake capacitance material, it is characterised in that including：
Ni(OH)2Anode electrode, the Ni (OH)2Anode electrode includes the first flexible substrate and is compound in first flexibility
The Ni (OH) of substrate2Nano-chip arrays transparent membrane；
The Ni (OH) is compound in described in being compound in2First graphene layer of nano-chip arrays transparent membrane；
It is compound in the dielectric substrate of first graphene layer；
It is compound in the second graphene layer of the dielectric substrate；
The FeOOH negative electrodes of second graphene layer are compound in, the FeOOH negative electrodes include being compound in described second
The FeOOH nano-wire arrays transparent membrane of graphene layer and it is compound in the second of the FeOOH nano-wire arrays transparent membrane
Flexible substrate；
It is coated on the Ni (OH)2The silver paste of anode electrode and FeOOH negative electrodes edge.
2. flexible and transparent all-solid-state supercapacitor according to claim 1, it is characterised in that the flexible substrate is selected from
ITO substrates.
3. flexible and transparent all-solid-state supercapacitor according to claim 1, it is characterised in that the dielectric substrate is selected from
KOH dielectric substrates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201621183658.1U CN206322594U (en) | 2016-11-03 | 2016-11-03 | A kind of flexible and transparent all-solid-state supercapacitor based on fake capacitance material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201621183658.1U CN206322594U (en) | 2016-11-03 | 2016-11-03 | A kind of flexible and transparent all-solid-state supercapacitor based on fake capacitance material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN206322594U true CN206322594U (en) | 2017-07-11 |
Family
ID=59263037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201621183658.1U Expired - Fee Related CN206322594U (en) | 2016-11-03 | 2016-11-03 | A kind of flexible and transparent all-solid-state supercapacitor based on fake capacitance material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN206322594U (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252093A (en) * | 2016-11-03 | 2016-12-21 | 广东工业大学 | A kind of flexible and transparent all-solid-state supercapacitor based on fake capacitance material and preparation method thereof |
| CN113998740A (en) * | 2021-10-25 | 2022-02-01 | 同济大学 | C-FeOOH lossless deformation self-supporting electrode with wolf tooth rod structure and preparation method |
| CN114597071A (en) * | 2022-03-25 | 2022-06-07 | 宜兴市昱元能源装备技术开发有限公司 | Solid-state energy storage unit |
-
2016
- 2016-11-03 CN CN201621183658.1U patent/CN206322594U/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252093A (en) * | 2016-11-03 | 2016-12-21 | 广东工业大学 | A kind of flexible and transparent all-solid-state supercapacitor based on fake capacitance material and preparation method thereof |
| CN113998740A (en) * | 2021-10-25 | 2022-02-01 | 同济大学 | C-FeOOH lossless deformation self-supporting electrode with wolf tooth rod structure and preparation method |
| CN113998740B (en) * | 2021-10-25 | 2022-10-14 | 同济大学 | C-FeOOH lossless deformation self-supporting electrode with wolf tooth rod structure and preparation method |
| CN114597071A (en) * | 2022-03-25 | 2022-06-07 | 宜兴市昱元能源装备技术开发有限公司 | Solid-state energy storage unit |
| CN114597071B (en) * | 2022-03-25 | 2024-04-12 | 宜兴市昱元能源装备技术开发有限公司 | Solid-state energy storage unit |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106904653B (en) | It the preparation method of vanadium dioxide nano material and is applied in magnesium chargeable battery | |
| CN206322594U (en) | A kind of flexible and transparent all-solid-state supercapacitor based on fake capacitance material | |
| CN103956483B (en) | The preparation method and application of cobalt acid zinc/nickel oxide core-shell nano linear array | |
| CN105206814B (en) | A kind of cubical preparation method of porous active crystal face nano titania of carbon coating exposure (001) of high performance lithium ionic cell cathode material | |
| CN106449132B (en) | A kind of mesoporous Co3O4Nano wire@NiCo2O4Nanometer sheet is classified nucleocapsid array material, preparation method and application | |
| CN104979566B (en) | Combination electrode and its production and use | |
| CN107256809B (en) | A kind of preparation method of transparent flexible supercapacitor | |
| CN104051720B (en) | A kind of material and its preparation and lithium ion anode active material, positive electrode, anode and battery containing the material | |
| CN110265643A (en) | A kind of Sb2O5The preparation method of/carbon cloth flexibility anode material of lithium-ion battery | |
| CN108892169A (en) | The preembedded Mg of stratiform magnesium ion0.3V2O5·1.1H2O nano material and its preparation method and application | |
| CN103346307A (en) | Lithium-ion battery negative material and preparation method thereof | |
| CN108615612A (en) | A kind of flower-shaped cobaltosic oxide-graphene composite material and preparation method thereof | |
| CN108899522A (en) | A kind of high-volume silicon-carbon negative electrode material, preparation method and application | |
| CN106711419A (en) | Core-shell NiO/C porous composite lithium ion battery negative electrode material | |
| CN110444821A (en) | The preparation method of flexible miniature alkaline zinc cell based on three-diemsnional electrode | |
| CN105932265B (en) | A kind of lithium-sulphur cell positive electrode, preparation method and applications | |
| CN102354614B (en) | Phosphide counter electrode for dye sensitized solar cell and preparation method for phosphide counter electrode | |
| CN108808080A (en) | Nano-composite gel electrolyte, lithium secondary battery and preparation method thereof | |
| CN109607521A (en) | A kind of doped graphene material and its preparation method and application | |
| CN108428882A (en) | A kind of zinc silicate/carbon micro-nano hierarchical structure compound and preparation method thereof | |
| CN106847544B (en) | A kind of preparation method of high specific capacitance flexible super capacitor negative electrode material | |
| CN107706003B (en) | A kind of hydro-thermal method prepares graphene/CaTi2O4(OH)2The method of composite granule and its product obtained | |
| CN104600277B (en) | A kind of sized nickel hydroxide/carbon nano composite material of doping zinc and cobalt and its preparation method and application | |
| CN110335766A (en) | Porous polyaniline electrode material based on MOF and its preparation method and application | |
| CN106935832A (en) | Lithium manganese phosphate composite, its preparation method and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170711 Termination date: 20191103 |