CN113053676A - Composite film electrode material, electrode and preparation method thereof - Google Patents
Composite film electrode material, electrode and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 90
- 239000007772 electrode material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229910003144 α-MnO2 Inorganic materials 0.000 claims abstract description 109
- 239000006185 dispersion Substances 0.000 claims abstract description 69
- 239000010408 film Substances 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000010409 thin film Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 229910021389 graphene Inorganic materials 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 239000012528 membrane Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002048 multi walled nanotube Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 10
- 239000002041 carbon nanotube Substances 0.000 abstract description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 8
- 238000003828 vacuum filtration Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003990 capacitor Substances 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002070 nanowire Substances 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 230000004083 survival effect Effects 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
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Abstract
The invention relates to the technical field of energy material storage, in particular to NH2‑rGO/CNT/α‑MnO2The following technical scheme, NH, is proposed for solving the problems of complicated preparation process, poor performance improvement effect of a thin film electrode, poor performance of an electrode material and the like2‑rGO/CNT/α‑MnO2An NWs composite thin film electrode material, the electrode material having the following composition: NH (NH)2‑rGO、CNT、α‑MnO2NWs，NH2‑rGO、CNT、α‑MnO2The NWs is prepared into the electrode material according to the proportion of 10-20 ml to 50 ml. The invention adopts NH2-rGO, commercial carbon nano-tube, manganese dioxide nano-wire and solvent to mix to obtain uniform dispersion liquid, the dispersion liquid is dried after vacuum filtration to obtain NH 2-rGO/CNT/alpha-MnO 2NWS composite film electrode material, the material is used in the direction of a super capacitor, and the material has the advantages of high capacity, good stability, high capacity of resisting corrosion, high yield and the likeThe high specific capacitance has certain flexibility and mechanical properties, can meet the requirements of assembled solid-state flexible capacitors on electrode materials, and provides a new idea for applying manganese oxide-based electrode materials to flexible electrode materials.
Description
Technical Field
The invention relates to energy material storageThe technical field, in particular to NH2-rGO/CNT/α-MnO2An NWs composite film material, an electrode and a preparation method thereof, relating to NH2-rGO/CNT/α-MnO2A preparation method of NWs composite film material, and also relates to NH2-rGO/CNT/α-MnO2NWs composite thin film electrodes.
Background
The energy is a material basis for human survival and development, wherein the super capacitor is used as a novel green energy storage device, has excellent power density and long cycle life, has wide application prospect in the fields of new energy technology, electric automobiles and the like, and the energy storage performance of the flexible super capacitor is influenced by the electrode material of the flexible super capacitor, so that the flexible electrode material needs to meet the requirements of good flexibility, high specific capacitance, excellent cycle stability and the like. Researches find that the prepared composite film electrode can make up the defects of the manganese oxide electrode material by adding a carbon material with high conductivity and long cycle life into the manganese oxide material.
Carbon-based materials have important practical significance in constructing electrodes required for high-strength, flexible ultralight supercapacitors, and graphene-based supercapacitors having different morphologies have shown promise in the electronics industry due to their high flexibility, good stability, excellent electrical conductivity, and lightness, and researchers have been working on improving electrochemical properties through structural optimization of graphene or carbon nanotubes to develop new electrode materials having carbon nanotubes or graphene-based materials of various geometries so far.
In recent years, the preparation of high-performance manganese oxide-based flexible electrode materials is taken as a starting point, the manganese oxide base material is modified and prepared by a doping technology, the preparation process is complicated, the treatment time is long, the preparation cost is high, the performance improvement effect on the thin film electrode is poor, and the prepared composite thin film electrode material has poor performance and influences the energy storage performance of the composite thin film electrode.
Disclosure of Invention
Technical problem to be solved
In view of the above-mentioned shortcomings of the prior art, the present invention provides an NH2-rGO/CNT/α-MnO2The NWs composite film electrode material, the electrode and the preparation method thereof solve the problems in the prior art.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme:
NH (hydrogen sulfide)2-rGO/CNT/α-MnO2An NWs composite thin film electrode material, the electrode material having the following composition: NH (NH)2-rGO、CNT、α-MnO2 NWs，NH2-rGO、CNT、α-MnO2The NWs is prepared into the electrode material according to the proportion of 10-20 ml to 50 ml.
Preferably, NH2-rGO/CNT/α-MnO2The preparation method of the NWs composite film electrode material comprises the following steps:
(1) providing graphene oxide aqueous dispersion liquid with the concentration of 0.1-1.0 g/L and CNT dispersion liquid with the concentration of 0.1-1 g/L for later use;
(2) preparation of NH2-rGO: mixing dimethylformamide and the graphene oxide aqueous dispersion, stirring for 1-1.5 h under the water bath condition, then adding a phenylenediamine solution, heating to 70-90 ℃, and continuously refluxing and stirring for 9-11 h to obtain NH2-rGO；
(3) Configuration of NH2-rGO aqueous dispersion: with the use of said NH2-NH with rGO configuration concentration of 0.1-1.0 g/L2-an aqueous dispersion of rGO;
(4) preparation of alpha-MnO2NWs: 20ml of KMnO was taken4The aqueous solution is added with 20ml of MnSO dropwise under the condition of stirring speed of 200-400r/min4.H2O aqueous solution and 20ml NH4Mixing the aqueous solution F, stirring for 10-30 min, performing hydrothermal reaction to obtain a precipitate, cleaning the precipitate until the supernatant is colorless, vacuum drying the precipitate at 60 ℃, and grinding to obtain alpha-MnO2NWs powder;
(5) configuration of alpha-MnO2NWs aqueous dispersion: adding alpha-MnO2Dispersing NWs powder into deionized water to prepare 1g/L alpha-MnO2An aqueous dispersion of NWs;
(6) preparing a uniform dispersion liquid: taking NH according to the ratio of 10-20 ml to 50ml2-rGO aqueous solution, CNT aqueous dispersion, alpha-MnO2NWs aqueous dispersion of NH2Mixing and ultrasonically treating an-rGO aqueous solution and a CNT aqueous dispersion for 10-30 minutes, and dropwise adding the mixture to alpha-MnO2Mixing and stirring the NWs aqueous dispersion for 5-10 h to obtain uniform dispersion;
(7) preparing a composite film electrode: vacuum-treating the uniform dispersion liquid, and drying at room temperature to obtain NH2-rGO/CNT/α-MnO2NWs composite thin film electrodes.
Preferably, the graphene oxide is prepared by a Hummers method;
and/or washing graphene oxide with 1:1 ethanol and deionized water for multiple times until the supernatant is colorless, and then dispersing the precipitate into the deionized water to prepare the graphene oxide aqueous dispersion with the concentration of 0.1-1.0 g/L.
Preferably, the water bath temperature in the step (2) is 30-40 ℃, and the concentration of the p-phenylenediamine solution is 3.0 g/L.
Preferably, ethanol and deionized water are used for washing the NH in the step (3)2Washing the rGO for multiple times until the supernatant is colorless and neutral, dispersing the precipitate into deionized water, and performing ultrasonic treatment to obtain NH with the concentration of 0.1-1.0 g/L2-an aqueous rGO solution; preferably, the time of the ultrasonic treatment is 30-60 min.
Preferably, the configuration of the CNT dispersion: dissolving CNT in deionized water, and ultrasonically cleaning for 1-2 h to obtain CNT dispersion liquid with the concentration of 0.1-1 g/L; preferably, the CNT is hydroxylated carbon nanotube obtained by activating common commercial multi-wall carbon nanotube with strong acid, and the CNT is concentrated with HNO3And (4) performing medium reflux activation to obtain the activated CNT.
Preferably, the temperature of the hydrothermal reaction in the step (4) is 180 ℃, and the reaction time is 20 h.
Preferably, said MnSO in step (4)4H2O aqueous solution, NH4The concrete preparation steps of the F aqueous solution and the KMnO4 aqueous solution are as follows:
s1: mixing MnSO4.H2Dissolving O in deionized water to obtain 0.025mol/L MnSO4.H2An aqueous solution of O;
s2: reacting NH4F is dissolved in deionized water to prepare 1.2mol/L NH4F, water solution;
s3: mixing KMnO4Dissolving in deionized water to obtain 0.05mol/L KMnO4An aqueous solution.
Preferably, in the step (7), the obtained sample is dried on the filter membrane at room temperature; preferably, the filter membrane is an organic filter membrane with a pore size of 0.22 μm.
Preferably, the electrode material of the composite thin film electrode has the following composition: NH (NH)2-rGO、CNT、α-MnO2 NWs，NH2-rGO、CNT、α-MnO2The NWs is used for preparing the electrode material according to the proportion of 10-20 ml to 50 ml; the electrode material adopts NH as defined in any one of claims 2 to 92-rGO/CNT/α-MnO2The NWs composite film electrode material is prepared by a preparation method.
(III) advantageous effects
Compared with the prior art, the invention provides NH2-rGO/CNT/α-MnO2The NWs composite film electrode material, the electrode and the preparation method thereof have the following beneficial effects:
1. the NH2-rGO/CNT/α-MnO2The combination of aminated graphene and multi-walled carbon nanotubes effectively improves the conductivity of the electrode material, the existence of amino improves the electrochemical activity of the material, the wettability of the material and electrolyte is improved, the existence of one-dimensional carbon nanotubes avoids graphene agglomeration to a certain extent, promotes the rapid diffusion of electrolyte ions in the transverse direction of a compact film material, and can provide pseudo capacitance through redox reaction to prepare the NWs composite film electrode material, and the electrode and the preparation method thereofThe integral specific capacity of the composite film electrode is improved;
2. the NH2-rGO/CNT/α-MnO2NWs composite film electrode material, electrode and preparation method thereof, and prepared NH2-rGO/CNT/α-MnO2The NWs composite film electrode has a stable and compact network structure and is based on NH in a composite material2-rGO, one-dimensional MnO2The synergy between the nano wire and the carbon nano tube realizes the performance improvement of the film electrode, so that the film electrode has good specific capacitance and rate capability;
3. the NH2-rGO/CNT/α-MnO2The NWs composite film electrode material, the electrode and the preparation method thereof are prepared by carrying out vacuum filtration on uniform dispersion liquid in the operation process to realize NH2-rGO/CNT/α-MnO2The preparation of the NWs composite film electrode is simplified, and the prepared composite film electrode has good flexibility and mechanical property.
Drawings
Fig. 1 is a flowchart of a method for preparing an electrode material of a composite thin film electrode according to embodiment 1 of the present invention.
FIG. 2 shows NH according to the present invention2-rGO/CNT/α-MnO2Scanning electron microscope images of the NWs composite thin film electrode material under low power;
FIG. 3 shows NH according to the present invention2-rGO/CNT/α-MnO2Scanning electron microscope images of the NWs composite thin film electrode material under high power;
FIG. 4 shows NH according to the present invention2-rGO/CNT/α-MnO2An optical photo of the NWs composite film electrode material in a bending state;
FIG. 5 shows NH according to the present invention2-rGO/CNT/α-MnO2NWs composite thin film electrode material and NH2-rGO/α-MnO2NWs composite thin film electrode material and CNT/alpha-MnO2Comparing the capacitance performance of the NWs composite film electrode material;
FIG. 6 shows NH proposed by the present invention2-rGO/CNT/α-MnO2A capacitance performance diagram of the NWs composite film electrode material;
FIG. 7 is a drawing showingNH proposed by the invention2-rGO/CNT/α-MnO2NWs composite thin film electrode material and NH2-rGO/α-MnO2NWs composite thin film electrode material and CNT/alpha-MnO2XRD pattern of NWs composite film electrode material;
FIG. 8 shows NH according to the present invention2-rGO/CNT/α-MnO2NWs composite thin film electrode material and NH2-rGO/α-MnO2NWs composite thin film electrode material and CNT/alpha-MnO2Impedance contrast graph of NWs composite thin film electrode material;
FIG. 9 shows NH proposed by the present invention2-rGO/CNT/α-MnO2Stress-strain curve diagram of NWs composite film electrode material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
Example one
The embodiment discloses an NH2-rGO/CNT/α-MnO2The NWs composite film electrode is characterized in that an electrode material of the composite film electrode comprises the following components: NH (NH)2-rGO、CNT、α-MnO2 NWs，NH2-rGO、CNT、α-MnO2The NWs is prepared into the electrode material according to the proportion of 10-20 ml to 50 ml.
Referring to fig. 1, the method for preparing the electrode material includes the following steps.
(1) Providing graphene oxide aqueous dispersion with the concentration of 0.1-1.0 g/L and CNT aqueous dispersion with the concentration of 0.1-1 g/L, wherein the CNT is hydroxylated carbon nano-tubes obtained by activating common commercial multi-walled carbon nano-tubes with strong acid, and the CNT is concentrated in HNO3And (5) medium reflux activation.
The graphene oxide can be prepared by a Hummers method.
The graphene oxide aqueous dispersion can be prepared by the following steps: washing the graphene oxide with ethanol and deionized water in a ratio of 1:1 for multiple times until the supernatant is colorless, and dispersing the precipitate into the deionized water to prepare the graphene oxide.
The CNT dispersion can be prepared by the following steps: and dissolving the CNT in deionized water, and then placing the CNT in an ultrasonic cleaner for treatment for 1-2 h to prepare the CNT.
(2) Preparation of NH2-rGO: mixing dimethylformamide and the graphene oxide aqueous dispersion (which can be placed in a reaction kettle), stirring for 1-1.5 h under the condition of water bath, wherein the temperature of the water bath is 30-40 ℃, then adding a phenylenediamine solution with the concentration of 3.0g/L (which can be placed in the reaction kettle), heating to 70-90 ℃, and continuously refluxing and stirring for 9-11 h to obtain NH2-rGO。
The aminated graphene is obtained by mixing dimethylformamide, and due to the existence of amino, the electrochemical activity of the material is improved, and the wettability of the material and an electrolyte is increased.
(3) Configuration of NH2-rGO aqueous dispersion: with the use of said NH2-NH with rGO configuration concentration of 0.1-1.0 g/L2-an aqueous dispersion of rGO.
NH2-the aqueous rGO solution can be prepared by: (ethanol and deionized water can be adopted) to clean NH2Washing the rGO for multiple times until the supernatant is colorless and neutral, dispersing the precipitate into deionized water, and performing ultrasonic treatment for 30-60 min to obtain NH with the concentration of 0.1-1.0 g/L2-an aqueous rGO solution.
(4) Preparation of alpha-MnO2NWs: 20ml of KMnO was taken4The aqueous solution is added with 20ml of MnSO dropwise under the condition of stirring speed of 200-400r/min4.H2O aqueous solution and 20ml NH4Mixing the aqueous solution F, stirring for 10-30 min, performing hydrothermal reaction at 180 ℃ for 20h to obtain a precipitate, cleaning the precipitate until the supernatant is colorless, performing vacuum drying on the precipitate at 60 ℃, and grinding to obtain alpha-MnO2NWs powder.
MnSO4Aqueous solution, NH4Aqueous solution of F and KMnO4The concrete preparation steps of the aqueous solution are as follows:
s1: mixing MnSO4.H2Dissolving O in deionized water to obtain 0.025mol/L MnSO4An aqueous solution;
s2: reacting NH4F is dissolved in deionized water to prepare 1.2mol/L NH4F, water solution;
s3: mixing KMnO4Dissolving in deionized water to obtain 0.05mol/L KMnO4An aqueous solution.
(5) Configuration of alpha-MnO2NWs aqueous dispersion: adding alpha-MnO2Dispersing NWs powder into deionized water to prepare 1g/L alpha-MnO2An aqueous dispersion of NWs.
(6) Preparing a uniform dispersion liquid: taking NH according to the ratio of 10-20 ml to 50ml2-rGO aqueous solution, CNT aqueous dispersion, alpha-MnO2NWs aqueous dispersion of NH2Mixing and ultrasonically treating an-rGO aqueous solution and a CNT aqueous dispersion for 10-30 minutes, and dropwise adding the mixture to alpha-MnO2And mixing and stirring the NWs aqueous dispersion for 5-10 hours to obtain the uniform dispersion. The one-dimensional carbon nano tube avoids graphene agglomeration and promotes the rapid diffusion of electrolyte ions in the transverse direction of the compact film material.
(7) Preparing a composite film electrode: vacuum-treating the uniform dispersion liquid, and drying at room temperature to obtain NH2-rGO/CNT/α-MnO2NWs composite thin film electrodes.
In this embodiment, the uniform dispersion is placed in a vacuum filtration machine for vacuum treatment, the vacuum filtration simplifies the preparation of the composite membrane electrode, and the sample is placed on an organic filter membrane with a pore size of 0.22 μm and dried at room temperature to obtain NH2-rGO/CNT/α-MnO2The NWs composite film electrode improves the conductivity of an electrode material and the integral specific capacity of the film electrode by combining the aminated graphene and the multi-walled carbon nano tube.
Please refer to fig. 2 to 9, wherein fig. 2 is NH2-rGO/CNT/α-MnO2Scanning electron microscope images of the NWs composite thin film electrode material under low power; FIG. 3 is NH2-rGO/CNT/α-MnO2Scanning electron microscope images of the NWs composite thin film electrode material under high power; FIG. 4 is NH2-rGO/CNT/α-MnO2An optical photo of the NWs composite film electrode material in a bending state; FIG. 5 is NH2-rGO/CNT/α-MnO2NWs composite thin film electrode material and NH2-rGO/α-MnO2NWs composite thin film electrode material and CNT/alpha-MnO2Comparing the capacitance performance of the NWs composite film electrode material; FIG. 6 is NH2-rGO/CNT/α-MnO2A capacitance performance diagram of the NWs composite film electrode material; FIG. 7 is NH2-rGO/CNT/α-MnO2NWs composite thin film electrode material and NH2-rGO/α-MnO2NWs composite thin film electrode material and CNT/alpha-MnO2XRD pattern of NWs composite film electrode material; FIG. 8 shows NH2-rGO/CNT/α-MnO2NWs composite thin film electrode material and NH2-rGO/α-MnO2NWs composite thin film electrode material and CNT/alpha-MnO2Impedance contrast graph of NWs composite thin film electrode material; FIG. 9 is NH2-rGO/CNT/α-MnO2Stress-strain curve diagram of NWs composite film electrode material. The beneficial effects of the invention can be verified as follows:
1. the conductivity of the electrode material is effectively improved by combining aminated graphene and multi-walled carbon nanotubes, the electrochemical activity of the material is improved by the presence of amino groups, the wettability of the material and electrolyte is improved, the graphene agglomeration is avoided to a certain extent by the presence of one-dimensional carbon nanotubes, the transverse rapid diffusion of electrolyte ions in a compact film material is promoted, pseudo-capacitance can be provided through redox reaction, and the integral specific capacity of the prepared composite film electrode is improved;
2. preparation of the resulting NH2-rGO/CNT/α-MnO2The NWs composite film electrode has a stable and compact network structure and is based on NH in a composite material2-rGO, one-dimensional MnO2The synergy between the nano wire and the carbon nano tube realizes the performance improvement of the film electrode, so that the film electrode has good specific capacitance and rate capability;
3. in the operation process, the catalyst can be prepared by carrying out vacuum filtration on the uniform dispersion liquid to realize NH2-rGO/CNT/α-MnO2The preparation of the NWs composite film electrode is simplified, and the prepared composite film electrode has good performanceFlexibility and mechanical properties.
Example two
This example provides an NH2-rGO/CNT/α-MnO2The preparation method of NWs composite thin film electrode material is substantially similar to the preparation method of the composite thin film electrode material described in the first embodiment, except that 20ml of NH is taken in step (6) of this embodiment2Ultrasonic treatment of the aqueous dispersion of-rGO for 20 minutes, and dropwise addition of the aqueous dispersion to 50ml of alpha-MnO2Mixing NWs water dispersion, stirring and stirring for 6h to obtain uniform dispersion, treating the uniform dispersion in a vacuum filter, drying the obtained sample on a filter membrane at room temperature to obtain NH2-rGO/α-MnO2The filter membrane used in the NWs composite membrane electrode and the vacuum filtration is an organic filter membrane with the aperture of 0.22 mu m.
The electrode material of the composite film electrode comprises the following components: NH (NH)2-rGO、α-MnO2 NWs，NH2-rGO、α-MnO2The electrode material was prepared with NWs at a ratio of 20ml to 50 ml.
EXAMPLE III
This example provides an NH2-rGO/CNT/α-MnO2A process for preparing a NWs composite thin film electrode material, which is similar to the first example, except that 20ml of CNT aqueous dispersion is ultrasonically treated for 20 minutes in step (6) of this example, and then added dropwise to 50ml of alpha-MnO2Mixing NWs water dispersion, stirring and stirring for 6h to obtain uniform dispersion, treating the uniform dispersion in a vacuum suction filter, drying the obtained sample on a filter membrane at room temperature to obtain CNT/alpha-MnO2The filter membrane used in the NWs composite membrane electrode and the vacuum filtration is an organic filter membrane with the aperture of 0.22 mu m.
The electrode material of the composite film electrode comprises the following components: CNT, alpha-MnO2 NWs，CNT、α-MnO2The electrode material was prepared with NWs at a ratio of 20ml to 50 ml.
Example four
This example provides an NH2-rGO/CNT/α-MnO2Preparation method of NWs composite film electrode material, differenceIn the present example, 10ml of NH was taken in step (6)2-rGO aqueous dispersion and 10ml CNT aqueous dispersion are sonicated for 20 minutes and added dropwise to 50ml of alpha-MnO2Mixing NWs water dispersion, stirring and stirring for 6h to obtain uniform dispersion, treating the uniform dispersion in a vacuum suction filter, drying the obtained sample on a filter membrane at room temperature to obtain CNT/alpha-MnO2The filter membrane used in the NWs composite membrane electrode and the vacuum filtration is an organic filter membrane with the aperture of 0.22 mu m.
The electrode material of the composite film electrode comprises the following components: NH (NH)2-rGO、CNT、α-MnO2 NWs，NH2-rGO、CNT、α-MnO2NWs was mixed as 10ml: the electrode material was prepared in a ratio of 10ml to 50 ml.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. NH (hydrogen sulfide)2-rGO/CNT/α-MnO2The NWs composite film electrode material is characterized by comprising the following components: NH (NH)2-rGO、CNT、α-MnO2 NWs，NH2-rGO、CNT、α-MnO2The NWs is prepared into the electrode material according to the proportion of 10-20 ml to 50 ml.
2. An NH according to claim 12-rGO/CNT/α-MnO2The preparation method of the NWs composite film electrode material is characterized by comprising the following steps of:
(1) providing graphene oxide aqueous dispersion liquid with the concentration of 0.1-1.0 g/L and CNT dispersion liquid with the concentration of 0.1-1 g/L for later use;
(2) preparation of NH2-rGO: mixing dimethylformamide and the graphene oxide aqueous dispersion, stirring for 1-1.5 h under the water bath condition, adding a phenylenediamine solution, heating to 70-90 ℃, and continuing refluxing and stirringStirring for 9-11 h to obtain NH2-rGO；
(3) Configuration of NH2-rGO aqueous dispersion: with the use of said NH2-NH with rGO configuration concentration of 0.1-1.0 g/L2-an aqueous dispersion of rGO;
(4) preparation of alpha-MnO2NWs: 20ml of KMnO was taken4The aqueous solution is added with 20ml of MnSO dropwise under the condition of stirring speed of 200-400r/min4·H2O aqueous solution and 20ml NH4Mixing the aqueous solution F, stirring for 10-30 min, performing hydrothermal reaction to obtain a precipitate, cleaning the precipitate until the supernatant is colorless, placing the precipitate at 60 ℃ for vacuum drying, and grinding to obtain alpha-MnO2NWs powder;
(5) configuration of alpha-MnO2NWs aqueous dispersion: adding alpha-MnO2Dispersing NWs powder into deionized water to prepare 1g/L alpha-MnO2An aqueous dispersion of NWs;
(6) preparing a uniform dispersion liquid: taking NH according to the ratio of 10-20 ml to 50ml2-rGO aqueous solution, CNT aqueous dispersion, alpha-MnO2NWs aqueous dispersion of NH2Mixing and ultrasonically treating an-rGO aqueous solution and a CNT aqueous dispersion for 10-30 minutes, and dropwise adding the mixture to alpha-MnO2Mixing and stirring the NWs aqueous dispersion for 5-10 h to obtain uniform dispersion;
(7) preparing a composite film electrode: vacuum-treating the uniform dispersion liquid, and drying at room temperature to obtain NH2-rGO/CNT/α-MnO2NWs composite thin film electrodes.
3. NH according to claim 22-rGO/CNT/α-MnO2The preparation method of the NWs composite film electrode material is characterized in that the graphene oxide is prepared by a Hummers method;
and/or washing graphene oxide with 1:1 ethanol and deionized water for multiple times until the supernatant is colorless, and then dispersing the precipitate into the deionized water to prepare the graphene oxide aqueous dispersion with the concentration of 0.1-1.0 g/L.
4. NH according to claim 22-rGO/CNT/α-MnO2The preparation method of the NWs composite film electrode material is characterized in that the water bath temperature in the step (2) is 30-40 ℃, and the concentration of the p-phenylenediamine solution is 3.0 g/L.
5. NH according to claim 22-rGO/CNT/α-MnO2The preparation method of the NWs composite film electrode material is characterized in that ethanol and deionized water are adopted to clean the NH in the step (3)2Washing the rGO for multiple times until the supernatant is colorless and neutral, dispersing the precipitate into deionized water, and performing ultrasonic treatment to obtain NH with the concentration of 0.1-1.0 g/L2-an aqueous rGO solution; preferably, the time of the ultrasonic treatment is 30-60 min.
6. NH according to claim 22-rGO/CNT/α-MnO2The preparation method of the NWs composite film electrode material is characterized in that the configuration of the CNT dispersion liquid is as follows: dissolving CNT in deionized water, and ultrasonically cleaning for 1-2 h to obtain CNT dispersion liquid with the concentration of 0.1-1 g/L; preferably, the CNT is hydroxylated carbon nanotube obtained by activating common commercial multi-wall carbon nanotube with strong acid, and the CNT is concentrated with HNO3And (4) performing medium reflux activation to obtain the activated CNT.
7. NH according to claim 22-rGO/CNT/α-MnO2The preparation method of the NWs composite film electrode material is characterized in that the temperature of the hydrothermal reaction in the step (4) is 180 ℃, and the reaction time is 20 hours.
8. NH according to claim 22-rGO/CNT/α-MnO2The preparation method of the NWs composite film electrode material is characterized in that the MnSO in the step (4)4H2O aqueous solution, NH4The concrete preparation steps of the F aqueous solution and the KMnO4 aqueous solution are as follows:
s1: mixing MnSO4·H2Dissolving O in deionized water to obtain 0.025mol/L MnSO4·H2An aqueous solution of O;
s2: reacting NH4F is dissolved in deionized water to prepare 1.2mol/L NH4F, water solution;
s3: mixing KMnO4Dissolving in deionized water to obtain 0.05mol/L KMnO4An aqueous solution.
9. NH according to claim 22-rGO/CNT/α-MnO2The preparation method of the NWs composite membrane electrode material is characterized in that in the step (7), an obtained sample is dried on a filter membrane at room temperature; preferably, the filter membrane is an organic filter membrane with a pore size of 0.22 μm.
10. NH (hydrogen sulfide)2-rGO/CNT/α-MnO2The NWs composite film electrode is characterized in that an electrode material of the composite film electrode comprises the following components: NH (NH)2-rGO、CNT、α-MnO2 NWs，NH2-rGO、CNT、α-MnO2The NWs is used for preparing the electrode material according to the proportion of 10-20 ml to 50 ml; the electrode material adopts NH as defined in any one of claims 2 to 92-rGO/CNT/α-MnO2The NWs composite film electrode material is prepared by a preparation method.
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