CN104499022A - Preparation and application of MnO2-SnO2/graphite nanometer array composite electrode material - Google Patents

Preparation and application of MnO2-SnO2/graphite nanometer array composite electrode material Download PDF

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CN104499022A
CN104499022A CN201410802627.9A CN201410802627A CN104499022A CN 104499022 A CN104499022 A CN 104499022A CN 201410802627 A CN201410802627 A CN 201410802627A CN 104499022 A CN104499022 A CN 104499022A
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mno
sno
graphite
electrode material
gnsa
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胡中爱
陈婵娟
任小英
强睿斌
胡海雄
吴红英
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Northwest Normal University
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Northwest Normal University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a preparation method of an MnO2-SnO2/graphite nanometer array composite electrode material. With an electrochemically activated and stripped graphite nanometer array as a base, and a mixed liquid of MnCl2.4H2O, NaNO3 and SnCl4.5H2O as an electroplate liquid, reduced electrodeposition of MnO2-SnO2 on the surface of the graphite nanometer array is carried out by using a constant potential method, so as to obtain the MnO2-SnO2/graphite nanometer array composite electrode material. An electrochemical test shows that the composite electrode has excellent super-capacitive property; and the specific capacitance reaches 4245F.m<-2>. According to a symmetrical supercapacitor assembled by the MnO2-SnO2/GNSAs composite electrode and the same electrolyte, the energy density reaches 0.43Wh.m<-2>; and the specific capacitance can still be kept at 70% of initial specific capacitance after circulating 4000 circles.

Description

MnO 2-SnO 2the preparations and applicatio of/graphite nano plate array combination electrode material
Technical field
The present invention relates to a kind of MnO 2-SnO 2the preparation of/graphite nano plate array combination electrode material, belongs to technical field of composite materials.The present invention also relates to this MnO simultaneously 2-SnO 2the application of/graphite nano plate array combination electrode material in assembling symmetric form ultracapacitor.
Technical background
Electrochemical techniques are a kind of important methods of preparation nano material, with other method (such as hydrothermal method, self-assembling technique etc.) compound, the material of agglomerate body or the macroscopic material with laminar microstructure prepared compare, when electrochemical techniques prepare electrode, deposit electrode material defines the settled layer with unique high-density and low porosity in collector electrode surface, and can be controlled the thickness of settled layer accurately by the parameter controlling galvanic deposit, size and the chemical group of crystal grain are graded.The combined electrode prepared by this method can directly as the electrode of electrochemical capacitor, effectively avoiding the combination electrode material prepared by other method adding dispersion agent and tackiness agent to carry out active substance causing active substance that the phenomenon of reuniting occurs in the secondary preparation process of electrode, in the synthesis of electrochemical capacitor electrode material, therefore attracted the favor of numerous investigator.
MnO 2because it is cheap, aboundresources, environmental friendliness, and there is higher theoretical ratio capacitance (1232Fg -1), be one of most potential electrode material for super capacitor.But because its energy gap is comparatively large, cause electroconductibility poor, under high current density, ratio capacitance decay is comparatively serious, the shortcoming such as cause the lower and cycle performance of the utilization ratio of its active substance poor that specific surface area is less, makes its performance fully to show.Therefore, research improves MnO 2specific conductivity, specific surface area and cyclical stability have very important meaning.Existing investigator is by MnO at present 2compound is carried out, if Li etc. is with KMnO with the carbon material with high-ratio surface sum high conductivity 4for manganese source, the CNTs with high conductivity is that supporter has prepared MnO 2/ CNTs matrix material, ratio capacitance is 201Fg -1, by AC/MnO 2the asymmetric electrical condenser of/CNTs assembling, energy density is 13.3Whkg -1, power density is 13.3Wkg -1.Dong etc. adopt in-situ synthesis MnO 2/ mesoporous carbon composite material, ratio capacitance is greater than 200Fg -1, the method not only increases MnO 2the rate of migration of surface electronic and the effective contact area increased between itself and electrolyte dissolution.Also investigator is had by MnO 2be wrapped on the higher metal oxide nano-material of electric conductivity, as Jiang etc. has synthesized Ni (OH) 2/ MnO 2matrix material, in neutral electrolyte, ratio capacitance is 355Fg -1, in alkaline electrolyte, ratio capacitance is 487.4Fg -1.Bao etc. are by ultra-thin MnO 2film, is wrapped in the Zn of high conductivity 2sO 4on, at 1Ag -1ratio capacitance 642.4Fg -1.Yang etc. adopt simple solution method by unbodied MnO 2be wrapped in SnO 2on nano wire, ratio capacitance is 637Fg -1.Metal oxide nano-material is wrapped in MnO 2the matrix material of surface gained has high specific surface area and high conductivity, thus matrix material is had than pure MnO 2more excellent chemical property, but adopt electrodip process by nano SnO 2well be wrapped in MnO 2film presents excellent chemical property, and there is not yet play-by-play by the process of the standby combined electrode assembling symmetric form ultracapacitor of this legal system.
Summary of the invention
The object of the present invention is to provide a kind of MnO 2-SnO 2/ Nano graphite chip arrays (MnO 2-SnO 2/ GNSA) preparation method of combination electrode material.
The present invention also aims to provide a kind of MnO 2-SnO 2the application of/GNSA combination electrode material in assembling symmetric form ultracapacitor.
MnO of the present invention 2-SnO 2the preparation of/GNSA combination electrode material, comprises following processing step:
1, the preparation of graphite nano plate array substrate
The cleaning of graphite rod: by level and smooth to bottom disc for graphite rod polishing, is placed on 6 ~ 10molL with the ultrasonic cleaning repeatedly of water -1hCl solution in etching 30 ~ 50min; Use the ultrasonic cleaning repeatedly of acetone and water again, dry;
Electrochemical activation peels off obtained Nano graphite chip arrays: be placed in 0.02 ~ 0.06molL by parallel for the stone mill of cleaning rod -1water phase surfactant mixture in, control voltage, at 1 ~ 8V, peels off 12 ~ 24h under 20 ~ 50 DEG C of constant temperature, forms Nano graphite chip arrays GNSA at graphite rod and electrolyte solution interface; After Nano graphite chip arrays GNSA being placed in acetone immersion 24 ~ 48h, repeatedly cleaning with high purity water, finally dry in 30 ~ 50 DEG C of air atmospheres, obtain graphite nano plate array substrate.Tensio-active agent can adopt sodium laurylsulfonate, Trisodium Citrate, Sodium dodecylbenzene sulfonate or sodium lauryl sulphate.
2, MnO 2-SnO 2the preparation of/graphite nano plate array combination electrode material
The Nano graphite chip arrays that obtains is peeled off as substrate, with MnCl using electrochemical activation 24H 2o, NaNO 3and SnCl 45H 2the mixing solutions of O is as electroplate liquid, and using graphite nano plate substrate as working electrode, platinum guaze is as to electrode, and saturated calomel electrode, as reference electrode, is 50 ~ 80 DEG C in temperature, deposits 1 ~ 10min, make cathodic reduction galvanic deposit MnO under the current potential of-0.3 ~-0.8 V 2-SnO 2on GNSA; After galvanic deposit terminates, rinse with water, dry, obtain MnO 2-SnO 2/ graphite nano plate array combination electrode material.
In described electroplate liquid, MnCl 24H 2the concentration of O is 0.1 ~ 0.5molL -1, NaNO 3concentration be 0.2 ~ 0.6molL -1, SnCl 45H 2the concentration of O is 0.01 ~ 0.05molL -1.
The preparation of symmetric form ultracapacitor: respectively with MnO 2-SnO 2/ GNSA combination electrode material as positive and negative electrode, with 0.5 ~ 1molL -1liNO 3for electrolytic solution, be assembled into symmetric form ultracapacitor.
Below by the MnO that field emission scanning electron microscope (FE-SEM), infrared spectrum (FTIR), X-ray diffraction (XRD) and electrochemical workstation CHI660B are prepared the present invention 2-SnO 2the chemical property of the properity of/GNSA combination electrode material and the symmetric form ultracapacitor of assembling carries out analytic explanation.
Fig. 1 is MnO prepared by the present invention 2-SnO 2field emission scanning electron microscope (FE-SEM) picture of/GNSAs combination electrode material and GNSA.Fig. 1 a is the FE-SEM figure of Nano graphite chip arrays GNSA.Can clearly find out, the GNSA that the number of plies does not wait is arranged parallel to each other and perpendicular to graphite rod substrate, form an open 2D array-like structure, this structure not only increases the contact area of electrolyte ion, and be conducive to absorption and the desorption of electrolyte ion, provide favourable condition for forming good electric double layer capacitance.GNSA surface, can the metal ion of adsorption zone positive charge containing the oxygen-containing functional group such as hydroxyl, carboxyl, epoxy group(ing), thus makes electrodeposition process smooth.Fig. 1 b is MnO 2-SnO 2the FE-SEM figure of/GNSA.As seen from the figure, by MnO that electrochemical process deposits 2-SnO 2be wrapped in GNSA surface, define a kind of special uneven laminate structure.
Fig. 2 is MnO prepared by the present invention 2-SnO 2the infrared spectrum of/GNSAs combined electrode and GNSA.3433cm -1the wide absorption peak at place belongs to the stretching vibration of O-H, 1628cm -1weak absorbing peak be the flexural vibration of O-H.2925cm -1the weak peak at place belongs to C-H stretching vibration, 1384cm -1the absorption peak at place is because in, phenolic hydroxyl group, the flexural vibration of C-OH cause, 1052cm -1locating more weak peak is stretching vibration in C-O.Be positioned at 704cm -1and 556cm -1strong peak be MnO 2and SnO 2the eigen vibration peak of Mn-O and Sn-O key in lattice.
Fig. 3 is MnO prepared by the present invention 2-SnO 2the XRD diffractogram of/GNSAs combined electrode and GNSA.In figure, curve a has a significantly strong diffraction peak in 2 θ=26.54 °, and belong to (002) crystal face diffraction of graphite, its peak type is regular, and peak width is narrower, shows to have good graphite-structure.Curve b is except the intrinsic peak of graphite, and in 2 θ=20.8, the diffraction peak at 36.52,54.86 ° of places belongs to MnO respectively 2(101), (210) and (402) crystal face, consistent with standard card (JCPDF 42-1316).In 2 θ=33.94, the diffraction peak at 51.78 places belongs to SnO respectively 2(101) and (211) crystal face, consistent with standard card (JCPDF 41-1445).
Fig. 4 is MnO prepared by the present invention 2-SnO 2/ GNSAs combined electrode is at 0.5 ~ 1molL -1liNO 3cyclic voltammetric (CV) curve in solution.A figure is that scanning speed equals 20mVs -1time, GNSA and MnO 2-SnO 2the CV curve of/GNSA, as seen from the figure, MnO 2-SnO 2the CV area under the curve of/GNSA is obviously greater than the CV area under the curve of GNSA, shows MnO 2-SnO 2/ GNSA has the ratio capacitance higher than GNSA.Significantly GNSA and MnO can be found out from figure 2-SnO 2the CV curve of/GNSA has a pair relatively weak redox peak, is because on GNSA, the redox reaction of oxygen-containing functional group causes.MnO in cathodic reduction galvanic deposit 2-SnO 2afterwards, the shape of CV curve does not roughly change, but the electric current under same potential window obviously increases, and the area of CV curve also increases thereupon, and this phenomenon describes GNSA and MnO 2-SnO 2between there is good electric double layer capacitance and fake capacitance forward act synergistically.Figure b be potential window at-1.8V, the CV graphic representation under different scanning rates.As seen from the figure, along with the increase of scanning speed, the shape of CV curve does not almost change, and MnO is described 2-SnO 2/ GNSA has good times capacity rate characteristic, and the energy storage of excellence and release performance.
Fig. 5 is MnO prepared by the present invention 2-SnO 2the CV graphic representation of the symmetric form ultracapacitor of/GNSAs combined electrode assembling.Wherein figure a is scanning speed is 20mVs -1time, GNSAs and MnO 2-SnO 2/ GNSAs is assembled into the CV graphic representation of symmetric form ultracapacitor.As can be seen from figure a, under the potential window of 1.8V, CV curve presents class rectangle close to desirable capacitance behavior.MnO 2-SnO 2the CV area under the curve that/GNSAs is assembled into symmetric form ultracapacitor is obviously greater than the area of GNSAs, and MnO is described 2-SnO 2the symmetric form ultracapacitor of/GNSAs assembling has more excellent ratio capacitance.Figure b is MnO 2-SnO 2/ GNSAs assembling symmetric form ultracapacitor at 1.8V potential window, the CV graphic representation under different scanning rates.From figure b, the charging and discharging of this symmetric form ultracapacitor can carry out under low and high scanning speed, and along with the increase of scanning speed, the shape of CV curve substantially large change does not occur, and MnO is described 2-SnO 2the electrical condenser of/GNSAs assembling has good times capacity rate characteristic.Figure c is that scanning speed is at 20mVs -1under, MnO 2-SnO 2symmetry type capacitance device CV curve synoptic diagram under different potentials window of/GNSAs assembling.Extend (1.4V to 1.8V) from the potential window of figure c, CV curve to positive potential district and expand, but the position at redox peak in curve remains unchanged substantially, but the area of CV curve increases along with the increase of potential window.
Fig. 6 is MnO prepared by the present invention 2-SnO 2the ratio capacitance of symmetric form ultracapacitor of/GNSAs combined electrode assembling, scanning speed, potential window, graph of relation between energy density and power density.Fig. 6 a is ratio capacitance and the relation curve between scanning speed and potential window, by observing and can be calculated, along with the increase of potential window, and MnO 2-SnO 2the ratio capacitance that/GNSAs is assembled into symmetric form ultracapacitor obviously increases.When potential window is 1.4V, scanning speed is 5mVs -1time, the ratio capacitance that GNSAs is assembled into symmetric form ultracapacitor is 149Fm -2, MnO 2-SnO 2the ratio capacitance that/GNSAs is assembled into symmetric form ultracapacitor is 871Fm -2, be 5mVs in scanning speed equally -1time, when potential window increases to 1.8V, the ratio capacitance that GNSAs is assembled into symmetric form ultracapacitor increases to 214Fm -2, MnO 2-SnO 2the ratio capacitance that/GNSAs is assembled into symmetric form ultracapacitor is high to 957Fm -2.Relatively high ratio capacitance is because the forward synergy of electric double layer capacitance and fake capacitance causes.Fig. 6 b is energy density and the relation curve between scanning speed and potential window.As seen from the figure, energy density is proportional increase along with the increase of potential window, and when potential window is 1.4V, scanning speed is 5mVs -1time, MnO 2-SnO 2the energy density that/GNSAs is assembled into symmetric form ultracapacitor is 0.24Whm -2, when potential window increases to 1.8V, energy density increases to 0.43Whm thereupon -2, be 1.8 times of initial energy density, but under identical potential window, along with the increase of scanning speed, energy density but slightly reduces.Fig. 6 c is power density and the relation curve between scanning speed and potential window, and as seen from the figure, power density is inconsistent along with the increase of potential window and the increase of energy density, and when potential window is 1.4V, scanning speed equals 5mVs -1time, power density is 3.05Wm -2but, when scanning speed increases to 50mVs -1time, its power density increases to 26.8Wm -2, when potential window increases to 1.8V, scanning speed equals 5mVs -1time, power density is 4.3Wm -2, scanning speed increases to 50mVs -1time, power density can reach 38Wm -2.By above-mentioned analysis, we are known, and power density increases along with the increase of sweeping speed.Fig. 6 d is the Ragone curve of power density and energy density.As seen from the figure, power density and energy density all increase successively along with the increase of potential window.Generally speaking, MnO 2-SnO 2/ GNSAs is assembled into symmetric form ultracapacitor to be had so excellent chemical property and derives from the open 2D network structure of GNSA, it is a kind of accessible interface for electrolyte solution provides, make the embedding of electrolyte ion and deviate to become to be more prone to, in addition, the open space of interlayer is conducive to the storage of electrolyte solution.
Fig. 7 is MnO prepared by the present invention 2-SnO 2the ac impedance spectroscopy of the title type ultracapacitor of/GNSAs combined electrode assembling.Test condition is: bias voltage is 0V, and range of frequency is 0.1Hz ~ 10kHz.Can find out, the shape of two curves is substantially identical, high frequency region MnO 2-SnO 2/ GNSAs is assembled into the curve of symmetric form ultracapacitor and the intercept of real axis is assembled into the large of symmetric form ultracapacitor compared with GNSAs, and MnO is described 2-SnO 2the measuring resistance that/GNSAs is assembled into symmetric form ultracapacitor is comparatively large, and do not occur semicircle shape curve, electrochemical polarization is not obvious, and charge transfer speed is described; The slope of low frequency range obviously increases, and shows MnO close to 90 ° 2-SnO 2/ GNSAs is assembled into the capacitance behavior that symmetric form ultracapacitor is tending towards desirable, and these characteristics are owing to MnO 2-SnO 2it is that ion provides straightway transmission path that/GNSAs is assembled into symmetric form ultracapacitor special construction.
Fig. 8 is MnO prepared by the present invention 2-SnO 2the symmetric form ultracapacitor of/GNSAs combined electrode assembling is 10Am in current density -2under cycle life graphic representation.As shown in Figure 8, the initial ratio capacitance of this symmetric form ultracapacitor is 957Fm -2, after 4000 charge and discharge cycles, ratio capacitance still can remain 70% of initial ratio capacitance, and this shows that this symmetric form ultracapacitor has excellent electrochemical stability.
In sum, the MnO for preparing of the present invention 2-SnO 2/ GNSAs combined electrode is using the direct electrode as symmetric form ultracapacitor, and this electrode can realize the synergistic effect of both performances, and has the premium properties that unitary electrode do not possess, and presents higher electrochemical capacitor performance.The MnO prepared by the present invention 2-SnO 2the symmetric form ultracapacitor of/GNSAs combined electrode assembling has excellent times capacity rate, energy density and good cyclical stability.
Accompanying drawing explanation
Fig. 1 is MnO prepared by the present invention 2-SnO 2field emission scanning electron microscope (FE-SEM) picture of/GNSA combination electrode material and GNSA.
Fig. 2 is MnO prepared by the present invention 2-SnO 2the infrared spectrum of/GNSA combined electrode and GNSA.
Fig. 3 is MnO prepared by the present invention 2-SnO 2the XRD diffractogram of/GNSA combined electrode and GNSA.
Fig. 4 is MnO prepared by the present invention 2-SnO 2/ GNSA combined electrode is at 0.5molL -1liNO 3cyclic voltammetric (CV) curve in solution.
Fig. 5 is MnO prepared by the present invention 2-SnO 2the CV graphic representation of the symmetric form ultracapacitor of/GNSA combined electrode assembling.
Fig. 6 is MnO prepared by the present invention 2-SnO 2the ratio capacitance of symmetric form ultracapacitor of/GNSA combined electrode assembling, scanning speed, potential window, graph of relation between energy density and power density.
Fig. 7 is MnO prepared by the present invention 2-SnO 2the ac impedance spectroscopy of the symmetric form ultracapacitor of/GNSA combined electrode assembling.
Fig. 8 is MnO prepared by the present invention 2-SnO 2the symmetric form ultracapacitor of/GNSA combined electrode assembling is 10Am in current density -2under cycle life graphic representation.
Embodiment
Below by specific embodiment to MnO of the present invention 2-SnO 2the chemical property of the preparation of/GNSA matrix material and the symmetry ultracapacitor of assembling thereof is described in further detail.
The instrument used and reagent: CHI660B type electrochemical workstation (Shanghai Chen Hua instrument company); W00707011 direct supply (Shanghai is Electrical Appliances Co., Ltd with all strength); ULTRA PLUS type scanning electronic microscope (German Carl zicss); RigaKuD/Max-2400 type X-ray diffraction (Rigaku company); Termo Satellite 5000 type Fourier transform infrared spectrometer; CTA2001A LAND battery test system (Wuhan Jin Nuo Electronics Co., Ltd.); HH-4 type constant water bath box (all over the country company limited in Shenzhen).Sodium dodecylbenzene sulfonate (SDBS, Yantai City is Chemical Co., Ltd. in pairs); High purity water (responsibility company limited of Shanghai HuaPu); Acetone (Red Star chemical plant, Beijing); Tin tetrachloride (Red Star chemical plant, Beijing); Manganous chloride (Tianjin Kai Xin chemical industry company limited); SODIUMNITRATE (Xi'an chemical reagent factory); Carbon-point (Battery Co., Ltd of Shanghai National).The water used in experimentation is high purity water, tests reagent used and is analytical pure.
Embodiment 1
(1) preparation of graphite nano plate array substrate GNSA; By level and smooth to bottom disc for graphite rod polishing, be placed on 6 ~ 10molL with the ultrasonic cleaning repeatedly of water -1hCl solution in etching 30 ~ 50min; Use the ultrasonic cleaning repeatedly of acetone and water again, dry.Configuration 0.02molL -1sodium dodecylbenzene sulfonate (SDBS) as electrolyte solution, two graphite of cleaning are placed in parallel in the middle of electrolyte solution, on two electrodes, apply permanent electromotive force 3V again, after peeling off 18h by anode, form GNSA array at graphite rod and electrolyte solution interface; GNSA is placed in after acetone invades bubble 24h, takes out and repeatedly rinse the electrode surface of gained with high purity water, finally drying in 30 ~ 50 DEG C of air atmospheres, obtain graphite nano plate array substrate GNSA.
(2) MnO 2-SnO 2the preparation of/GNSA combined electrode: GNSA as working electrode, platinum guaze and saturated calomel electrode (SCE) respectively as to electrode and reference electrode, with 0.5molL -1mnCl 24H 2o, 0.5molL -1naNO 3and 0.05molL -1snCl 45H 2the mixing solutions of O is electroplate liquid, under 50 DEG C of constant temperatures, applies negative potential-0.7V, cathodic reduction galvanic deposit MnO 2-SnO 2on GNSA; Depositing time is 2min; After galvanic deposit terminates, rinse with high purity water, dry, obtain MnO 2-SnO 2/ GNSA combined electrode.
MnO 2-SnO 2the electrochemical property test of/GNSA: with MnO 2-SnO 2/ GNSA is as working electrode, and with platinum guaze for being that reference electrode composition three-electrode system carries out electrochemical property test to electrode, with SCE, electrolytic solution is 0.5molL -1liNO 3solution, potential window-1.2-0.6V.Be 5-50mVs in scanning speed -1shi Jinhang cyclic voltammetry scan.When scanning speed is 5mVs -1, ratio capacitance is 4245 Fm -2; When scanning speed is 50mVs -1, ratio capacitance is 3190 Fm -2.
(3) assembling of symmetric form ultracapacitor: respectively with MnO 2-SnO 2/ GNSA combination electrode material as positive and negative electrode, with 0.5molL -1liNO 3for electrolytic solution, be assembled into symmetric form ultracapacitor.
The electrochemical property test of symmetric form ultracapacitor: carry out electrochemical property test under two electrode systems, electrolytic solution is 0.5molL -1liNO 3solution, potential window 0-1.8V.Be 5-50mVs in scanning speed -1shi Jinhang cyclic voltammetry scan, carries out ac impedance measurement when bias voltage is 0V.When scanning speed is 5mVs -1, ratio capacitance is 957 Fm -2, energy density is 0.43Whm -2, power density is 4.3Wm -2; When scanning speed is 50mVs -1, ratio capacitance is 852 Fm -2, energy density is 0.38Whm -2, power density is 38Wm -2.
Cycle life is tested: carrying out cycle life test with two electrode systems of above-mentioned composition at LAND test macro, is 10Am in current density -2under, the initial ratio capacitance of this symmetric form ultracapacitor is 957Fm -2, after 4000 charge and discharge cycles, ratio capacitance still can remain 70% of initial ratio capacitance.Can draw through above-mentioned test, this combined electrode has more excellent capacitive property and power density, has the potential becoming electrode material for super capacitor.
Embodiment 2
(1) preparation of graphite nano plate array substrate GNSA; By level and smooth to bottom disc for graphite rod polishing, be placed on 7molL with the ultrasonic cleaning repeatedly of water -1hydrochloric acid soln in etch 30min; Use the ultrasonic cleaning repeatedly of acetone and water again, dry.Configuration 0.03molL -1sodium dodecylbenzene sulfonate (SDBS) as electrolyte solution, two graphite of cleaning are placed in parallel in the middle of electrolyte solution, on two electrodes, apply permanent positive potential 1V again, after peeling off 12h by anode, form GNSA array at graphite rod and electrolyte solution interface; GNSA is placed in after acetone soaks 24h, takes out and repeatedly rinse the electrode surface of gained with high purity water, finally drying in 35 DEG C of air atmospheres, obtain graphite nano plate array substrate GNSA.
(2) MnO 2-SnO 2the preparation of/GNSA combined electrode: GNSA as working electrode, platinum guaze and saturated calomel electrode (SCE) respectively as to electrode and reference electrode, with 0.1molL -1mnCl 24H 2o, 0.2molL -1naNO 3and 0.01molL -1snCl 45H 2the mixing solutions of O is electroplate liquid, under 55 DEG C of constant temperatures, applies negative potential-0.3V, cathodic reduction galvanic deposit MnO 2-SnO 2on GNSA, electrodeposition time is 1min; After galvanic deposit terminates, rinse with high purity water, dry, obtain MnO 2-SnO 2/ GNSA combined electrode.
MnO 2-SnO 2the electrochemical property test of/GNSA: with MnO 2-SnO 2/ GNSA is as working electrode, and platinum guaze is for being that reference electrode composition three-electrode system carries out electrochemical property test to electrode, SCE, and electrolytic solution is 0.5molL -1liNO 3solution, potential window-1.2-0.6V.At scanning speed 5-50mVs -1shi Jinhang cyclic voltammetry scan, when scanning speed is 5mVs -1, ratio capacitance is 3445 Fm -2; When scanning speed is 50mVs -1, ratio capacitance is 2390 Fm -2.
(3) assembling of symmetric form ultracapacitor: respectively with MnO 2-SnO 2/ GNSA combination electrode material as positive and negative electrode, with 0.5molL -1liNO 3for electrolytic solution, be assembled into symmetric form ultracapacitor.
The electrochemical property test of symmetric form ultracapacitor: carry out electrochemical property test under two electrode systems, electrolytic solution is 0.5molL -1liNO 3solution, potential window 0-1.8V.Be 5-50mVs in scanning speed -1shi Jinhang cyclic voltammetry scan, carries out ac impedance measurement when bias voltage is 0V.When scanning speed is 5mVs -1, ratio capacitance is 871 Fm -2, energy density is 0.23Whm -2, power density is 3.05Wm -2; When scanning speed is 50mVs -1, ratio capacitance is 766 Fm -2, energy density is 0.20Whm -2, power density is 26Wm -2.
Cycle life is tested: carrying out cycle life test with two electrode systems of above-mentioned composition at LAND test macro, is 10Am in current density -2under, the initial ratio capacitance of this symmetric form ultracapacitor is 871Fm -2, after 3000 charge and discharge cycles, ratio capacitance still can remain 67% of initial ratio capacitance.Can draw through above-mentioned test, this combined electrode has more excellent capacitive property and power density, has the potential becoming electrode material for super capacitor.
Embodiment 3
(1) preparation of graphite nano plate array substrate GNSA; By level and smooth to bottom disc for graphite rod polishing, be placed on 10molL with the ultrasonic cleaning repeatedly of water -1hydrochloric acid soln in etch 30min; Use the ultrasonic cleaning repeatedly of acetone and water again, dry.Configuration 0.06molL -1sodium dodecylbenzene sulfonate (SDBS) as electrolyte solution, two graphite of cleaning are placed in parallel in the middle of electrolyte solution, on two electrodes, apply permanent positive potential 8V again, after peeling off 24h by anode, form GNSA array at graphite rod and electrolyte solution interface; GNSA is placed in after acetone soaks 48h, takes out and repeatedly rinse the electrode surface of gained with high purity water, finally drying in 50 DEG C of air atmospheres, obtain graphite nano plate array substrate GNSA.
(2) MnO 2-SnO 2the preparation of/GNSA combined electrode: GNSA as working electrode, platinum guaze and saturated calomel electrode (SCE) respectively as to electrode and reference electrode, with 0.2molL -1mnCl 24H 2o, 0.3molL -1naNO 3and 0.02molL -1snCl 45H 2the mixing solutions of O is electroplate liquid, under 80 DEG C of constant temperatures, applies negative potential-0.8V, cathodic reduction galvanic deposit MnO 2-SnO 2on GNSA, electrodeposition time is 10min; After galvanic deposit terminates, rinse with high purity water, dry, obtain MnO 2-SnO 2/ GNSA combined electrode.
MnO 2-SnO 2the electrochemical property test of/GNSA: with MnO 2-SnO 2/ GNSA is as working electrode, and with platinum guaze for being that reference electrode composition three-electrode system carries out electrochemical property test to electrode, with SCE, electrolytic solution is 0.5molL -1liNO 3solution, potential window-1.2-0.6V.Be 5-50mVs in scanning speed -1shi Jinhang cyclic voltammetry scan, when scanning speed is 5mVs -1, ratio capacitance is 3645 Fm -2; When scanning speed is 50mVs -1, ratio capacitance is 2590 Fm -2.
(3) assembling of symmetric form ultracapacitor: respectively with MnO 2-SnO 2/ GNSA combination electrode material as positive and negative electrode, with 0.5molL -1liNO 3for electrolytic solution, be assembled into symmetric form ultracapacitor.
The electrochemical property test of symmetric form ultracapacitor: carry out electrochemical property test under two electrode systems, electrolytic solution is 0.5molL -1liNO 3solution, potential window 0-1.8V.Be 5-50mVs in scanning speed -1shi Jinhang cyclic voltammetry scan, carries out ac impedance measurement when bias voltage is 0V.When scanning speed is 5mVs -1, ratio capacitance is 891 Fm -2, energy density is 0.27Whm -2, power density is 3.3Wm -2; When scanning speed is 50mVs -1, ratio capacitance is 786 Fm -2, energy density is 0.24Whm -2, power density is 29Wm -2.
Cycle life is tested: carrying out cycle life test with two electrode systems of above-mentioned composition at LAND test macro, is 10Am in current density -2under, the initial ratio capacitance of this symmetric form ultracapacitor is 891Fm -2, after 3000 charge and discharge cycles, ratio capacitance still can remain 61% of initial ratio capacitance.Can draw through above-mentioned test, this combined electrode has more excellent capacitive property and power density, has the potential becoming electrode material for super capacitor.
Embodiment 4
(1) preparation of graphite nano plate array substrate GNSA; By level and smooth to bottom disc for graphite rod polishing, be placed on 8molL with the ultrasonic cleaning repeatedly of water -1hydrochloric acid soln in etch 30min; Use the ultrasonic cleaning repeatedly of acetone and water again, dry.Configuration 0.05molL -1sodium dodecylbenzene sulfonate (SDBS) as electrolyte solution, two graphite of cleaning are placed in parallel in the middle of electrolyte solution, on two electrodes, apply permanent positive potential 5V again, after peeling off 20h by anode, form GNSA array at graphite rod and electrolyte solution interface; GNSA is placed in after acetone soaks 36h, takes out and repeatedly rinse the electrode surface of gained with high purity water, finally drying in 45 DEG C of air atmospheres, obtain graphite nano plate array substrate GNSA.
(2) MnO 2-SnO 2the preparation of/GNSA combined electrode: GNSA as working electrode, platinum guaze and saturated calomel electrode (SCE) respectively as to electrode and reference electrode, with 0.3molL -1mnCl 24H 2o, 0.5molL -1naNO 3and 0.04molL -1snCl 45H 2the mixing solutions of O is electroplate liquid, under 60 DEG C of constant temperatures, applies negative potential-0.5V, cathodic reduction galvanic deposit MnO 2-SnO 2on GNSA, electrodeposition time is 3min; After galvanic deposit terminates, rinse with high purity water, dry, obtain MnO 2-SnO 2/ GNSA combined electrode.
MnO 2-SnO 2the electrochemical property test of/GNSA: with MnO 2-SnO 2/ GNSA is as working electrode, and with platinum guaze for being that reference electrode composition three-electrode system carries out electrochemical property test to electrode, with SCE, electrolytic solution is 0.5molL -1liNO 3solution, potential window-1.2-0.6V.Be 5-50mVs in scanning speed -1shi Jinhang cyclic voltammetry scan, when scanning speed is 5mVs -1, ratio capacitance is 3845 Fm -2; When scanning speed is 50mVs -1, ratio capacitance is 2791 Fm -2.
(3) assembling of symmetric form ultracapacitor: respectively with MnO 2-SnO 2/ GNSA combination electrode material as positive and negative electrode, with 0.5molL -1liNO 3for electrolytic solution, be assembled into symmetric form ultracapacitor.
The electrochemical property test of symmetric form ultracapacitor: carry out electrochemical property test under two electrode systems, electrolytic solution is 0.5molL -1liNO 3solution, potential window 0-1.8V.Be 5-50mVs in scanning speed -1shi Jinhang cyclic voltammetry scan, carries out ac impedance measurement when bias voltage is 0V.When scanning speed is 5mVs -1, ratio capacitance is 911 Fm -2, energy density is 0.32Whm -2, power density is 3.6Wm -2; When scanning speed is 50mVs -1, ratio capacitance is 806 Fm -2, energy density is 0.28Whm -2, power density is 32Wm -2.
Cycle life is tested: carrying out cycle life test with two electrode systems of above-mentioned composition at LAND test macro, is 10Am in current density -2under, the initial ratio capacitance of this symmetric form ultracapacitor is 911Fm -2, after 3000 charge and discharge cycles, ratio capacitance still can remain 63% of initial ratio capacitance.Can draw through above-mentioned test, this combined electrode has more excellent capacitive property and power density, has the potential becoming electrode material for super capacitor.
Embodiment 5
(1) preparation of graphite nano plate array substrate GNSA; By level and smooth to bottom disc for graphite rod polishing, be placed on 9molL with the ultrasonic cleaning repeatedly of water -1hydrochloric acid soln in etch 30min; Use the ultrasonic cleaning repeatedly of acetone and water again, dry.Configuration 0.04molL -1sodium dodecylbenzene sulfonate (SDBS) as electrolyte solution, two graphite of cleaning are placed in parallel in the middle of electrolyte solution, on two electrodes, apply permanent positive potential 3.5V again, after peeling off 15h by anode, form GNSA array at graphite rod and electrolyte solution interface; GNSA is placed in after acetone soaks 30h, takes out and repeatedly rinse the electrode surface of gained with high purity water, finally drying in 35 DEG C of air atmospheres, obtain graphite nano plate array substrate GNSA.
(2) MnO 2-SnO 2the preparation of/GNSA combined electrode: GNSA as working electrode, platinum guaze and saturated calomel electrode (SCE) respectively as to electrode and reference electrode, with 0.4molL -1mnCl 24H 2o, 0.5molL -1naNO 3and 0.03molL -1snCl 45H 2the mixing solutions of O is electroplate liquid, under 65 DEG C of constant temperatures, applies negative potential-0.6V, cathodic reduction galvanic deposit MnO 2-SnO 2on GNSA, electrodeposition time is 5min; After galvanic deposit terminates, rinse with high purity water, dry, obtain MnO 2-SnO 2/ GNSA combined electrode.
MnO 2-SnO 2the electrochemical property test of/GNSA: with MnO 2-SnO 2/ GNSA is as working electrode, and with platinum guaze for being that reference electrode composition three-electrode system carries out electrochemical property test to electrode, with SCE, electrolytic solution is 0.5molL -1liNO 3solution, potential window-1.2-0.6V.Be 5-50mVs in scanning speed -1shi Jinhang cyclic voltammetry scan, when scanning speed is 5mVs -1, ratio capacitance is 3834 Fm -2; When scanning speed is 50mVs -1, ratio capacitance is 2990 Fm -2.
(3) assembling of symmetric form ultracapacitor: respectively with MnO 2-SnO 2/ GNSA combination electrode material as positive and negative electrode, with 0.5molL -1liNO 3for electrolytic solution, be assembled into symmetric form ultracapacitor.
The electrochemical property test of symmetric form ultracapacitor: carry out electrochemical property test under two electrode systems, electrolytic solution is 0.5molL -1liNO 3solution, potential window 0-1.8V.Be 5-50mVs in scanning speed -1shi Jinhang cyclic voltammetry scan, carries out ac impedance measurement when bias voltage is 0V.When scanning speed is 5mVs -1, ratio capacitance is 931 Fm -2, energy density is 0.37Whm -2, power density is 3.95Wm -2; When scanning speed is 50mVs -1, ratio capacitance is 832 Fm -2, energy density is 0.33Whm -2, power density is 35Wm -2.
Cycle life is tested: carrying out cycle life test with two electrode systems of above-mentioned composition at LAND test macro, is 10Am in current density -2under, the initial ratio capacitance of this symmetric form ultracapacitor is 931Fm -2, after 4000 charge and discharge cycles, ratio capacitance still can remain 68% of initial ratio capacitance.Can draw through above-mentioned test, this combined electrode has more excellent capacitive property and power density, has the potential becoming electrode material for super capacitor.

Claims (8)

1. a MnO 2-SnO 2the preparation method of/graphite nano plate array combination electrode material peels off the Nano graphite chip arrays that obtains as substrate, with MnCl using electrochemical activation 24H 2o, NaNO 3and SnCl 45H 2the mixing solutions of O is as electroplate liquid, and using graphite nano plate substrate as working electrode, platinum guaze is as to electrode, and saturated calomel electrode, as reference electrode, is 50 ~ 80 DEG C in temperature, deposits 1 ~ 10min under the current potential of-0.3 ~-0.8 V; After galvanic deposit terminates, rinse with water, dry, obtain MnO 2-SnO 2/ graphite nano plate array combination electrode material.
2. MnO as claimed in claim 1 2-SnO 2the preparation method of/graphite nano plate array combination electrode material, is characterized in that: electrochemical activation is peeled off the technique obtaining Nano graphite chip arrays and is: be placed in 0.02 ~ 0.06molL by parallel for the stone mill of cleaning rod -1water phase surfactant mixture in, control voltage, at 1 ~ 8V, peels off 12 ~ 24h under 20 ~ 50 DEG C of constant temperature, forms Nano graphite chip arrays at graphite rod and electrolyte solution interface; After Nano graphite chip arrays being placed in acetone immersion 24 ~ 48h, taking-up high purity water cleans repeatedly, dries, obtains graphite nano plate array substrate.
3. MnO as claimed in claim 2 2-SnO 2the preparation method of/graphite nano plate array combination electrode material, is characterized in that: the cleaning of described graphite rod is: by level and smooth to bottom disc for graphite rod polishing, be placed on 6 ~ 10molL with water ultrasonic cleaning -1hCl solution in etching 30 ~ 50min; Use the ultrasonic cleaning repeatedly of acetone and water again, dry.
4. MnO as described in Claims 2 or 3 2-SnO 2the preparation method of/graphite nano plate array combination electrode material, is characterized in that: described tensio-active agent is sodium laurylsulfonate, Trisodium Citrate, Sodium dodecylbenzene sulfonate or sodium lauryl sulphate.
5. MnO as claimed in claim 1 2-SnO 2the preparation method of/graphite nano plate array combination electrode material, is characterized in that: in described electroplate liquid, MnCl 24H 2the concentration of O is 0.1 ~ 0.5molL -1, NaNO 3concentration be 0.2 ~ 0.6molL -1, SnCl 45H 2the concentration of O is 0.01 ~ 0.05molL -1.
6. MnO as claimed in claim 1 2-SnO 2the preparation method of/graphite nano plate array combination electrode material, is characterized in that: described drying is dried in 30 ~ 50 DEG C of air atmospheres.
7. the MnO for preparing of method as claimed in claim 1 2-SnO 2the application of/graphite nano plate array combination electrode material in assembling symmetric form ultracapacitor.
8. MnO as claimed in claim 7 2-SnO 2the application of/graphite nano plate array combination electrode material in assembling symmetric form ultracapacitor, is characterized in that: respectively with MnO 2-SnO 2/ graphite nano plate array combination electrode as the positive pole of ultracapacitor and negative pole, with 0.1 ~ 0.5molL -1liNO 3solution is that electrolyte solution assembles.
CN201410802627.9A 2014-12-22 2014-12-22 Preparation and application of MnO2-SnO2/graphite nanometer array composite electrode material Pending CN104499022A (en)

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CN107653447A (en) * 2017-08-10 2018-02-02 上海博丹环境工程技术股份有限公司 A kind of mineral carbon load stannic oxide electrode and preparation method
CN108538609A (en) * 2018-01-02 2018-09-14 北京化工大学 A kind of iron Cu oxide/copper base electrode material and preparation method thereof
CN109449005A (en) * 2018-11-16 2019-03-08 华中师范大学 Integrate supercapacitor

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107653447A (en) * 2017-08-10 2018-02-02 上海博丹环境工程技术股份有限公司 A kind of mineral carbon load stannic oxide electrode and preparation method
CN107653447B (en) * 2017-08-10 2019-05-10 上海博丹环境工程技术股份有限公司 A kind of mineral carbon load stannic oxide electrode and preparation method
CN108538609A (en) * 2018-01-02 2018-09-14 北京化工大学 A kind of iron Cu oxide/copper base electrode material and preparation method thereof
CN108538609B (en) * 2018-01-02 2019-10-18 北京化工大学 A kind of iron Cu oxide/copper base electrode material and preparation method thereof
CN109449005A (en) * 2018-11-16 2019-03-08 华中师范大学 Integrate supercapacitor

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