CN103762091A - Cellular porous manganese dioxide nanofiber preparing method and application of cellular porous manganese dioxide nanofiber in supercapacitor - Google Patents

Cellular porous manganese dioxide nanofiber preparing method and application of cellular porous manganese dioxide nanofiber in supercapacitor Download PDF

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CN103762091A
CN103762091A CN201410003332.5A CN201410003332A CN103762091A CN 103762091 A CN103762091 A CN 103762091A CN 201410003332 A CN201410003332 A CN 201410003332A CN 103762091 A CN103762091 A CN 103762091A
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nanofiber
mno
cellular porous
ultracapacitor
fiber
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于杰
赵磊
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Shenzhen Graduate School Harbin Institute of Technology
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Shenzhen Graduate School Harbin Institute of Technology
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Abstract

The invention relates to a cellular porous manganese dioxide (MnO2) nanofiber preparing method and the application of cellular porous manganese dioxide nanofibers in a supercapacitor. The preparing method comprises the steps of (1) preparing polyacrylonitrile (PAN) fibers with the electrostatic spinning method, (2) conducting stabilizing treatment on the polymer fibers obtained with the method at a proper temperature and in an oxygen atmosphere, (3) conducting carbonization heat treatment on the stabilized fibers at a proper temperature and in an NH3 atmosphere, and (4) obtaining the cellular porous MnO2 nanofiber after the prepared carbon nanofibers react with a potassium permanganate (KMnO4) solution. According to the MnO2 nanofiber, the diameter of each cell is 50 nm-350 nm, the diameter of each pore is 10 nm-80 nm, and the wall thickness of each pore is 2.5 nm-20 nm. Compared with the prior art, the supercapacitor prepared with the cellular porous MnO2 nanofiber as the electrode material has excellent performance, and the working voltage reaches 2.2 V-2.7 V. The cellular porous MnO2 nanofiber is suitable for the supercapacitor.

Description

A kind of preparation method of cellular porous manganese dioxide nano fiber and supercapacitor applications thereof
Technical field
The invention belongs to new material technology field, relate to a kind of cellular porous MnO 2the preparation method of nanofiber and supercapacitor applications thereof.
Background technology
Ultracapacitor is a kind of novel energy-storing device between traditional capacitor and storage battery, have that power density is high, the speed that discharges and recharges is fast, have extended cycle life, abundant advantage (the Chemical Society Reviews2012 such as cheap of stable performance, raw material types, 41,797-828; Nature Materials2008,7,845-854).Compare with lithium ion battery, low energy density limited its extensive use (Nano letters2010,10,4683-4868).According to its energy computing formula E=1/2CV 2, the raising of energy density need to be from starting with than electric capacity and two aspects of operating voltage.Ultracapacitor can be divided into double electric layer capacitor and fake capacitance device according to energy storage mechanism.Double electric layer capacitor is to form electric double layer and energy storage by electrode surface, there is the speed of discharging and recharging fast, the outstanding advantages of the high and good cycling stability of power density, shortcoming is that specific energy is on the low side, business sells active carbon super capacitor energy density generally below 10Wh/kg at present.Fake capacitance device is the Quick Oxidation reduction reaction energy storage occurring by material surface, with respect to double electric layer capacitor, has higher ratio electric capacity and specific energy.Fake capacitance device electrode material is mainly metal oxide, wherein RuO 2there is large (the Electrochemical and Solid-State Letters of operation interval; 2012; 15; A60-A63); than electric capacity high (Journal of Electrochemical Society, 1995,142; the advantage such as 2699-2703), but expensively limited its scale application.MnO 2there is higher ratio electric capacity (theoretical value 1370F/g), and cheap a, asepsis environment-protecting, possess the condition of the commercial Application of realizing.MnO 2counterfeit reaction mainly betides the nearly surf zone of material, and deep regions can not get application.Conventionally material with carbon element as the backing material of metal oxide to obtain desirable nanostructure and to improve conductivity, although carbon/MnO 2in composite material, show relatively high ratio electric capacity, as: nanometer MnO 2composite microporous carbon reach 600F/g (Journal of Physical Chemistry B, 2006,110,6015-6019), MnO 2the ratio electric capacity that/carbon nano-tube/poly aniline three is compound reach 427F/g (Nano letters, 2010,10,2727-2733), but their MnO 2bearing capacity is only 26% and 60%, and when considering bearing capacity completely, their ratio electric capacity is only 200F/g.At present, MnO 2the operation interval of counterfeit reaction is only 1V left and right, and this has also greatly limited the raising of its energy density.
In order to improve MnO 2bearing capacity, expansion real work voltage and raising energy density, need to design novel nanostructure to improve its effective ratio area and obtain diffusion admittance smoothly.
Electrospinning carbon nano-fiber is a kind of Novel Carbon Nanomaterials that utilizes electrostatic spinning technique to prepare, and utilizes polymer if PAN is as presoma, makes precursor fibre, then can obtain carbon nano-fiber through charing heat treatment through electrospinning process.Electrospinning carbon nano-fiber is for ultracapacitor more existing research report (Advanced Materials2007,19,2341 – 2346; Journal of Power Sources2007,196,9862 – 9867).Although the specific area of electrospinning carbon nano-fiber own is not high, the structure of its continuous fiber random alignment makes can not reunite between its fiber, thereby provides natural foundation for obtaining superior performance.
The present invention is based in ultracapacitor that water system operating voltage is on the low side, MnO 2the problems such as bearing capacity is low, utilance is low, specific energy is on the low side, preparation cost is high, by the KMnO of carbon nano-fiber and low concentration 4there is at normal temperatures chemical reaction and prepare cellular porous MnO 2nanofiber.By controlling reaction condition, make carbon nano-fiber complete reaction, obtain a kind of MnO of the cellular porous structure being formed by nanometer sheet completely 2nanofiber.MnO 2fiber has honeycomb loose structure, between sheet and sheet, does not reunite, and honeycomb hole wall thickness is 2.5～20nm, and aperture is 50～350nm.The effective ratio area that the honeycomb loose structure that this thin-walled has a fine dispersion is conducive to keep large, reduce electric charge the evolving path and improve stock utilization, thereby improve energy density.
Summary of the invention
The object of the invention is to overcome MnO 2specific area is low, and poorly conductive is easily reunited, and makes the shortcomings such as ultracapacitor specific energy is on the low side, provide a kind of prepare easy, can control pattern and there is high performance cellular porous MnO 2the preparation method of nanofiber, and provide a kind of with cellular porous MnO 2nanofiber is the ultracapacitor assembling method of electrode material.Described MnO 2nanofiber has cellular porous structure, its fibre diameter is between 50～350nm, honeycomb wall thickness is between 2.5～20nm, and honeycomb hole diameter is between 10～80nm, and thin honeycomb wall and large specific area are conducive to ion fast transport between electrode and electrolyte.MnO in the present invention 2have birnessite structure, wide interplanar distance is conducive to proton and ion, at material internal, redox reaction fast occurs, and improves fake capacitance.In the present invention, the preparation of ultracapacitor is to adopt cellular porous MnO 2nanofiber does not directly add any binding agent and conductive agent as electrode material.
A kind of cellular porous MnO provided by the invention 2the preparation method of nanofiber and supercapacitor applications thereof, comprise the steps:
(1) preparation of precursor fiber: utilize electrospinning process electrospinning PAN to prepare precursor fiber;
(2) stabilization processes of the precursor fiber of carbon nano-fiber: the precursor fiber that step (1) is made carries out the fiber that stabilization processes obtains stabilisation under air or oxygen atmosphere, at suitable temperature;
(3) the charing heat treatment of the fiber of stabilisation: the fiber of the stabilisation that step (2) is made is at NH 3under atmosphere, charing heat treatment at 1000～1100 ℃, obtains carbon nano-fiber;
(4) carbon nano-fiber and the KMnO that step (3) are obtained 4solution reaction obtains cellular porous MnO 2nanofiber.
In described step (1), the preparation of precursor fiber refers to: PAN is dissolved in to the electrospinning solution of appropriate solvent preparation debita spissitudo, then carries out electrostatic spinning, make precursor fiber.Electro-spinning equipment is the DW-P503-2ACCD type high voltage source that Tianjin Dong Wen high voltage source Co., Ltd produces.Utilize graphite paper, Copper Foil or aluminium foil as collecting substrate, spinning nozzle is between 5～30cm apart from collecting substrate distance, and voltage is between 10～40kV.Wherein, the molecular weight ranges of described PAN is 20,000～200,000, and described solvent is a kind of in dimethyl formamide (DMF), ethanol, dimethylacetylamide (DMAC).PAN concentration is the mass volume ratio of its quality and described DMF, ethanol, tri-kinds of solvents of DMAC, and scope is 3～10wt%, and the diameter of the precursor fiber obtaining is between 100-400nm.
Stabilization processes in described step (2) refers to: the precursor fiber that step (1) is made is heated to suitable temperature insulation reasonable time, then naturally cools to room temperature, obtains the fiber of stabilisation.Stabilization temperature is 200～290 ℃, and temperature retention time is 0.5～2h.
The heat of carbonization of described step (3) stabilisation fiber is processed and is referred to: the stabilisation fiber that step (2) is made is at NH 3under atmosphere, through 1000～1100 ℃ of heat of carbonizations, process, obtain carbon nano-fiber.This step concrete technology is that the fiber of stabilisation is put into tube furnace, passes into NH 3or contain NH 3mist, be heated to 1000～1100 ℃ of carbonizations, insulation naturally cools to room temperature after 1～3h, obtains carbon nano-fiber.
Carbon nano-fiber in described step (4) is prepared carbon nano-fiber in step (3).KMnO 4concentration is 0.5～10mMol/L, Nano carbon fibers peacekeeping KMnO 4the temperature of reaction is 20～30 ℃, and the reaction time is 5min～168h.The addition of carbon fiber and KMnO 4the mass volume ratio of solution is that 0.01g/L is between 1g/L.Prepared MnO 2nanofiber has cellular porous structure, and honeycomb hole wall thickness is 2.5～20nm, cellular porous MnO 2the diameter of nanometer sheet is 50～350nm, and the crystal structure of this nanometer sheet is birnessite structure, and (001) interplanar distance is 0.68nm, is conducive to proton or ion intercalation, improves fake capacitance reaction, obtains high ratio electric capacity.The cellular porous MnO that in solution, reaction generates 2nanofiber cleans repeatedly with deionized water, is carried on afterwards glass sheet surface, puts in the baking oven of 60 ℃ and dries and obtain final sample.
A kind of ultracapacitor of the present invention, by the cellular porous MnO making 2nanofiber, as electrode material, is assembled into water system symmetry ultracapacitor.The collector of described ultracapacitor is a kind of in nickel sheet, stainless steel substrates, titanium sheet or graphite paper; The barrier film of described ultracapacitor is a kind of in glass fibre or filter paper.
A method of preparing ultracapacitor of the present invention, comprising: by the cellular porous MnO preparing 2nanofiber, directly as electrode material, is cut into rectangle or circular proper area by itself and barrier film, subsequently by MnO 2nanofiber is directly attached to the both sides of soaking the barrier film of 24h in electrolyte solution, finally again collector is attached to MnO 2the both sides of nanofiber membrane electrode, edge seals or puts into battery case punching press with polytetrafluoroethylene glue and obtains ultracapacitor.
The barrier film that described ultracapacitor is selected is a kind of in glass fibre membrane or filter paper, the optional Na of electrolyte 2sO 4, K 2sO 4or H 2sO 4in a kind of, collector is a kind of in nickel sheet, stainless steel substrates, titanium sheet, battery case or graphite paper.
The beneficial effect that the present invention compared with prior art has: MnO prepared by prior art 2nanometer sheet mainly contains two kinds, and a kind of is pulverous, this MnO 2when nanometer sheet is used, easily reunite, cause effective ratio area to reduce; Another kind is the directional nano sheet that grows in substrate surface, and the surface for growing nano sheet is limited in this case, can only in two-dimensional surface, obtain one deck nanometer sheet.The present invention is by carbon nano-fiber and low concentration KMnO 4solution reaction and obtain cellular porous MnO by controlling the rational reaction time 2nanometer sheet, the hole wall of this material is thin, and lamella, perpendicular to the growth of nanometer sheet surface orientation, has obtained three-dimensional structure (be all comprised of nanometer sheet, centre is carbon fiber-containing core not), has improved MnO 2the space availability ratio of electrode material and bearing capacity, prevent the generation of agglomeration.In addition, the cellular porous MnO that prepared by the present invention 2nanometer sheet has birnessite structure, and its (001) face interplanar distance is 0.68nm, is conducive to proton or ion at MnO 2there is absorption and embedding dealkylation reaction in surface, improves adsorption ability and redox reaction ability, thereby carry high specific capacitance.Utilize cellular porous MnO 2the ultracapacitor that nanofiber is prepared as electrode material has better performance with respect to prior art, and the operating voltage of the aqueous super capacitor that it is assembled into is 2.2～2.7V, than electric capacity, is 246F/g, and energy density is 41.1Wh/kg.With three-electrode system, the test of electrode material is shown to the Na at 1M 2sO 4in solution, obtain the operating voltage of 2.2～2.4V, the ratio electric capacity of 292F/g, the energy density of 196.1Wh/kg.At 1M K 2sO 4the titanium sheet of usining in solution carries out to it operating voltage that three electrode tests obtain 2.7V as collector.
Accompanying drawing explanation
Fig. 1 is by 1000 ℃ of carbon nano-fibers and 2mM KMnO in the invention process example 1 4the MnO that solution reaction 12h obtains 2the transmission electron microscope macrograph of nanofiber;
Fig. 2 is by 1000 ℃ of carbon nano-fibers and 2mM KMnO in the invention process example 1 4the MnO that solution reaction 12h obtains 2the transmission electron microscope high power photo of nanofiber;
Fig. 3 is by 1000 ℃ of carbon nano-fibers and 2mM KMnO in the invention process example 2 4the MnO that solution reaction 48h obtains 2the electron scanning micrograph of nanofiber;
Fig. 4 is by 1000 ℃ of carbon nano-fibers and 2mM KMnO in the invention process example 2 4the MnO that solution reaction 48h obtains 2the transmission electron microscope photo of nanofiber;
Fig. 5 is by 1000 ℃ of carbon nano-fibers and 2mM KMnO in the invention process example 3 4the MnO that solution reaction 96h obtains 2the electron scanning micrograph of nanofiber;
Fig. 6 is by 1000 ℃ of carbon nano-fibers and 2mM KMnO in the invention process example 4 4the MnO that solution reaction 168h obtains 2the electron scanning micrograph of nanofiber;
Fig. 7 is by 1100 ℃ of carbon nano-fibers and 0.5mM KMnO in the invention process example 5 4the MnO that solution reaction 48h obtains 2the electron scanning micrograph of nanofiber;
Fig. 8 is by 1000 ℃ of carbon nano-fibers and 0.5mM KMnO in the invention process example 6 4the MnO that solution reaction 168h obtains 2the electron scanning micrograph of nanofiber;
Fig. 9 reacts the MnO that 12h obtains in the invention process example 7 2three electrode cyclic voltammetry curves of nanofiber;
Figure 10 reacts the MnO that 12h obtains in the invention process example 7 2three electrode constant current charge-discharge curves of nanofiber;
Figure 11 reacts the MnO that 12h obtains in the invention process example 7 2the cyclic voltammetry curve of the ultracapacitor of nanofiber;
Figure 12 reacts the MnO that 12h obtains in the invention process example 7 2the constant current charge-discharge curve of the ultracapacitor of nanofiber;
Figure 13 reacts the MnO that 48h obtains in the invention process example 8 2three electrode cyclic voltammetry curves of nanofiber;
Figure 14 reacts the MnO that 48h obtains in the invention process example 8 2three electrode constant current charge-discharge curves of nanofiber;
Figure 15 reacts the MnO that 48h obtains in the invention process example 8 2the cyclic voltammetry curve of the ultracapacitor of nanofiber;
Figure 16 reacts the MnO that 48h obtains in the invention process example 8 2the ultracapacitor constant current charge-discharge curve of nanofiber;
Figure 17 reacts the MnO that 168h obtains in the invention process example 9 2three electrode cyclic voltammetry curves of nanofiber;
Figure 18 reacts the MnO that 168h obtains in the invention process example 9 2the ultracapacitor constant current charge-discharge curve of nanofiber;
Figure 19 reacts the MnO that 48h obtains in the invention process example 10 2nanofiber is aided with the three electrode cyclic voltammetry curves that titanium sheet is collector.
Embodiment
Below by the instantiation explanation approach that realizes of the present invention, core summary of the invention is low concentration KMnO 4solution and NH 3the reaction process of the carbon nano-fiber that under atmosphere, carbonization obtains, obtains cellular porous MnO by controlling reaction temperature and time 2nanofiber.Embodiment comprises two parts: embodiment 1～6th, cellular porous MnO 2the preparation technology of nanofiber; Embodiment 7～10th, utilizes embodiment 1,2,4 prepared cellular porous MnO 2nanofiber is as three electrode performances and the performance that is assembled into ultracapacitor of electrode material.
Embodiment 1:1000 ℃ carbon nano-fiber and 2mM KMnO 4the cellular porous MnO that solution reaction 12h obtains 2nanofiber
PAN is dissolved in to preparation quality volume ratio in DMF solvent and, for the electrospinning solution that (wt/v) is 3%, with electrospinning process, prepares precursor fiber subsequently.PAN used is purchased from Aldrich company, molecular weight M w=150000.High voltage source is the DW-P503-2ACCD type high voltage source that Tianjin Dong Wen high voltage source Co., Ltd produces, ceiling voltage 50kV.During electrospinning, utilize graphite paper as collecting substrate, spinning nozzle is apart from collecting substrate 15cm, and voltage is set to 20kV, and spray silk syringe needle diameter is 0.4mm.Then the PAN precursor fibre of being prepared by above-mentioned electrospinning is put into conventional tube furnace, carries out stabilization processes in air.Heating rate with 5 ℃/min is heated to 250 ℃, and insulation 2h, then naturally cools to room temperature, obtains the fiber of stabilisation.Finally the fiber of stabilisation is carried out to heat of carbonization processing.Detailed process is that the fiber of stabilisation is put into conventional tube furnace, with the flow velocity of 80mL/min, passes into NH 3gas; Heating rate with 5 ℃/min is heated to 1000 ℃, and insulation 2h, then naturally cools to room temperature, obtains the carbon nano-fiber of 1000 ℃.Under 25 ℃ of conditions, 1000 ℃ of carbon nano-fibers of 1mg are put into the KMnO of 20mL 2mM 4in solution, allow carbon nano-fiber and KMnO 4solution reacts, and after 12h reaction, obtains MnO 2nanofiber.In this process, without any need for stirring, by the variation of time, control course of reaction, obtain the MnO with birnessite structure 2nanofiber.Fig. 1 is the MnO of prepared reaction 12h 2the high power photo of the transmission electron microscope of nanofiber, can find out that fiber surface grows the MnO that a lot of sizes are little and thin 2nanometer sheet.Fig. 2 is the MnO that 12h reaction obtains 2the high power photo of the transmission electron microscope of nanofiber, can find out KMnO 4solution is complete reaction not, and there is the existence of carbon fiber core in centre.The MnO obtaining 2nanofiber average diameter is 115nm, and the thickness of sheet is 2.5～6nm.This MnO as seen from Figure 2 2interplanar distance in nanometer sheet is 0.68nm, has birnessite structure, and the embedding that this structure is conducive to proton or ion takes off, and improves redox reaction ability, carries high specific capacitance.
Embodiment 2:1000 ℃ carbon nano-fiber and 2mM KMnO 4the cellular porous MnO that reaction 48h obtains 2nanofiber
In this embodiment carbon nano-fiber with KMnO 4the time lengthening of reaction has arrived 48h, and other condition is all identical with embodiment 1.
Fig. 3 is the cellular porous MnO that reaction 48h obtains 2the electron scanning micrograph of nanofiber.Compared to Figure 1, this structure has cellular porous structure, cellular porous fibre diameter average out to 190nm wherein, and honeycomb aperture is 20～50nm, honeycomb wall thickness is 4～7nm.Fig. 4 is obtained MnO 2the transmission electron microscope photo of nanofiber, compares with Fig. 2 in embodiment 1, cellular porous MnO 2nanofiber is all comprised of cellular porous nanometer sheet, and inner without carbon nano-fiber, this structure is different from general MnO 2sheet, has improved MnO greatly 2bearing capacity in practical application.Cellular thin-walled porous nano-sheet is conducive to electrolyte ion inner and surperficial embedding and absorption in cellular porous nanometer sheet, thereby reduce resistance, improves performance.
Embodiment 3:1000 ℃ carbon nano-fiber and 2mM KMnO 4the cellular porous MnO that reaction 96h obtains 2nanofiber
Reaction time in this embodiment is 96h, and other condition is all identical with embodiment 1.Fig. 5 is 1000 ℃ of carbon nano-fibers and 2mM KMnO 4the cellular porous MnO of reaction 96h 2the electron scanning micrograph of nanofiber.Compare with Fig. 1 and Fig. 3, honeycomb, hole wall is thicker, and sheet is larger, the average 280nm of cellular porous fibre diameter, honeycomb aperture 20～60nm, honeycomb hole wall thickness 10～15nm, honeycomb sheet average length 115nm.
Embodiment 4:1000 ℃ carbon nano-fiber and 2mM KMnO 4the cellular porous MnO that reaction 168h obtains 2nanofiber
The reaction time adopting in this embodiment is 168h, and other condition is all identical with embodiment 1.Fig. 6 is 1000 ℃ of carbon nano-fibers and 2mM KMnO 4the cellular porous MnO that reaction 168h obtains 2the electron scanning micrograph of nanofiber.Compare with Fig. 1, Fig. 3 and Fig. 5, this fiber is thicker, and honeycomb hole wall is thicker, and honeycomb sheet is larger.Cellular porous MnO wherein 2the average diameter of nanofiber is 320nm, and honeycomb aperture is 30～70nm, and honeycomb wall thickness is 13～20nm.
Embodiment 5:1100 ℃ carbon nano-fiber and 2mM KMnO 4the MnO that solution reaction 48h obtains 2nanofiber
1100 ℃ of carbon nano-fibers and 2mM KMnO for this example 4solution reaction 48h obtains thinner cellular porous MnO 2nanofiber.The consumption that is material in reaction from example 1 difference is different, the carbon nano-fiber of 1100 ℃ of carbonizations of 1mg is joined to the 2mM KMnO of 15mL 4in solution, react, other condition is all identical with embodiment 1.As can be seen from Figure 7, the MnO obtaining in this example 2the average diameter of nanofiber is 80nm, and honeycomb aperture is 10～30nm, and honeycomb wall thickness is 2.5～6nm.
Embodiment 6:1000 ℃ carbon nano-fiber and 0.5mM KMnO 4the MnO that reaction 168h obtains 2nanofiber
Fig. 8 is 1000 ℃ of carbon nano-fibers and 0.5mM KMnO 4the cellular porous MnO that solution reaction 168h obtains 2the electron scanning micrograph of nanofiber, adopts 1000 ℃ of carbon nano-fibers and low concentration 0.5mM KMnO 4the MnO that solution reaction 168h obtains 2the surface of nanofiber has carefully, thin feature, and there is alveolate texture subregion, and the average fibre diameter of this structure is 85nm, and honeycomb wall thickness is 2.5～6nm, and average honeycomb aperture is 25nm, maximum sheet length is 80nm.
Assembling and the performance of embodiment 7 three electrodes and ultracapacitor
The MnO obtaining with embodiment 1 reaction 12h 2nanofiber carries out cyclic voltammetric and the constant current charge-discharge test of three electrodes and ultracapacitor.
Three electrode tests: first nickel foam being cut into size is 1 * 2cm 2rectangle, then with ethanol, clean nickel foam surface, by area, be 1 * 1cm subsequently 2region is wetting, and quality is the MnO of 360 μ g 2nanofiber is pressed onto wetting nickel foam surface directly as electrode, and wherein calomel electrode is reference electrode, and platinum filament is as to electrode.Three electrodes are put into and in electrolytic cell, carry out three electrode tests.
Ultracapacitor assembling step is as follows: (1) is by MnO 2nanometer sheet tunica fibrosa, fibreglass diaphragm are washed into area 1 * 1cm 2disk; (2) by the glass fibre element barrier film of disk shape at 1M/L Na 2sO 4in solution, soak 24h; (3) by MnO step (1) Suo Shu 2nanometer sheet tunica fibrosa is directly attached to the both sides of the fibreglass diaphragm soaking in step (2), is attached to subsequently both sides (each MnO of stainless steel disk collector 2nanometer sheet tunica fibrosa electrode quality is 250 μ g); (4) collector that is loaded with electrode material, barrier film in step (3) is put in button cell shell and with stamping machine and encapsulated.
Utilize electrochemical workstation (model C HI760C, Shanghai Chen Hua Instrument Ltd. produces) to carry out cyclic voltammetric (CV) and constant current charge-discharge test to it.Fig. 9 and Figure 10 are three electrode CV and the constant current charge-discharge curves in this example, and during CV test, sweep speed is 100mV/s, and during charge-discharge test, current density is respectively 5A/g, 8A/g and 10A/g.Test result shows, the ultracapacitor operating voltage obtaining is up to 2.2V, and the ratio electric capacity that the charging and discharging curve in Figure 10 calculates under the current density of 5A/g, 8A/g and 10A/g is respectively 164F/g, 149F/g and 105F/g.Figure 11 and Figure 12 are CV curve and the constant current charge-discharge curves of the ultracapacitor of this example assembling, and during CV test, sweep speed is 100mV/s, and current density during charge-discharge test is 3A/g.Test result shows, the ultracapacitor operating voltage obtaining is up to 2.2V.The energy density that charging and discharging curve as shown in Figure 12 calculates is 15Wh/kg.
Assembling and the performance of embodiment 8 three electrodes and ultracapacitor
The cellular porous MnO obtaining with embodiment 2 reaction 48h 2nanofiber carries out cyclic voltammetric and the constant current charge-discharge test thereof of three electrodes and ultracapacitor.
In the three electrode preparations of this embodiment and the assembling process of ultracapacitor, except electrode material is different with electrode quality, remaining is all identical with the assemble method of ultracapacitor with three electrodes of embodiment 7.The cellular porous MnO of three electrodes and ultracapacitor test in this embodiment 2the quality of nanometer sheet tunica fibrosa is respectively 1mg and 900 μ g (each electrode quality is 450 μ g).Figure 13 and Figure 14 are this example three electrode CV and constant current charge-discharge curve, and the sweep speed of CV test is 10～200mV/s, and the current density of charge-discharge test is 2.5A/g, 3A/g, 5A/g and 8A/g.Test shows, the operating voltage height of the ultracapacitor that Figure 13 obtains is 2.2V.By the charging and discharging curve shown in Figure 14, calculating the ratio electric capacity obtaining under known 2.5A/g current density is 292F/g, and energy density is 196.1Wh/kg.Compare the MnO of the cellular porous feature in this embodiment with example 7 2electrode material possesses good chemical property.The rational alveolate texture of nanometer sheet, the advantage such as specific area is large, and hole wall is thin, is conducive to carry high specific capacitance and specific energy.
Figure 15 and Figure 16 are CV curve and the constant current charge-discharge curves of the ultracapacitor of this example assembling, and the sweep speed of CV test is from 20～200mV/s, and during charge-discharge test, current density is 3～10A/g.Figure 15 CV test shows that the operating voltage of ultracapacitor is 2.2V, all presents rectangle under all sweep speeds.As shown in Figure 16, under 3A/g current density, discharging and recharging the ratio electric capacity that obtains ultracapacitor is 246F/g, and energy density is 41.1Wh/kg, and power density is 3.3kW/kg; Energy density under 10A/g current density is 15Wh/kg, and power density is 11.2kW/kg.
Assembling and the performance of embodiment 9 three electrodes and ultracapacitor
The MnO preparing with embodiment 2 reaction 168h 2nanofiber carries out three electrode CV tests and the test of ultracapacitor constant current charge-discharge.Except electrode material is different with electrode quality, the preparation of the electrode of this embodiment is all identical with the assemble method of ultracapacitor with three electrodes of embodiment 7 with ultracapacitor assembling process.Cellular porous MnO in the electrode quality of three electrode tests and ultracapacitor in this embodiment 2the quality of nanometer sheet tunica fibrosa is respectively 300 μ g and 1.55mg (in ultracapacitor, each electrode quality is 775 μ g).Figure 17 is the CV curve of three electrode tests under different operating interval, and wherein, sweep speed is 100mV/s, and electromotive force is from-change to-1.2V～1.2V of 0.6V～0.6V, and voltage changes to 2.4V from 1.2V.Result shows the MnO that 168h obtains 2nanofiber electrode can be under the voltage of 2.4V steady operation.Figure 18 is the constant current charge-discharge curve in the current density change process of ultracapacitor from 0.5A/g to 8A/g, and wherein, under the current density of 0.5A/g, electrode material obtains the specific energy of 13Wh/kg.
Compare with embodiment 8, in this example, extend the reaction time to bring MnO 2the increase of content, this is conducive to H in solution +ion is embedded in birnessite structure, has increased hydrogen overpotential and has improved operating voltage.On the other hand, overlong time causes lamella blocked up, according to MnO 2the known adsorption and oxidation reduction reaction of reaction mechanism is only at MnO 2he Jin top layer, top layer occur, so the honeycomb porous MnO that 168h reaction obtains 2the ratio electric capacity of nano-fiber electrode material will be lower than the result of embodiment 8.
Assembling and the performance of embodiment 10 3 electrodes and ultracapacitor
This embodiment is in embodiment 2, to react the cellular porous MnO that 48h obtains 2nanofiber is usingd titanium sheet as collector and at 1M K 2sO 4test result in solution.As can be seen from Figure 19, from the scan speed change process of 20-200mV/s, CV curve keeps stable operating voltage, and electromotive force is from-1.5V～1.2V, and voltage reaches 2.7V, higher than the decomposition voltage (1.23V) of water.Cellular porous MnO 2nanofiber has high specific area, and thin hole wall is convenient to electrolyte intermediate ion de-in absorption and the embedding on electrode surface and nearly surface.Titanium collector has high hydrogen overpotential and oxygen overpotential and has guaranteed that collector is withstand voltage and provide necessary condition for electrode material obtains high voltage.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.

Claims (10)

1. a cellular porous MnO 2the preparation method of nanofiber, is characterized in that: comprise the following steps:
(1) prepare the precursor fiber of carbon nano-fiber: utilize electrospinning process to process polyacrylonitrile (PAN) macromolecule, obtain precursor fiber;
(2) precursor fiber step (1) being made carries out the fiber that stabilization processes obtains stabilisation at suitable atmosphere and temperature;
(3) fiber of stabilisation step (2) being made, suitably carrying out charing heat treatment at atmosphere and temperature, obtains carbon nano-fiber;
(4) carbon nano-fiber and the KMnO that step (3) are made 4solution at room temperature reacts and obtains cellular porous MnO 2nanofiber.
2. preparation method according to claim 1, is characterized in that: in described step (1), containing carbon polymer, be polyacrylonitrile, molecular weight is 20,000～200,000.
3. preparation method according to claim 1, is characterized in that: in described step (2), stabilization processes is to carry out in air or oxygen-containing atmosphere, and stabilization processes temperature is 200～290 ℃, and the stabilization processes time is 0.5～2h.
4. preparation method according to claim 1, is characterized in that: the reaction atmosphere in described step (3) is NH 3, flow is between 20～100mL/min; Charing treatment temperature is 1000～1100 ℃, and carbonization time is 0.5～2h.
5. preparation method according to claim 1, is characterized in that: KMnO in described step (4) 4the concentration of solution is 0.5～10mM/L, Nano carbon fibers peacekeeping KMnO 4reaction temperature be 20～30 ℃, the reaction time is that 5min is to 168h.
6. preparation method according to claim 1, is characterized in that: the cellular porous MnO obtaining in described step (4) 2the diameter of nanofiber is 50～350nm, and honeycomb aperture is 10～80nm, and honeycomb hole wall thickness is 2.5～20nm.
7. a ultracapacitor, is characterized in that: the cellular porous MnO that the arbitrary claim of claim 1-6 is made 2nanofiber, as electrode material, is assembled into water system symmetry ultracapacitor.
8. ultracapacitor according to claim 7, is characterized in that: the collector of described ultracapacitor is a kind of in nickel sheet, stainless steel substrates, titanium sheet or graphite paper; The barrier film of ultracapacitor is a kind of in glass fibre or filter paper.
9. a preparation method for the ultracapacitor described in the arbitrary claim of claim 7-8, is characterized in that: by barrier film and cellular porous MnO 2nanofiber is cut into rectangle or circular proper area, subsequently by MnO 2nanofiber is directly attached to the barrier film two sides of soaking 24h in electrolyte solution, finally again rectangle or circular collector sheet is attached to MnO 2the both sides of nanofiber membrane electrode, edge seals or puts into battery case punching press with polytetrafluoroethylene glue and obtains ultracapacitor.
10. preparation method according to claim 9, is characterized in that: described ultracapacitor electrolyte used is Na 2sO 4,, K 2sO 4, Li 2sO 4or H 2sO 4in a kind of.
CN201410003332.5A 2014-01-03 2014-01-03 Cellular porous manganese dioxide nanofiber preparing method and application of cellular porous manganese dioxide nanofiber in supercapacitor Pending CN103762091A (en)

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CN105070511A (en) * 2015-08-05 2015-11-18 清华大学 Fibrous supercapacitor and fabrication method thereof
CN105070511B (en) * 2015-08-05 2017-09-26 清华大学 A kind of fibrous ultracapacitor and preparation method thereof
CN105271422A (en) * 2015-10-08 2016-01-27 吉林大学 Method for preparing ultralight manganese dioxide aerogel
CN105513822A (en) * 2016-02-05 2016-04-20 扬州大学 Method for preparing electrode materials with hollow carbon fibers coated with manganese dioxide
CN106868714A (en) * 2017-02-20 2017-06-20 南通市中和化纤有限公司 PAN micro nanometer fiber films are spun in heavy metal ion adsorbed liquid spray
CN107799323A (en) * 2017-10-24 2018-03-13 东华大学 A kind of hollow MnO2The preparation method of nano-fiber electrode material
CN107988660A (en) * 2017-11-14 2018-05-04 哈尔滨工业大学深圳研究生院 A kind of thermal chemical vapor deposition prepares the method and its application of three-dimensional grapheme fiber
CN109950457A (en) * 2017-12-21 2019-06-28 北京金羽新能科技有限公司 A kind of water system ion energy storage device
CN109574161A (en) * 2019-01-30 2019-04-05 东莞理工学院 A kind of MnO2Compound porous carbon material electrode and its application in capacitive deionization desalination
CN111223676A (en) * 2020-01-14 2020-06-02 益阳市万京源电子有限公司 Supercapacitor material based on hollow nanotube and preparation method thereof
CN111223676B (en) * 2020-01-14 2021-06-25 益阳市万京源电子有限公司 Supercapacitor material based on hollow nanotube and preparation method thereof
CN111986931A (en) * 2020-07-24 2020-11-24 华南理工大学 Manganese oxide nano-structure electrode material and preparation method and application thereof
CN113871212A (en) * 2021-11-29 2021-12-31 桂林电子科技大学 Manganese dioxide/carbon film composite material with core-shell structure and preparation method and application thereof
CN113871212B (en) * 2021-11-29 2022-12-27 桂林电子科技大学 Manganese dioxide/carbon film composite material with core-shell structure and preparation method and application thereof
CN114709556A (en) * 2022-04-22 2022-07-05 河北工业大学 Zinc ion battery diaphragm for inhibiting dendritic crystal growth and preparation method thereof
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