CN111146008A - Manganese molybdenum sulfide/graphene composite electrode material used as supercapacitor and preparation method thereof - Google Patents
Manganese molybdenum sulfide/graphene composite electrode material used as supercapacitor and preparation method thereof Download PDFInfo
- Publication number
- CN111146008A CN111146008A CN201911219117.8A CN201911219117A CN111146008A CN 111146008 A CN111146008 A CN 111146008A CN 201911219117 A CN201911219117 A CN 201911219117A CN 111146008 A CN111146008 A CN 111146008A
- Authority
- CN
- China
- Prior art keywords
- rgo
- electrode material
- molybdenum sulfide
- deionized water
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 39
- DJSLFLGZKHRAPB-UHFFFAOYSA-N [S].[Mo].[Mn] Chemical compound [S].[Mo].[Mn] DJSLFLGZKHRAPB-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000007772 electrode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 229910016895 MnMoO4 Inorganic materials 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000004073 vulcanization Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910015667 MoO4 Inorganic materials 0.000 claims description 2
- 238000005234 chemical deposition Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 26
- 238000004146 energy storage Methods 0.000 abstract description 7
- 239000011232 storage material Substances 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- -1 transition metal sulfide Chemical class 0.000 abstract description 2
- 238000009388 chemical precipitation Methods 0.000 abstract 1
- 239000006260 foam Substances 0.000 abstract 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 235000015393 sodium molybdate Nutrition 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000009862 microstructural analysis Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
A manganese molybdenum sulfide/graphene composite electrode material used as a super capacitor and a preparation method thereof belong to the technical field of energy storage materials and can solve the problem that the existing transition metal sulfide used as an electrode material is applied to the super capacitorDissolving sodium molybdate and manganese nitrate in deionized water, fully stirring uniformly, pouring into a reaction kettle, immersing foam nickel which is cleaned and coated with reduced graphene oxide by a chemical precipitation method into the reaction kettle, and reacting at 120 ℃ for 6 hours to obtain MnMoO4@ rGO/NF. And then carrying out hydrothermal vulcanization on the composite material to obtain the manganese molybdenum sulfide/graphene composite material. The super capacitor electrode material has the advantages of abundant and easily-obtained raw material reserves, low price, excellent super capacitor performance, large specific capacitance, large working voltage window, and high energy density and rate capability.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to a manganese molybdenum sulfide/graphene composite electrode material used as a super capacitor and a preparation method thereof.
Background
With the deterioration of human living environment and the decrease of available resources and energy, people have paid more and more attention and research to the improvement of novel energy storage devices and the performance thereof, and how to develop energy storage devices with high power density and high energy density has become a research hotspot of scholars at home and abroad. In the field of electrochemical energy storage, lithium ion batteries, fuel cells and supercapacitors are considered as three new energy storage systems with great development potential. As a new type of rechargeable battery, lithium ion batteries have been widely used for development, but their slow charging/discharging speed limits their application in high power applications. The Super Capacitor (SCs), also called electrochemical capacitor, is a novel energy storage device, has the advantages of both traditional capacitors and secondary batteries, is a high-efficiency and practical energy storage device, can provide higher specific capacitance than common capacitors, higher power density than batteries and longer cycle life, well fills the gap between the two, is considered as an ideal device of electronics and electric automobiles, and has wide application prospect in various fields of human society. Based on the electronic storage mechanism, SCs can be classified into Electrochemical Double Layer Capacitors (EDLCs) and pseudocapacitors. EDLCs store charge by a physical adsorption-desorption process, while pseudocapacitors store charge based on faradaic redox reactions. However, the relatively low energy density still becomes the biggest obstacle for supercapacitor applications.
It is clear from the development history of supercapacitors for decades that the renewal of electrode materials has a significant effect on the performance of supercapacitors. Early supercapacitors achieved much greater capacitance than conventional capacitors due to the use of high surface area carbon materials. However, in the middle of several decades, the development of supercapacitors has been in a standstill due to the continuous use of carbon materials as electrode materials. With the rapid development of nanotechnology at the end of the last century, the importance of pore size in carbon materials with high surface area has been increasingly recognized, and it is very important to study electrode materials with excellent electrochemical properties in order to further promote the performance improvement and commercial application of supercapacitors. The electrode materials of supercapacitors can be roughly divided into three main categories: carbon materials, transition metal oxide materials, and conductive polymer materials. Among them, transition metal oxides are receiving attention in the field of supercapacitor electrode materials due to their good capacitance properties. In 1971, Trastti et al discovered the use of a noble metal oxide RuO2The prepared electrode, which shows typical capacitance characteristics, is widely studied because it has high conductivity and possesses three different oxidation states. However, the cost is high and the electrode material has a certain toxicity, so people are forced to actively research the electrode material which is cheap, high in performance and environment-friendly. Wherein transition metal sulfide (MnS, MoS)2) Equal material relative RuO2Is cheaper and more environmentally friendly and is widely researched. The material can generate reversible oxidation-reduction reaction in the charge-discharge process of the capacitor, and the prepared super capacitor has high energy density and large specific capacitance.
Disclosure of Invention
The invention aims to provide a manganese molybdenum sulfide/graphene composite electrode material of a super capacitor, which has high specific capacitance, good rate performance and excellent energy density, and a preparation method thereof.
The invention adopts the following technical scheme:
a manganese molybdenum sulfide/graphene composite electrode material of a super capacitor has the following structural general formula: MnMoS-x/rGO/NF, wherein x is different vulcanization reaction time, and x is more than or equal to 1 and less than or equal to 7.
A preparation method of a manganese molybdenum sulfide/graphene composite electrode material of a supercapacitor comprises the following steps:
firstly, growing reduced graphene oxide on a foamed nickel substrate by adopting a chemical deposition method: adding graphene oxide into deionized water, performing ultrasonic dispersion to obtain brown dispersion liquid, then adding a reducing agent into the dispersion liquid, uniformly stirring to obtain a mixed solution A, immersing a foamed nickel substrate cleaned by acetone, hydrochloric acid and absolute ethyl alcohol into the mixed solution A, performing hydrothermal bath reduction for 6 hours at 90 ℃, taking out the foamed nickel substrate, washing residues, placing the foamed nickel substrate in a drying oven, and drying for 12 hours at 60 ℃ to obtain the foamed nickel substrate with reduced graphene oxide, wherein the foamed nickel substrate is marked as rGO/NF;
secondly, growing manganese molybdate on the foamed nickel substrate on which the reduced graphene oxide grows by using a hydrothermal method: mixing Na2MoO4·2H2Dissolving O in deionized water to obtain solution B, and adding Mn (NO)3)2·6H2Dissolving O in deionized water to obtain a solution C, slowly pouring the solution B into the solution C, fully stirring to obtain a mixed solution D, transferring the mixed solution D into a reaction kettle, putting rGO/NF into the reaction kettle, keeping the mixed solution D at 120 ℃ for 6 hours, taking out and cleaning to obtain the composite material MnMoO4@rGO/NF;
Thirdly, preparing the manganese molybdenum sulfide/graphene composite electrode material by a hydrothermal method: mixing Na2S·9H2Dissolving O in deionized water, stirring for dissolving, transferring to a reaction kettle, and adding MnMoO4And @ rGO/NF is put into a reaction kettle, kept for 1-7h at 120 ℃, taken out, cleaned and dried to obtain the manganese molybdenum sulfide/graphene composite material with the chemical general formula of MnMoS-x/rGO/NF.
In the first step, the ratio of the graphene oxide to the deionized water is 1 mg: 3mL, wherein the reducing agent is ascorbic acid, and the mass ratio of the reducing agent to the graphene oxide is 3: 1.
In the second step, Na is2MoO4·2H2The ratio of O to deionized water was 1 mmol: 10mL of Mn (NO)3)2·6H2The ratio of O to deionized water was 1 mmol: 10 mL.
In the third step, Na is described2S·9H2The ratio of O to deionized water was 1 mmol: 80 mL.
Wherein, MnMoO4The mass of the @ rGO/NF composite material is 1.5 mg cm-2. The mass of the MnMoS-x/rGO/NF composite material is 2.0 mg cm-2。
Designing a three-electrode system based on the MnMoS-x/rGO/NF composite material: the working electrode is a MnMoS-x/rGO/NF composite material electrode, the counter electrode is a platinum sheet electrode, the reference electrode is a calomel electrode,
an electrochemical workstation model CHI660E was used as the test instrument.
The MnMoS-x/rGO/NF composite material electrode is applied to the fields of super capacitors or lithium ion batteries and other batteries and electric elements with high current requirements.
The invention has the following beneficial effects:
the MnMoS-x/rGO/NF composite material electrode is applied to the fields of super capacitors or lithium ion batteries and other batteries and electrical components requiring high current.
The defects of low conductivity, large volume change rate and poor circulation stability when the metal sulfide is used as the electrode material of the supercapacitor can be overcome by adding the graphene;
in addition, the foamed nickel with high porosity, large specific surface area and good conductivity is used as a current collector, and the obtained electrode material with a three-dimensional network structure supported by the foamed nickel can show more excellent electrochemical performance.
The vulcanization time in the invention has obvious influence on the micro-morphology of the composite material and the specific capacitance of the super capacitor. When the sulfurization reaction is carried out for 3 hours, the prepared manganese molybdenum sulfide has uniform nano spherical morphology, and the specific capacitance of the manganese molybdenum sulfide serving as a positive electrode material of a super capacitor is up to 3274.1F g-1In addition, the manganese molybdenum sulfide/reduced graphene oxide is used as a device anode material, and the activated carbon is used as a cathode materialThe energy density of the assembled super capacitor device reaches 59.8W-h kg-1The excellent performance of the material can be used as an electrode material to be applied to the fields of super capacitors, lithium ion batteries and the like.
Drawings
FIG. 1 shows MnMoO obtained in examples 1 to 5 of the present invention4The XRD curves of the manganese molybdenum sulfide/graphene composite material of @ rGO/NF and MnMoS-x/rGO/NF with different vulcanization times are shown.
Wherein: a, MnMoO4@rGO/NF;b,MnMoS-1/rGO/NF;c,MnMoS-3/rGO/NF;d,MnMoS-5/rGO/NF;e,MnMoS-7/rGO/NF。
FIG. 2 shows MnMoO obtained in examples 1 to 5 of the present invention4Scanning electron microscope photos of the @ rGO/NF and MnMoS-x/rGO/NF composite materials with different vulcanization times: a-b, MnMoO4/rGO/NF;c-d,MnMoS-1/rGO/NF;e-f,MnMoS-3/rGO/NF;g-h,MnMoS-5/rGO/NF;i-j,MnMoS-7/rGO/NF。
FIG. 3 shows MnMoO obtained in examples 1 to 5 of the present invention4@ rGO/NF and cyclic voltammetry curves of MnMoS-x/rGO/NF composite materials with different vulcanization times.
FIG. 4 shows MnMoO obtained in examples 1 to 5 of the present invention4Constant current charge-discharge relation curve of @ rGO/NF and MnMoS-x/rGO/NF composite material with different vulcanization time.
FIG. 5 shows MnMoO obtained in examples 1 to 5 of the present invention4Specific capacitance-charge-discharge current density relation curves of/rGO/NF and MnMoS-x/rGO/NF composite materials with different vulcanization times.
Detailed Description
Detecting, analyzing and characterizing the microstructure and the electrochemical performance of the prepared composite material:
microstructural analysis was performed with a scanning electron microscope, model MIRA 3;
electrochemical performance testing was performed with CHI660E electrochemical workstation.
Example 1
Ultrasonically decomposing 10 mg of graphene oxide in 30 mL of distilled water, adding 30 mg of ascorbic acid after a uniform brown solution is formed, ultrasonically stirring uniformly, placing foamed nickel cleaned by acetone, hydrochloric acid and absolute ethyl alcohol in a dispersion liquid, depositing for 6 hours at 90 ℃ in a water bath kettle, washing the surface of a sample by deionized water, and drying for 12 hours at 60 ℃ to obtain rGO/NF.
4 mmol of Na2MoO4·2H2Dissolving O in 40 ml deionized water to obtain solution B, and adding 4 mmol Mn (NO)3)2·6H2O was dissolved in 40 ml of deionized water to obtain solution C. Slowly pouring the solution B into the solution C, fully stirring to obtain a mixed solution D, transferring the mixed solution D into a reaction kettle, putting rGO/NF into the reaction kettle, keeping the rGO/NF at 120 ℃ for 6 hours, taking out and cleaning to obtain the composite material MnMoO4@rGO/NF;
The prepared MnMoO is added4The @ rGO/NF composite material is used as the anode material of the super capacitor to carry out electrochemical performance test in a three-electrode system (electrolyte is 2 mol/L KOH), and the specific capacitance of the material is 2004.8F g-1。
Example 2
Adding 1mmol of Na2S·9H2Dissolving O in 80mL deionized water, stirring for dissolving, transferring to a reaction kettle, and adding MnMoO4And @ rGO/NF is put into a reaction kettle and is kept for 1h at the temperature of 120 ℃, and the reaction kettle is taken out, cleaned and dried to obtain the manganese molybdenum sulfide/graphene composite material with the chemical general formula of MnMoS-1/rGO/NF.
The prepared composite is named as MnMoS-1/rGO/NF, and is used as a positive electrode material of a super capacitor to carry out electrochemical performance test in a three-electrode system (electrolyte is 2 mol/L KOH), and the specific capacitance of the composite is 2145.2F g-1。
Example 3
Adding 1mmol of Na2S·9H2Dissolving O in 80mL deionized water, stirring for dissolving, transferring to a reaction kettle, and adding MnMoO4And @ rGO/NF is put into a reaction kettle and is kept for 3 hours at the temperature of 120 ℃, and after being taken out, cleaned and dried, the manganese molybdenum sulfide/graphene composite material with the chemical general formula of MnMoS-3/rGO/NF is obtained.
The prepared compound is named as MnMoS-3/rGO/NF and is used as a positive electrode material of a super capacitor in a three-electrode system (the electrolyte is 2 mo)L/L KOH) and has a specific capacitance of 3274.1F g-1。
Example 4
Adding 1mmol of Na2S·9H2Dissolving O in 80mL deionized water, stirring for dissolving, transferring to a reaction kettle, and adding MnMoO4And @ rGO/NF is put into a reaction kettle, kept for 5 hours at 120 ℃, taken out, cleaned and dried to obtain the manganese molybdenum sulfide/graphene composite material with the chemical general formula of MnMoS-5/rGO/NF.
The prepared composite is named as MnMoS-5/rGO/NF, and is used as a positive electrode material of a super capacitor to carry out electrochemical performance test in a three-electrode system (electrolyte is 2 mol/L KOH), and the specific capacitance of the composite is 3042.1F g-1。
Example 5
Adding 1mmol of Na2S·9H2Dissolving O in 80mL deionized water, stirring for dissolving, transferring to a reaction kettle, and adding MnMoO4And @ rGO/NF is put into a reaction kettle, is kept for 7 hours at the temperature of 120 ℃, is taken out, cleaned and dried to obtain the manganese molybdenum sulfide/graphene composite material with the chemical general formula of MnMoS-7/rGO/NF.
The prepared composite is named as MnMoS-7/rGO/NF, and is used as a positive electrode material of a super capacitor to carry out electrochemical performance test in a three-electrode system (electrolyte is 2 mol/L KOH), and the specific capacitance of the composite is 2613.6F g-1。
Example 6
Mixing acetylene black, activated carbon and polyvinylidene fluoride according to the mass ratio of 8:1:1, uniformly grinding, coating on foamed nickel, drying at 60 ℃ for 12 hours, then using the mixture as a negative electrode material, assembling an asymmetric supercapacitor device by using a manganese molybdenum sulfide/graphene composite material as a positive electrode material, and carrying out electrochemical performance test on the asymmetric supercapacitor device; the power density of the prepared asymmetric device of the super capacitor is 402.4W kg-1It shows up to 59.8W h kg-1The energy density of (1).
Claims (5)
1. The manganese molybdenum sulfide/graphene composite electrode material of the supercapacitor is characterized in that: has the following structural general formula: MnMoS-x/rGO/NF, wherein x is different vulcanization reaction time, and x is more than or equal to 1 and less than or equal to 7.
2. The preparation method of the manganese molybdenum sulfide/graphene composite electrode material of the supercapacitor according to claim 1, characterized by comprising the following steps: the method comprises the following steps:
firstly, growing reduced graphene oxide on a foamed nickel substrate by adopting a chemical deposition method: adding graphene oxide into deionized water, performing ultrasonic dispersion to obtain brown dispersion liquid, then adding a reducing agent into the dispersion liquid, uniformly stirring to obtain a mixed solution A, immersing a foamed nickel substrate cleaned by acetone, hydrochloric acid and absolute ethyl alcohol into the mixed solution A, performing hydrothermal bath reduction for 6 hours at 90 ℃, taking out the foamed nickel substrate, washing residues, placing the foamed nickel substrate in a drying oven, and drying for 12 hours at 60 ℃ to obtain the foamed nickel substrate with reduced graphene oxide, wherein the foamed nickel substrate is marked as rGO/NF;
secondly, growing manganese molybdate on the foamed nickel substrate on which the reduced graphene oxide grows by using a hydrothermal method: mixing Na2MoO4·2H2Dissolving O in deionized water to obtain solution B, and adding Mn (NO)3)2·6H2Dissolving O in deionized water to obtain a solution C, slowly pouring the solution B into the solution C, fully stirring to obtain a mixed solution D, transferring the mixed solution D into a reaction kettle, putting rGO/NF into the reaction kettle, keeping the mixed solution D at 120 ℃ for 6 hours, taking out and cleaning to obtain the composite material MnMoO4@rGO/NF;
Thirdly, preparing the manganese molybdenum sulfide/graphene composite electrode material by a hydrothermal method: mixing Na2S·9H2Dissolving O in deionized water, stirring for dissolving, transferring to a reaction kettle, and adding MnMoO4And @ rGO/NF is put into a reaction kettle, kept for 1-7h at 120 ℃, taken out, cleaned and dried to obtain the manganese molybdenum sulfide/graphene composite material with the chemical general formula of MnMoS-x/rGO/NF.
3. The preparation method of the manganese molybdenum sulfide/graphene composite electrode material of the supercapacitor according to claim 2, wherein the preparation method comprises the following steps: in the first step, the ratio of the graphene oxide to the deionized water is 1 mg: 3mL, wherein the reducing agent is ascorbic acid, and the mass ratio of the reducing agent to the graphene oxide is 3: 1.
4. The preparation method of the manganese molybdenum sulfide/graphene composite electrode material of the supercapacitor according to claim 2, wherein the preparation method comprises the following steps: in the second step, Na is2MoO4·2H2The ratio of O to deionized water was 1 mmol: 10mL of Mn (NO)3)2·6H2The ratio of O to deionized water was 1 mmol: 10 mL.
5. The preparation method of the manganese molybdenum sulfide/graphene composite electrode material of the supercapacitor according to claim 2, wherein the preparation method comprises the following steps: in the third step, Na is described2S·9H2The ratio of O to deionized water was 1 mmol: 80 mL.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911219117.8A CN111146008A (en) | 2019-12-03 | 2019-12-03 | Manganese molybdenum sulfide/graphene composite electrode material used as supercapacitor and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911219117.8A CN111146008A (en) | 2019-12-03 | 2019-12-03 | Manganese molybdenum sulfide/graphene composite electrode material used as supercapacitor and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111146008A true CN111146008A (en) | 2020-05-12 |
Family
ID=70517502
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911219117.8A Pending CN111146008A (en) | 2019-12-03 | 2019-12-03 | Manganese molybdenum sulfide/graphene composite electrode material used as supercapacitor and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111146008A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112875756A (en) * | 2021-02-19 | 2021-06-01 | 苏州科技大学 | Manganese molybdate nanoflower/graphene three-dimensional structure and high-specific-volume supercapacitor performance improvement method |
CN114388823A (en) * | 2022-01-14 | 2022-04-22 | 福州大学 | Three-dimensional NiFe-LDH/rGO @ NF catalytic material for fuel cell and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109637834A (en) * | 2018-11-01 | 2019-04-16 | 太原理工大学 | A kind of cobalt molybdenum sulphide/graphene composite material of the morphology controllable for supercapacitor and preparation method thereof |
-
2019
- 2019-12-03 CN CN201911219117.8A patent/CN111146008A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109637834A (en) * | 2018-11-01 | 2019-04-16 | 太原理工大学 | A kind of cobalt molybdenum sulphide/graphene composite material of the morphology controllable for supercapacitor and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
ZHI SHUO YAN等: "One-step synthesis of MnS/MoS2/C through the calcination and sulfurization of a bi-metal–organic framework for a high-performance supercapacitor and its photocurrent investigation", 《DALTON TRANS.》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112875756A (en) * | 2021-02-19 | 2021-06-01 | 苏州科技大学 | Manganese molybdate nanoflower/graphene three-dimensional structure and high-specific-volume supercapacitor performance improvement method |
CN112875756B (en) * | 2021-02-19 | 2022-09-06 | 苏州科技大学 | Manganese molybdate nanoflower/graphene three-dimensional structure and high-specific-volume supercapacitor performance improvement method |
CN114388823A (en) * | 2022-01-14 | 2022-04-22 | 福州大学 | Three-dimensional NiFe-LDH/rGO @ NF catalytic material for fuel cell and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106229498B (en) | Cathode material suitable for water-based metal ion battery and preparation method thereof | |
CN107275105B (en) | Electrode material for super capacitor and preparation method thereof | |
CN108364793A (en) | CoNiFe-LDH/ multi-layer graphene high-performance composite energy-storage materials and preparation method thereof | |
CN107275109B (en) | The preparation method of manganese dioxide composite material electrode for ultracapacitor | |
CN104176783B (en) | The preparations and applicatio method of the coated manganese dioxide nanowire of a kind of nitrogen carbon material | |
CN109637834A (en) | A kind of cobalt molybdenum sulphide/graphene composite material of the morphology controllable for supercapacitor and preparation method thereof | |
CN108133831B (en) | Ni3S2Preparation method of @ rGO @ LDHs | |
CN109192523B (en) | A kind of Ni (OH)2Preparation method of multilayer graphene composite material | |
CN112830523B (en) | Molybdenum-doped cobaltosic oxide for super capacitor and preparation method thereof | |
CN111048325A (en) | Morphology-controllable nickel manganese sulfide/graphene composite material used as supercapacitor and preparation method thereof | |
CN103361698A (en) | Method for preparing supercapacitor electrode material by means of coelectrodeposition | |
CN109390162A (en) | A kind of manganese cobalt sulfide/redox graphene composite material and preparation method with excellent electrochemical performance | |
CN104577064A (en) | Method for preparing carbon coated nano flaky tin oxide material | |
CN111146016A (en) | Flaky nickel sulfide/nickel-vanadium double hydroxide/graphene composite material for super capacitor and preparation method thereof | |
CN111146008A (en) | Manganese molybdenum sulfide/graphene composite electrode material used as supercapacitor and preparation method thereof | |
CN109817475B (en) | Preparation method and application of bismuth-nickel sulfide positive electrode material | |
CN111268745A (en) | NiMoO4@Co3O4Core-shell nano composite material, preparation method and application | |
CN106024414A (en) | Manganese dioxide/polypyrrole composite electrode free of binder, preparation method and application of manganese dioxide/polypyrrole composite electrode | |
CN101399120A (en) | Novel hybrid supercapacitor | |
CN111039332B (en) | Preparation method and application of multifunctional double-layer nanowire layered composite material | |
CN108265283A (en) | The In-situ sulphiding preparation Ni of Ni substrate in eutectic type ionic liquid3S2Method | |
CN112467077A (en) | Universal electrochemical modification preparation method for effectively enhancing electricity storage performance of multiple transition metal oxides | |
CN111986929A (en) | Preparation method of cobalt manganate/nickel sulfide core-shell array structure electrode material | |
CN115376838B (en) | Wide-voltage window aqueous electrolyte for forming SEI film based on physical process, and preparation method and application thereof | |
CN110610817A (en) | Based on Mn3O4Supercapacitor made of graphene composite material and preparation method of supercapacitor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200512 |
|
RJ01 | Rejection of invention patent application after publication |