CN105304352A - Method for preparing manganese dioxide/nickel hydroxide composite nano sheet by using nickel foam self-reaction and application of manganese dioxide/nickel hydroxide composite nano sheet to supercapacitor - Google Patents
Method for preparing manganese dioxide/nickel hydroxide composite nano sheet by using nickel foam self-reaction and application of manganese dioxide/nickel hydroxide composite nano sheet to supercapacitor Download PDFInfo
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- CN105304352A CN105304352A CN201510658588.4A CN201510658588A CN105304352A CN 105304352 A CN105304352 A CN 105304352A CN 201510658588 A CN201510658588 A CN 201510658588A CN 105304352 A CN105304352 A CN 105304352A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a method for preparing a manganese dioxide/nickel hydroxide composite nano sheet by using nickel foam self-reaction and application of the manganese dioxide/nickel hydroxide composite nano sheet to a supercapacitor. According to the method, the nickel foam directly reacts with a potassium permanganate solution, so that the manganese dioxide/nickel hydroxide composite nano sheet can be obtained; in the reaction of the nickel foam and the potassium permanganate solution, the nickel foam reduces potassium permanganate to manganese dioxide, and at the same time, the nickel foam itself is oxidized into nickel hydroxide, and therefore, the composite nano sheet can be obtained; the nano sheet is vertically grown on the surface of the foam nickel to form a uniform film layer; and in this reaction, the foam nickel is also used as a reducing agent and a current collector, and electrode preparation can be completed in one step. The method has the advantages of simple process, low cost and large-area preparation. With the method adopted, an obtained composite electrode material has high specific capacitance and excellent cyclic stability, and has a bright application prospect.
Description
Technical field
Patent of the present invention relates to the method and the supercapacitor applications thereof that utilize nickel foam autoreaction to prepare manganese dioxide/nickel hydroxide composite nano plate, belongs to new material technology field.
Background technology
Ultracapacitor, also known as electrochemical capacitor, is a kind of novel energy-storing device between traditional capacitor and battery.Compared with traditional capacitor, ultracapacitor has higher specific capacitance, and its specific capacitance is more than ten times of traditional capacitor.
[1]compared with battery, ultracapacitor has higher specific power, can abrupt release ultrahigh current, has that the discharge and recharge time is short, efficiency for charge-discharge is high, service life cycle is long, an advantage such as memory-less effect and basic Maintenance free,
[1,2]it has filled up the blank between traditional capacitor and this two classes energy-storage travelling wave tube of battery, and likely improve energy density further and expand range of application, in mobile communication, information technology, consumer electronics, electric automobile, Aero-Space and science and techniques of defence etc., there is of crucial importance and wide application prospect, become the focus of countries in the world research, various countries formulate immediate objective and distant view development plan one after another, are classified as key strategy research object.
From the angle of electrode material and stored energy principle, ultracapacitor can be divided into double electric layers supercapacitor and fake capacitance ultracapacitor.
[2,3]double electric layer capacitor utilizes the interfacial electric double layer formed between electrode and electrolyte to carry out stored charge, the number of storing electricity depends on the size of electrode material specific area, thus its electrode often adopts the material with carbon element with bigger serface, as active carbon, Graphene and carbon nano-tube etc.
[2,4-7]these material with carbon elements are generally by high-temperature heat treatment or High Temperature Gas phase reaction preparation, and complex process, equipment requirement is higher, and energy consumption is large, and thus cost is higher.Double electric layers supercapacitor has the large advantage of power density, but its ratio capacitance and energy density less, thus limit its range of application.
[2]pseudocapacitors utilizes the redox reaction of the Rapid reversible occurred in electrode material surface or nearly superficial layer to realize accumulate, pseudocapacitors can obtain much higher ratio capacitance and energy density compared with double electric layers supercapacitor, therefore has good application prospect.
[3]fake capacitance electrode material for super capacitor mainly uses transition metal oxide and conducting polymer, as manganese dioxide, nickel oxide, cobalt oxide, polyaniline and polypyrrole etc.
[3,8-12]wherein, manganese dioxide has the advantages such as very high theoretical ratio capacitance (~ 1370F/g), high voltage, rich reserves, environmental friendliness and low cost because of it and is subject to the especially attention of people.
[11]the method preparing manganese bioxide electrode material at present mainly contains hydro thermal method, electrodeposition process and chemical reduction method etc.
[13-16]it is comparatively complicated that hydro thermal method and electrodeposition process prepare electrode material process, and equipment requirement is higher, produces difficulty in enormous quantities comparatively large, make application cost higher.The fake capacitance oxide material that chemical preparation goes out is generally powder type, and being prepared into electrode needs the processes such as slurrying, film, drying, compacting, and technique is loaded down with trivial details, and cost is high.Need to add binding agent and conductive agent in pulping process simultaneously, thus cause the decline of capacitor performance.Although the method such as electro-deposition and hydro-thermal also can Direct precipitation oxide material thus avoid the above-mentioned loaded down with trivial details technique preparing electrode on a current collector, its depositional area is less, needs professional equipment simultaneously, and cost is higher, is unfavorable for large-scale application.
Prior art CN102709058A provides a kind of method that electrochemical deposition method prepares ultracapacitor manganese dioxide-nickel hydroxide composite electrode material, for pole plate carries out cathodic electrochemical deposition in potassium permanganate and nickel nitrate mixed aqueous solution electrolyte with nickel foam, nickel sheet or titanium sheet, post-depositional polar board surface washed with de-ionized water, to dry, namely obtain with nickel foam, nickel sheet or titanium sheet be substrate, top layer has the combination electrode material of manganese dioxide-nickel hydroxide laminated film.This patent does not provide the information of depositional area.This kind of method shortcoming shows following four each and every one aspects: 1) need to use electroplating device, add equipment cost; 2) need in electrochemical deposition production process to consume a large amount of electric energy, add production cost, do not meet green requirements of the times of producing simultaneously; 3) area of the electrode material deposited is limited to the power of used electroplating device, is difficult to freely expand depositional area; 4) the circulate capacity retention of 500 times of the electrode material prepared by is only 82.8%, far can not meet the life requirements of supercapacitor applications.
At present, set up the simple preparation technology of the high-performance super capacitor being applicable to suitability for industrialized production, reduce production cost and energy resource consumption, the progress for ultracapacitor industry is significant.
List of references
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Summary of the invention
Patent of the present invention is based on Problems existing in above-mentioned electrode material for super capacitor preparation and device assembling process, a kind of nickel foam autoreaction is provided to prepare manganese dioxide/nickel hydroxide composite nano plate and the application at electrode material for super capacitor and device thereof thereof, the preparation of the method electrode material does not need the equipment of high cost, energy resource consumption is not had in production process, can large area prepare, simultaneously, active material direct growth on a current collector, electrode is prepared a step and is completed, and eliminates the technology for preparing electrode such as slurrying film.The technology of the present invention makes the preparation technology of ultracapacitor greatly simplify, cost and cheap.Meanwhile, prepared electrode material and ultracapacitor have excellent performance.
In order to overcome the deficiency that existing electrode material for super capacitor preparation technology flow process is complicated, be not suitable for large-scale production, high expensive; the invention provides a kind of novel electrode material preparation method; the method is without the need to the equipment and process flow process of complexity; not only effectively can reduce production cost, and prepared electrode material has excellent chemical property.The present invention is based on following chemical reaction:
3Ni+2KMnO
4+4H
2O＝3Ni(OH)
2+2MnO
2+2KOH
Utilize this reaction can prepare the composite nano plate of manganese dioxide and nickel hydroxide at ambient temperature.The method is very simple, and only Commercial foam nickel need be soaked certain hour in liquor potassic permanganate can obtain required electrode material.In this reaction, nickel foam is simultaneously as collector and reducing agent, and electrode preparation can a step complete.The present invention is the composite oxide material utilizing this reaction to prepare manganese dioxide and nickel hydroxide both at home and abroad first.
Described liquor potassic permanganate concentration is 0.005-0.2molL
-1, preferred concentration is 0.05molL
-1.The described reaction time is 12-48h, and the preferred reaction time is 24h.Described reaction condition is normal temperature neutral environment.
The whole preparation process of the present invention only needs to carry out at normal temperatures, without the need to using special installation, only needs the container containing liquor potassic permanganate.Owing to not needing Special Equipment, prepare area and do not limit by equipment, only depend on and hold the container of reaction solution and the size of foam nickel base, can large area preparation.During by liquid for the assembling of prepared electrode material and solid-state super capacitor, because electrode material is grown directly upon on nickel foam collector, therefore do not need to add binding agent and conductive agent, eliminate complicated technology for preparing electrode, the simple environmental protection of method, effectively can reduce production cost, be suitable for large-scale production.
Because a lot of metal simple-substance is as cobalt, iron, vanadium, molybdenum, tungsten, zinc etc. can reduce liquor potassic permanganate, and therefore this method can also be generalized to other metal to prepare different composite electrode material for super capacitor.
The concrete technical scheme of the present invention
The invention provides the method that nickel foam autoreaction prepares manganese dioxide/nickel hydroxide composite nano plate, comprise, under normal temperature, nickel foam is soaked certain hour in liquor potassic permanganate, utilize the redox reaction that the potassium permanganate in nickel foam and solution occurs, one deck manganese dioxide/nickel hydroxide composite nano plate can be generated in nickel foam.
Wherein, described liquor potassic permanganate concentration is preferably 0.005-0.2molL
-1.
Wherein, the described reaction time is preferably 12-48h.
Wherein, described reaction temperature is preferably 20-30 DEG C.
The preparation method of described a kind of manganese dioxide/nickel hydroxide composite nano plate, is preferably,
(1) the Commercial foam nickel of clip certain size, respectively acetone, deionized water for ultrasonic cleaning 15min after at 0.1molL
-1watery hydrochloric acid in soak 5min, then in deionized water ultrasonic cleaning to neutral;
(2) 0.005-0.2molL is prepared
-1the liquor potassic permanganate of variable concentrations, immerses the nickel foam of wash clean in solution, soak different time 12-48h at 20-30 DEG C after, by washed with de-ionized water, and finally vacuumize 12h and get final product at 60 DEG C.
Described soak time is preferably 24h.
A kind of manganese dioxide/nickel hydroxide composite nano plate, is prepared by aforesaid preparation method.
Described manganese dioxide/nickel hydroxide composite nano plate, thickness is 2-7nm, and the loose structure size of nanometer sheet composition is less than 50nm.
A kind of ultracapacitor, the aforesaid a kind of manganese dioxide/nickel hydroxide composite nano plate of described supercapacitor applications is as electrode material for super capacitor.
Aforesaid a kind of ultracapacitor, preferably,
Described ultracapacitor is liquid symmetrical ultracapacitor, and the step of assembling liquid symmetrical ultracapacitor comprises:
(1) compound concentration is 1molL respectively
-1metabisulfite solution, 1molL
-1potassium hydroxide solution and 1molL
-1potassium hydroxide and 0.5molL
-1the mixed solution of sodium sulphate,
(2) use glass fiber filter paper as diaphragm of supercapacitor, the electrode material of clip two pieces of formed objects, soaks 5min in the electrolytic solution by electrode material and barrier film,
(3) barrier film is sandwiched in the middle of two cube electrode materials and can forms liquid ultracapacitor;
Or described ultracapacitor is solid-state symmetrical ultracapacitor, the step of assembling solid-state symmetrical ultracapacitor comprises:
(1) prepare PVA/KOH solid electrolyte, 3.4gKOH and 6gPVA added in 60ml deionized water, at 85 DEG C of temperature, stir 1h,
(2) use glass fiber filter paper as diaphragm of supercapacitor, the electrode material of clip two pieces of formed objects, soaks 5min in the electrolytic solution by electrode material and barrier film,
(3) electrode material after immersion and barrier film are taken out, barrier film is sandwiched in the middle of two cube electrode materials, then leave standstill 12h and make its natural drying obtain solid-state super capacitor;
Or described ultracapacitor is solid asymmetric ultracapacitor, assembling solid asymmetric ultracapacitor comprises:
(1) activated carbon negative electrode material is prepared.By active carbon, acetylene black and polytetrafluoroethylene are sized mixing according to the ratio mixing of 8:1:1, at nickel foam surface coating, claim its quality after dry,
(2) prepare PVA/KOH solid-state electrolytic solution, 17gKOH and 30gPVA added in 300mL deionized water, at 85 DEG C of temperature, stir 1h,
(3) use glass fiber filter paper as diaphragm of supercapacitor, clip one cube electrode material, soaks 5min in the electrolytic solution by positive and negative electrode material and barrier film,
(4) electrode material after immersion and barrier film are taken out, barrier film is sandwiched in the middle of positive and negative electrode material, then leave standstill 12h and make its natural drying obtain solid-state super capacitor.
Beneficial effect of the present invention
(1) electrode material prepared by the method demonstrates good chemical property in three electrode test systems.At 1molL
-1potassium hydroxide+0.5molL
-11.25mAcm in sodium sulphate mixed electrolytic solution
-2current density under carry out charge-discharge test, electrode material area ratio electric capacity and quality can reach 4.38Fcm respectively than electric capacity
-2and 2916.7Fg
-1(based on manganese dioxide/nickel hydroxide composite nano plate gross mass).
(2) in bipolar electrode system, capacitor shows desirable capacitive property, and liquid and solid-state symmetrical ultracapacitor can reach 578.5mFcm respectively
-2and 269.2mFcm
-2area ratio electric capacity.
(3) in bipolar electrode system, liquid and solid-state symmetrical ultracapacitor and obtain 20 μ Whcm respectively
-2(power density is 30 μ Wcm
-2) and 9 μ Whcm
-2(power density is 60 μ Wcm
-2) higher energy density.
(4) liquid state prepared of this method and solid-state symmetric capacitor are at 12.5mAcm
-2current density under carry out 25000 charge and discharge cycles after ratio capacitance conservation rate be respectively 82.2% and 92.3%, possess the electrochemical stability of superelevation, have very important meaning in actual applications.
(5) because the voltage of single symmetric capacitor is 0.5V, 4 areas are 2 × 2cm by we
2the series connection of solid-state symmetrical ultracapacitor after, under the electric current of 2mA, charge to 2V, successfully can drive a commercial red LED (1.8V).
(6) significant advantage of this method is preparation large area electrode material for super capacitor and device, and we utilize this method to prepare full-size is 25 × 100cm
2electrode material, assembling 4 same areas is according to the method described above 25 × 50cm
2solid-state symmetrical ultracapacitor, after series connection, under the electric current of 50mA, charge to 2V, successfully can drive the array being arranged in " HIT " printed words by 23 red LED.
(7) electrode material prepared of this method and activated carbon negative electrode material form asymmetric solid-state super capacitor, and have shown superior performance, and quality reaches 292Fg respectively than electric capacity and energy density
-1and 91.3Whkg
-1.2 same areas are 10 × 10cm
2solid asymmetric ultracapacitor series connection after charge to 3V, successfully can drive the array being arranged in " HITSZ " printed words by 165 blue leds.
(8) compared with the existing method preparing oxide electrode material and ultracapacitor, the technology of the present invention does not need Special Equipment, prepare area huge, active material directly grows on a current collector, electrode is prepared a step and is completed, electrode material and device packaging technology simplify all greatly, thus cost reduces greatly.
(9) although the present invention's material type prepared relative to prior art CN102709058A seemingly, but CN102709058A is prepared based on electrochemical deposition method, the present invention is based on natural solution oxide reduction reaction preparation, the two technical thought is completely different, and documents is difficult to realize the corresponding effect of the present invention, be mainly reflected in following aspect: 1) the present invention is without any need for special equipment, eliminate equipment cost, and the required electrochemical deposition equipment of prior art CN102709058A; 2) there is no power consumption in electrode material production process of the present invention, greatly reduce production cost, achieve green production, and prior art CN102709058A will consume a large amount of electric energy in electrochemical deposition process; 3) the present invention has very outstanding advantage in extensive deposition, produce due to electrode material in the present invention and do not need to use any equipment, so depositional area does not limit by equipment, freely depositional area can be expanded by the size simply expanding reaction vessel, and the restriction of the powered chemical deposition equipment of prior art CN102709058A depositional area; 4) material prepared by the present invention is the nanometer sheet of vertical oriented growth; and the material prepared by prior art CN102709058A is the nano wire of particle or disorderly orientation, the cyclical stability of electrode material of the present invention is caused greatly to be better than prior art CN102709058A.
Accompanying drawing explanation
Fig. 1 is the process schematic that the invention process example 1 prepares manganese dioxide/nickel hydroxide composite nano plate.
Fig. 2 is the electron scanning micrograph (SEM) of nanometer sheet prepared by the invention process example 1.
The X-ray diffraction spectrum (XRD) of Fig. 3 nanometer sheet prepared by the invention process example 1.
Fig. 4 is Mn2p (a), Ni2p (b) and O1s (c) x-ray photoelectron spectroscopy (XPS) of nanometer sheet prepared by the invention process example 1.
Fig. 5 is low power (a) and high-resolution (b) transmission electron microscope (TEM) photo of nanometer sheet prepared by the invention process example 1.
Fig. 6 is that nanometer sheet material prepared by the invention process example 1 is at 1molL
-1potassium hydroxide+0.5molL
-1charging and discharging curve in sodium sulphate mixed electrolytic solution under different current density.
Fig. 7 is the optical photograph of the broad-area electrode material prepared by the invention process example 2, and Fig. 7 (a) is the nickel foam color contrast before and after reaction, and Fig. 7 (b) is the large area nickel foam photo after growing mixed nanometer sheet.
Fig. 8 is the charging and discharging curve of sample prepared by the invention process example 3.
Fig. 9 is the charging and discharging curve of sample prepared by the invention process example 4.
Figure 10 is the charging and discharging curve of the ultracapacitor prepared by the invention process example 5.
Figure 11 is the working stability linearity curve of the ultracapacitor prepared by the invention process example 5.
Figure 12 is area prepared by the invention process example 6 is 2 × 2cm
2the constant current charge-discharge curve of ultracapacitor.
Figure 13 is area prepared by the invention process example 6 is 2 × 2cm
2the working stability linearity curve of ultracapacitor.
Figure 14 is 4 areas prepared by embodiment 6 is 2 × 2cm
2the optical photograph that 2V drives a red LED (1.8V) is charged to after solid-state symmetrical ultracapacitor series connection.
Figure 15 is 4 areas prepared by embodiment 6 is 25 × 50cm
2the optical photograph of " HIT " printed words array that 2V drives to be made up of 23 red LED is charged to after solid-state symmetrical ultracapacitor series connection.
Figure 16 is the charging and discharging curve of the ultracapacitor prepared by the invention process example 7.
Figure 17 is the working stability linearity curve of the ultracapacitor prepared by the invention process example 7.
Figure 18 is 2 areas prepared by embodiment 7 is 10 × 10cm
2the optical photograph of " HITSZ " printed words array that 3V drives to be made up of 165 blue leds is charged to after the series connection of solid asymmetric ultracapacitor.
The specific embodiment of the invention
Below in conjunction with drawings and Examples, the present invention is further described.Following embodiment further illustrates of the present invention, instead of limitation of the present invention.Below by instantiation, realization means of the present invention is described.The following stated is only better embodiment of the present invention, and all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Embodiment 1: the preparation of manganese dioxide/nickel hydroxide composite nano plate
This examples show grows manganese dioxide/nickel hydroxide composite nano plate in the foam nickel base that area is less, and concrete preparation process is as follows:
(1) by regular-type foam nickel (thickness 1mm, 110ppi, the 320gm of market purchase
-2) be cut into 2 × 4cm
2size, in deionized water after ultrasonic cleaning 15min at 0.1molL
-1soak 5min in watery hydrochloric acid, then ultrasonic cleaning is extremely neutral in deionized water.
(2) 30mL deionized water is put into the plastic containers that length, width and height are 3.2cm × 3.2cm × 5cm, pour the potassium permanganate of 0.237g subsequently into, stir and be made into 0.05molL
-1liquor potassic permanganate.Then the nickel foam of wash clean is immersed, take out after soaking 24h at normal temperatures, become colorless to deionized water by washed with de-ionized water, finally at 60 DEG C, vacuumize 12h can obtain composite nano plate electrode material.
Fig. 1 is composite nano plate preparation process schematic diagram, can find out that this method is very simple, can obtain required electrode material through simple immersion.Fig. 2 is the electron scanning micrograph (SEM) of prepared electrode material, and the material prepared by photo display has nanometer sheet structure.Nanometer sheet thickness is 2-7nm, and nanometer sheet is connected to each other and forms porous pattern, and the hole dimension between nanometer sheet is generally at below 50nm.Fig. 3 is the X-ray diffraction spectrum (XRD) of prepared nanometer sheet, is MnO through the nanometer sheet prepared by contrast standard spectrum (JCPDSNo.42-1316, JCPDSNo.38-0715)
2with Ni (OH)
2compound phase, diffraction surfaces corresponding to diffraction maximum marks in the drawings.Fig. 4 is Mn2p (a), Ni2p (b) and O1s (c) x-ray photoelectron spectroscopy (XPS) of prepared nanometer sheet, test shows that in nanometer sheet, main component is Mn, Ni and O, and chemical state and the proportioning of three kinds of elements meet MnO
2with Ni (OH)
2compound, shows that nanometer sheet is by MnO further
2with Ni (OH)
2composition.Fig. 5 is low power (a) and high-resolution (b) transmission electron microscope (TEM) photo of sample, and the thickness measuring nanometer sheet is 2-7nm, consistent with SEM test result.The high-resolution TEM photo analysis of single nanometer sheet is shown that each nanometer sheet is by MnO
2with Ni (OH)
2microcell forms.Fig. 6 is that prepared nanometer sheet material is at 1molL
-1potassium hydroxide+0.5molL
-1charging and discharging curve in sodium sulphate mixed electrolytic solution under different current density, calculates based on MnO from discharge curve
2/ Ni (OH)
2the quality of active material is 2916.7Fg than electric capacity
-1, area ratio electric capacity is 4.38Fcm
-2, show that prepared nanometer sheet has excellent electrochemical properties.
Embodiment 2: the preparation of manganese dioxide/nickel hydroxide composite nano plate
This examples show grows manganese dioxide/nickel hydroxide composite nano plate in large-area foam nickel base, and preparation technology parameter is substantially identical with embodiment 1, difference be nickel foam chip size, the reaction vessel size of joining amount of solution and using.Detailed process is as follows:
(1) 25 × 100cm will be of a size of
2nickel foam (thickness 1mm, 110ppi, 320gm
-2) ultrasonic cleaning 15min in deionized water, at 0.1molL after taking-up
-1soak 5min in watery hydrochloric acid, then ultrasonic cleaning is extremely neutral in deionized water.
(2) 10L deionized water is put into the plastic containers that length, width and height are 60cm × 40cm × 38cm, pour the potassium permanganate of 79g subsequently into, stir and be made into 0.05molL
-1liquor potassic permanganate.Then the nickel foam of wash clean is immersed, take out after soaking 24h at normal temperatures, become colorless to deionized water by washed with de-ionized water, finally at 60 DEG C, vacuumize 12h can obtain large-area composite nano plate electrode material.
Fig. 7 is the optical photograph of prepared broad-area electrode material, and figure (a) is the nickel foam color contrast before and after reaction, and figure (b) is the large area nickel foam photo after growing mixed nanometer sheet.After reaction, nickel foam becomes reacted brown color from the grey before reaction, to show after simple reaction the new product of nickel foam Surface Creation.Structural characterization and electro-chemical test obtain the result identical with embodiment 1, and the material prepared by confirmation is MnO
2with Ni (OH)
2composite nano plate, super capacitor excellent, structures and characteristics stable and consistent everywhere when simultaneously confirming large area deposition.
Embodiment 3: the preparation of manganese dioxide/nickel hydroxide composite nano plate
In this embodiment, the soak time of nickel foam in liquor potassic permanganate is 30h, and other condition is identical with embodiment 1.Test result shows, prepared nanometer sheet pattern, structure and composition and embodiment 1 difference little.Fig. 8 is the charging and discharging curve of sample prepared by this embodiment, and its quality is respectively 2806Ag than electric capacity and area ratio electric capacity
-1and 5.05Fcm
-2, its quality declines to some extent than electric capacity compared with embodiment 1, but area ratio electric capacity is higher.
Embodiment 4: the preparation of manganese dioxide/nickel hydroxide composite nano plate
The concentration of the liquor potassic permanganate used in this embodiment is 0.1molL
-1, the soak time of nickel foam in liquor potassic permanganate is 12h, and other condition is identical with embodiment 1.Test result shows, the product obtained remains MnO
2with Ni (OH)
2composite nano plate, its appearance structure is roughly the same with embodiment 1, but the thickness of nanometer sheet slightly increases.Fig. 9 is the charging and discharging curve of sample prepared by this embodiment, and its quality is respectively 2777.8Fg than electric capacity and area ratio electric capacity
-1and 3.75Fcm
-2, its quality declines to some extent than electric capacity compared with embodiment 1, but advantage to be growth time shorter.
Embodiment 5: the assembling of water base symmetrical ultracapacitor
(1) 1molL is prepared
-1potassium hydroxide+0.5molL
-1the mixed solution of sodium sulphate.
(2) use glass fiber filter paper as diaphragm of supercapacitor, electrode material prepared by embodiment 1 is cut into 2 × 2cm
2size, soaks 5min in the electrolytic solution by electrode material and barrier film.
(3) barrier film is sandwiched in the middle of two cube electrode materials and can forms liquid symmetrical ultracapacitor.
Figure 10 is the charging and discharging curve of the ultracapacitor of this embodiment assembling, and operating voltage is 0.5V.Capacitor shows desirable capacitive property, at 0.125mAcm
-2current density under, the area ratio electric capacity of liquid symmetrical ultracapacitor reaches 578.5mFcm
-2.Figure 11 is the working stability linearity curve of assembled ultracapacitor, at 12.5mAcm
-2current density under carry out circulate 25000 ratio capacitance of constant current charge-discharge and keep 82.2%, there is excellent cyclical stability.
Embodiment 6: the assembling of solid-state symmetrical ultracapacitor
This embodiment assembles the different solid-state super capacitor of two kinds of sizes.Step is as follows:
(1) prepare PVA/KOH solid electrolyte, 300gPVA and 170gKOH is mixed, adds 6L deionized water, vigorous stirring 1h at 85 DEG C.
(2) use glass fiber filter paper as diaphragm of supercapacitor.Electrode material prepared by embodiment 1 is cut into 2 × 2cm
2size, is cut into 25 × 50cm by electrode material prepared by embodiment 2
2size, soaks 5min in the electrolytic solution by above-mentioned electrode material and barrier film.
(3) barrier film after above-mentioned immersion and electrode material are assembled into ultracapacitor, during assembling by diaphragm clip between two pieces of measure-alike electrode materials, leave standstill 12h natural drying, obtain respectively being of a size of 2 × 2cm
2with 25 × 50cm
2solid-state super capacitor.
Test shows that assembled solid-state symmetrical ultracapacitor has good performance.Figure 12 is 2 × 2cm
2the constant current charge-discharge curve of ultracapacitor, voltage range is 0.5V, calculates and shows that it is at 0.25mAcm
-2current density under area ratio electric capacity reach 269.2mFcm
-2.Figure 13 is its stable circulation linearity curve, at 12.5mAcm
-2current density under the constant current charge-discharge ratio capacitance conservation rate after 25000 times that circulates be 92.3%, demonstrate job stability excellent especially.By 42 × 2cm
2be charged to 2V after solid-state symmetrical ultracapacitor series connection and can drive a red LED (1.8V), as shown in figure 14.By 4 25 × 50cm
2" HIT " array that 2V can drive 23 red LED compositions is charged to, as shown in figure 15 after solid-state super capacitor series connection.
Embodiment 7: the assembling of solid-state symmetrical ultracapacitor
(1) activated carbon negative electrode material is prepared.By active carbon, acetylene black and polytetrafluoroethylene are sized mixing according to the ratio mixing of 8:1:1, are being of a size of 1 × 1cm respectively
2with 10 × 10cm
2nickel foam surface coating, claim its quality after dry.
(2) prepare PVA/KOH solid-state electrolytic solution, 30gPVA and 17gKOH is mixed, adds 300mL deionized water, vigorous stirring 1h at 85 DEG C.
(3) use glass fiber filter paper as diaphragm of supercapacitor, electrode material prepared by embodiment 1 is cut into 1 × 1cm
2size, is cut into 10 × 10cm by electrode material prepared by embodiment 2
2size, soaks 5min in the electrolytic solution by above-mentioned positive and negative electrode material and barrier film.
(4) electrode material after immersion and barrier film are taken out, barrier film is sandwiched in the middle of positive and negative electrode material, then leave standstill 12h and make its natural drying obtain solid-state super capacitor.
Test shows that assembled solid asymmetric ultracapacitor has good performance.Figure 16 is 1 × 1cm
2the constant current charge-discharge curve of ultracapacitor, voltage range is 1.5V, calculates and shows that it is at 1Ag
-1current density under quality reach 292Fg than electric capacity
-1, energy density reaches 91.3Whkg
-1(750Wkg
-1).Figure 17 is its stable circulation linearity curve, at 2Ag
-1current density under the constant current charge-discharge ratio capacitance conservation rate after 20000 times that circulates be 94%, demonstrate job stability excellent especially.By 2 10 × 10cm
2" HITSZ " array that 3V can drive 165 blue led compositions is charged to, as shown in figure 18 after the series connection of solid asymmetric ultracapacitor.
Claims (10)
1. nickel foam autoreaction prepares the method for manganese dioxide/nickel hydroxide composite nano plate, it is characterized in that, under normal temperature, nickel foam is soaked certain hour in liquor potassic permanganate, utilize the redox reaction that the potassium permanganate in nickel foam and solution occurs, one deck manganese dioxide/nickel hydroxide composite nano plate can be generated in nickel foam.
2. nickel foam autoreaction according to claim 1 prepares the method for manganese dioxide/nickel hydroxide composite nano plate, it is characterized in that, described liquor potassic permanganate concentration is 0.005-0.2molL
-1.
3. nickel foam autoreaction according to claim 1 prepares the method for manganese dioxide/nickel hydroxide composite nano plate, it is characterized in that, the described reaction time is 12-48h.
4. nickel foam autoreaction according to claim 1 prepares the method for manganese dioxide/nickel hydroxide composite nano plate, it is characterized in that, described reaction temperature is 20-30 DEG C.
5. nickel foam autoreaction according to claim 1 prepares the method for manganese dioxide/nickel hydroxide composite nano plate, it is characterized in that,
(1) the Commercial foam nickel of clip certain size, respectively acetone, deionized water for ultrasonic cleaning 15min after at 0.1molL
-1watery hydrochloric acid in soak 5min, then in deionized water ultrasonic cleaning to neutral;
(2) 0.005-0.2molL is prepared
-1the liquor potassic permanganate of variable concentrations, immerses the nickel foam of wash clean in solution, soak different time 12-48h at 20-30 DEG C after, by washed with de-ionized water, and finally vacuumize 12h and get final product at 60 DEG C.
6. nickel foam according to claim 5 prepares the method for manganese dioxide/nickel hydroxide composite nano plate, it is characterized in that, described soak time is 12,24,36 or 48h.
7. manganese dioxide/nickel hydroxide composite nano plate, is characterized in that, is prepared by the nickel foam autoreaction method described in the arbitrary claim of claim 1-6.
8. a kind of manganese dioxide/nickel hydroxide composite nano plate according to claim 7, is characterized in that, described manganese dioxide/nickel hydroxide composite nano plate thickness is 2-7nm, and the loose structure size of nanometer sheet composition is less than 50nm.
9. a ultracapacitor, is characterized in that, a kind of manganese dioxide/nickel hydroxide composite nano plate of described supercapacitor applications claim 7 or 8 is used as electrode material for super capacitor.
10. a kind of ultracapacitor according to claim 9, is characterized in that,
Described ultracapacitor is liquid symmetrical ultracapacitor, and the step of assembling liquid symmetrical ultracapacitor comprises:
(1) compound concentration is 1molL respectively
-1metabisulfite solution, 1molL
-1potassium hydroxide solution and 1molL
-1potassium hydroxide and 0.5molL
-1the mixed solution of sodium sulphate,
(2) use glass fiber filter paper as diaphragm of supercapacitor, the electrode material of clip two pieces of formed objects, soaks 5min in the electrolytic solution by electrode material and barrier film,
(3) barrier film is sandwiched in the middle of two cube electrode materials and can forms liquid ultracapacitor;
Or described ultracapacitor is solid-state symmetrical ultracapacitor, the step of assembling solid-state symmetrical ultracapacitor comprises:
(1) prepare PVA/KOH solid electrolyte, 3.4gKOH and 6gPVA added in 60mL deionized water, at 85 DEG C of temperature, stir 1h,
(2) use glass fiber filter paper as diaphragm of supercapacitor, the electrode material of clip two pieces of formed objects, soaks 5min in the electrolytic solution by electrode material and barrier film,
(3) electrode material after immersion and barrier film are taken out, barrier film is sandwiched in the middle of two cube electrode materials, then leave standstill 12h and make its natural drying obtain solid-state super capacitor;
Or described ultracapacitor is solid asymmetric ultracapacitor, assembling solid asymmetric ultracapacitor comprises:
(1) activated carbon negative electrode material is prepared.By active carbon, acetylene black and polytetrafluoroethylene are sized mixing according to the ratio mixing of 8:1:1, at nickel foam surface coating, claim its quality after dry,
(2) prepare PVA/KOH solid electrolyte, 17gKOH and 30gPVA added in 300mL deionized water, at 85 DEG C of temperature, stir 1h,
(3) use glass fiber filter paper as diaphragm of supercapacitor, clip one cube electrode material, soaks 5min in the electrolytic solution by positive and negative electrode material and barrier film,
(4) electrode material after immersion and barrier film are taken out, barrier film is sandwiched in the middle of positive and negative electrode material, then leave standstill 12h and make its natural drying obtain solid-state super capacitor.
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