CN104091948B - Electrochemistry storage magnesium combination electrode of a kind of high power capacity and stable circulation and preparation method thereof - Google Patents
Electrochemistry storage magnesium combination electrode of a kind of high power capacity and stable circulation and preparation method thereof Download PDFInfo
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- 239000011777 magnesium Substances 0.000 title claims abstract description 47
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 46
- 230000005518 electrochemistry Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000004087 circulation Effects 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 69
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 43
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 239000002086 nanomaterial Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 8
- 239000006230 acetylene black Substances 0.000 claims abstract description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 8
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011149 active material Substances 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 238000001125 extrusion Methods 0.000 claims abstract description 4
- 239000006260 foam Substances 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 239000011684 sodium molybdate Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical class [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 235000015393 sodium molybdate Nutrition 0.000 claims description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 8
- XMMDVXFQGOEOKH-UHFFFAOYSA-N n'-dodecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCNCCCN XMMDVXFQGOEOKH-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000003595 mist Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims 1
- 229920000131 polyvinylidene Polymers 0.000 claims 1
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000407826 Amblystegium serpens Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ZTHNOZQGTXKVNZ-UHFFFAOYSA-L dichloroaluminum Chemical compound Cl[Al]Cl ZTHNOZQGTXKVNZ-UHFFFAOYSA-L 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
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- 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
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- Y02E60/10—Energy storage using batteries
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- Condensed Matter Physics & Semiconductors (AREA)
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- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of capacity electrochemistry high and stable circulation and store magnesium combination electrode and preparation method, its electrochemistry storage magnesium active material is MoS2-The composite nano materials of nanometer watt/Graphene, MoS in composite nano materials2The ratio of the amount of substance of nanometer watt and Graphene is 1:1-1:3, MoS2The nanometer watt layer structure for few number of plies, the average number of plies is 4-5 layer, the component of combination electrode and mass percentage content thereof are: MoS2Nanometer watt/Graphene composite nano materials is 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%. Preparation process: first prepare MoS2Nanometer watt/Graphene composite nano materials, by composite nano materials and acetylene black and Kynoar furnishing pastel, is coated onto this pastel on the foam copper of collector equably, and after vacuum drying, roll extrusion obtains. Electrochemistry storage magnesium combination electrode of the present invention has high reversible storage magnesium capacity, has extensive use.
Description
Technical field
The present invention relates to electrochemistry storage magnesium electrode and preparation method thereof, relate in particular to MoS2Nanometer watt/Graphene electrochemistryThe preparation method of storage magnesium combination electrode, belongs to technical field of new energy application.
Background technology
Along with the development of modern mobile communication, new-energy automobile and intelligent grid, novel electrochmical power source is in modern societyIn played more and more important effect. Traditional secondary cell, if lead-acid accumulator is because it is containing harmful metallic element Pb,Its application is restricted. Lithium ion battery has the excellent properties such as high specific energy, memory-less effect, environmental friendliness, is movingIn the Portable movable such as mobile phone and notebook computer electrical equipment, be widely used. As electrokinetic cell, lithium ion batteryAlso be with a wide range of applications at aspects such as electric bicycle, electric automobile and intelligent grids. But due to lithium ion batteryNever solution carefully and lithium resource limited of security, lithium ion battery is wide as electrokinetic cell and storage batteryGeneral application still also exists a lot of work to do. Along with the development of new-energy automobile and the large-scale application of storage battery urgently needFind the secondary cell that a kind of energy substitutes a kind of cheapness, environmental friendliness and the height ratio capacity of existing secondary cell system. Due toDivalence magnesium ion has less radius, can electrochemical intercalation and deintercalation in the compound of some layer of structure, as inorganic transitionMetal oxide, sulfide etc. Magnesium also has aboundresources in addition, cheap, specific energy is high, nontoxic and process convenient etc. excellentPoint. Therefore, rechargeable magnesium ion battery also becomes the research system of a new secondary cell in recent years. But up to the presentElectrode material as high performance electrochemistry storage magnesium is still little.
MoS2Having and layer structure like graphite-like, is the S-Mo-S of very strong covalent bonds in its layer, layer and layerBetween be weak Van der Waals force. MoS2Weak interlaminar action power and larger interlamellar spacing allow to react at it by insertionInterlayer is introduced external atom or molecule. Such characteristic makes MoS2Material can be used as the material of main part that inserts reaction. Therefore,MoS2It is a kind of electrode material of rising electrochemistry storage magnesium. Li etc. have prepared nanoscale by hydro-thermal reaction approachMoS2，Studied its electrochemistry storage magnesium performance, but its electrochemistry storage magnesium capacity is lower, only has 50-60mAh/g (X.L.Li,Y.D.Li,J.Phys.Chem.B,2004，108：13893)。
Two-dimensional nano material has the characteristic of numerous excellences with its unique pattern, its research has caused that people's is greatly emergingInterest. Graphene is most typical two-dimensional nano material, and its unique two-dimensional nano chip architecture makes physics, the chemistry of its numerous uniquenessesWith performances such as mechanics, there is important scientific research meaning and technology application prospect widely. Graphene has high ratio tableArea, high conduction and heat conductivility, high charge mobility, excellent mechanical property, these excellent characteristics make graphiteAlkene is before nano electron device, the novel field such as catalyst material and electrochemistry energy storage and energy conversion have a wide range of applicationsScape.
The immense success that the discovery of Graphene and research thereof obtain has excited people to grind other inorganic two-dimensional nano materialsThe very big interest of studying carefully, as the transition metal dichalcogenide of individual layer or few number of plies etc. Recently, Graphene concept expands from material with carbon elementExhibition is to the inorganic compound of other layer structures, namely for the inorganic material of layer structure, and in the time that its number of plies reduces (8 layersBelow), while especially reducing to individual layer, its electronic property or band structure can produce obvious variation, thereby cause its demonstrationThe physics and chemistry characteristic different from corresponding body phase material. Except Graphene, as body phase MoS2Reduce to few number of plies (especiallyWhile being individual layer), show and the visibly different physics of body phase material, chemical characteristic. Research shows the MoS of individual layer or few number of plies2Nanometer sheet has better electrochemistry storage magnesium performance. But as the electrode material of electrochemistry storage magnesium, MoS2Between layersLow electric conductivity has affected the performance of its application.
Due to MoS2Nanometer sheet and Graphene have similar two-dimensional nano sheet pattern, and both are at microscopic appearance and crystal knotOn structure, there is good similitude. If by MoS2The composite of nanometer sheet and the compound preparation of Graphene, Graphene is receivedThe high conduction performance of rice sheet can further improve the electric conductivity of composite, strengthens in electrochemistry storage magnesium electrode course of reactionElectronics transmission, can further improve the electrochemistry storage magnesium performance of composite. With common MoS2Nanometer sheet comparison, little receivesThe MoS of rice watt shape pattern2Not only there is more edge, more short magnesium ion diffusion admittance can be provided, and loadOn Graphene, there is more contact area with electrolyte. Therefore MoS2The composite nano materials of nanometer watt/Graphene canShow the electrochemistry storage magnesium performance significantly strengthening.
But, up to the present, use MoS2Nanometer watt/Graphene composite nano materials is as the electricity of electroactive substanceChemistry storage magnesium combination electrode and preparation thereof have not been reported. First the present invention is raw material with graphene oxide and sodium molybdate, passes throughThe hydrothermal method that Gemini surface active agent is assisted and heat treatment subsequently, prepared MoS2The composite Nano of nanometer watt/GrapheneMaterial, then uses MoS2The composite nano materials of nanometer watt/Graphene, as the active material of electrochemistry storage magnesium, has been prepared electrificationLearn the combination electrode of storage magnesium. The present invention prepares MoS2Nanometer watt/Graphene composite nano materials electrochemistry storage magnesium combination electrodeMethod has simply, facilitates and be easy to expand industrial applications a little.
Summary of the invention
The object of the present invention is to provide a kind of capacity electrochemistry high and stable circulation to store magnesium combination electrode and preparation thereofMethod, the electrochemistry storage magnesium active material of this combination electrode is MoS2-The composite nano materials of nanometer watt/Graphene, composite NanoMoS in material2The ratio of the amount of substance of nanometer watt and Graphene is 1:1 ~ 1:3, described MoS2The nanometer watt knot of the stratiform for few number of pliesStructure, the component of combination electrode and mass percentage content thereof are: MoS2Nanometer watt/Graphene composite nano materials 80%, acetylene black10%, carboxymethyl cellulose 5%, Kynoar 5%.
In technique scheme, the layer structure of few number of plies refers to the layer structure of the number of plies below 6 layers or 6 layers.
As preferably, described MoS2The average number of plies of nanometer watt is 4-5 layer.
The preparation method that above-mentioned capacity electrochemistry high and stable circulation is store magnesium combination electrode carries out according to the following steps:
(1) be dispersed in deionized water ultrasonic graphene oxide, add Gemini surface active agent N-dodecyl Asia thirdThe two ammonium bromides (seeing accompanying drawing 1) of base diamines, and fully stir, then add successively Cys and sodium molybdate, and constantly stirCys and sodium molybdate are dissolved completely, and the ratio of the amount of substance of Cys and sodium molybdate consumption is 5:1, sodium molybdateWith the ratio of the amount of substance of graphene oxide be 1:1-1:3;
(2) mixed dispersion step (1) being obtained is transferred in hydrothermal reaction kettle, and adds deionized water to adjust bodyAmass to 80% of hydrothermal reaction kettle nominal volume the concentration of the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamineFor 0.01-0.02mol/L, the content of graphene oxide is 30-65mmol/L, this reactor is put in constant temperature oven,At 230-250 DEG C, after hydro-thermal reaction 24h, allow it naturally cool to room temperature, with centrifugation collection hydro-thermal solid product, and useDeionized water is fully washed, vacuum drying at 100 DEG C, by the hydro-thermal solid product obtaining in nitrogen/hydrogen mixed gas atmosphereHeat treatment 2h at 800 DEG C, in mist, hydrogen volume mark is 10%, finally prepares MoS2Nanometer watt/GrapheneComposite nano materials;
(3) by the MoS of above-mentioned preparation2Nanometer watt/Graphene composite nano materials is as the electrochemistry storage magnesium activity of electrodeMaterial, is stirring with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%The lower uniform pastel of furnishing that fully mixes, each constituent mass percentage is: MoS2Nanometer watt/Graphene composite nano materials80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%, is coated onto described pastel equably as collectorFoam copper on, vacuum drying at 110 DEG C, roll extrusion obtains MoS2Nanometer watt/Graphene electrochemistry storage magnesium combination electrode.
Above-mentioned graphene oxide adopts improved Hummers method preparation.
Hydrothermal method system of assisting with the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamine of the present inventionStandby MoS2The method of nanometer watt/Graphene composite nano materials has the following advantages: graphene oxide surface and edge are with veryMany oxygen-containing functional groups (as hydroxyl, carbonyl, carboxyl), these oxygen-containing functional groups make graphene oxide more easily be dispersed in water or haveIn machine liquid, but these oxygen-containing functional groups make graphene oxide surface with negative electrical charge, make graphene oxide with negativeThe MoO of electric charge4 2-Ion is incompatible, and the present invention passes through electrostatic interaction first by Gemini surface active agent N-dodecyl propylidene twoThe two ammonium bromides of amine are adsorbed onto graphene oxide surface, make it with part positive charge, due to electrostatic interaction, and MoO4 2-Ion just veryEasily interact and combine with the graphene oxide that has adsorbed Gemini surface active agent. The more important thing is, with commonSingle cationic surfactant is compared, and in the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamine, is just having 2 bandsThe quaternary ammonium hydrophilic radical of electric charge, has enough hydrophilies, and between electronegative graphene oxide, has stronger mutually quietElectro ultrafiltration; The two ammonium bromides of N-dodecyl trimethylene diamine also have 2 hydrophobic long alkyl chain groups (seeing accompanying drawing 1), hydrophobicityStronger. The two ammonium bromides of N-dodecyl trimethylene diamine are adsorbed on Graphene surface, and its hydrophobic grouping is irregular with bendingThere is (seeing accompanying drawing 2) in " brush head " form, this version has caused water-heat process and heat treatment back loading at Graphene tableThe MoS of face2There is the pattern of nanometer watt, this undersized MoS2Nanometer watt has more edge, as electrochemistry storage magnesium materialMaterial, can provide more short magnesium ion diffusion admittance, contributes to strengthen its electrochemistry storage magnesium performance; In addition, MoS2NanometerWatt/graphene composite material can increase the contact area of itself and electrolyte, can further contribute to improve its electrochemistryEnergy. Therefore the present invention MoS2The electrochemistry storage magnesium richness that nanometer watt/graphene composite material is prepared as electroactive substanceCombination electrode has high electrochemistry storage magnesium capacity, excellent cycle performance and significantly enhancing large current density electrical characteristics.
Brief description of the drawings
The two ammonium bromide structural representations of Fig. 1 Gemini surface active agent N-dodecyl trimethylene diamine.
Fig. 2 Gemini surface active agent is adsorbed on the schematic diagram on graphene oxide surface.
The MoS that Fig. 3 embodiment 1 prepares2The XRD figure of nanometer watt/Graphene composite nano materials.
The MoS that Fig. 4 embodiment 1 prepares2SEM shape appearance figure and the transmission electricity of nanometer watt/Graphene composite nano materialsMirror photo.
MoS prepared by the comparative example of Fig. 5 embodiment 12The TEM of nanometer sheet and Graphene composite nano materials and HRTEM shineSheet.
, detailed description of the invention
Further illustrate the present invention below in conjunction with embodiment.
Graphene oxide in following example adopts improved Hummers method preparation: 0oUnder C ice bath, by 10.0Mmol (0.12g) graphite powder dispersed with stirring, in the 50mL concentrated sulfuric acid, slowly adds KMnO under constantly stirring4, institute adds KMnO4'sQuality is 4 times of graphite powder, stirs 50 minutes, in the time of temperature rise to 35 DEG C, slowly adds 50mL deionized water, then stirs30 minutes, add the H of 15mL mass fraction 30%2O2, stir 30 minutes, through centrifugation, use successively mass fraction 5%HCl solution, deionized water and acetone cyclic washing after obtain graphene oxide.
Embodiment 1.
1) be dispersed in 60mL deionized water ultrasonic 2.5mmol graphene oxide, then add 0.8mmol Shuangzi tableThe two ammonium bromides of surface-active agent N-dodecyl trimethylene diamine, and fully stir, then add successively 0.76g (6.25mmol)Cys and 0.3g (1.25mmol) sodium molybdate (Na2MoO42H2O), and constantly stir and make Cys and molybdic acidSodium dissolves completely, with extremely about 80mL of deionized water adjustment volume;
2) obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100mL, this reactor is put into constant temperature ovenIn, after hydro-thermal reaction 24h, allow it naturally cool to room temperature at 230 DEG C, collect solid product with centrifugation, and use deionizationWater fully washs, vacuum drying at 100 DEG C, by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 DEG CHeat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepares MoS2The composite Nano material of nanometer watt/GrapheneMaterial, MoS in composite nano materials2With the ratio of Graphene amount of substance be 1:2. With XRD, SEM and TEM are to the prepared MoS that obtains2The composite nano materials of nanometer watt/Graphene characterizes, and XRD analysis result (seeing accompanying drawing 3) shows in composite nano materialsMoS2For the layer structure of few number of plies, the average number of plies is 4-5 layer. SEM pattern and TEM photo (seeing accompanying drawing 4) have also shown loadMoS on Graphene2Have little nanometer watt pattern, its number of plies is between 2-6, and most numbers of plies are 4 layers, with XRD analysis oneCause,
3) by the MoS of above-mentioned preparation2Nanometer watt/Graphene composite nano materials is as the electrode activity thing of electrochemistry storage magnesiumMatter, with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5% under agitationFully mix the uniform pastel of furnishing, this pastel is coated onto to (foam copper hole on the foam copper of collector equablyRate is greater than 90%), vacuum drying at 110 DEG C, then roll extrusion obtains MoS2Nanometer watt/Graphene electrochemistry storage magnesium combination electrode, multipleIn composite electrode, each constituent mass percentage is: MoS2Nanometer watt/Graphene composite nano materials 85%, acetylene black 10%, carboxymethylCellulose 5%, Kynoar 5%.
Electrochemistry storage magnesium performance test: taking combination electrode as working electrode, as to electrode, electrolyte is with metal magnesium sheetThe Mg[AlCl2 (C4H9) of 0.25mol/L is (C2H5)] 2 tetrahydrofuran solution is electrolyte, porous polypropylene film(Celguard-2300) be barrier film, in the suitcase that is full of argon gas, be assembled into test battery. Multiple with constant current charge-discharge testThe electrochemistry storage magnesium performance of composite electrode, charge and discharge cycles is carried out on programme controlled auto charge and discharge instrument, charging and discharging currentsDensity 50mA/g, voltage range 0.3 ~ 3.0V. Electrochemical results shows: MoS2Nanometer watt/graphene combination electrodeThe initial reversible capacity of electrochemistry storage magnesium is 285mAh/g, and after 50 circulations, reversible capacity is 272mAh/g, has shown high ratioCapacity and excellent stable circulation performance; In the time of high current charge-discharge (charging and discharging currents is 800mA/g), its capacity is 223MAh/g, has shown its high power charging-discharging characteristic (with comparative example comparison below) significantly strengthening.
Comparative example
Adopt DTAB cationic surfactant, prepared MoS by above-mentioned similar approach2NanometerSheet/Graphene electrochemistry storage magnesium combination electrode, concrete preparation process is as follows:
Be dispersed in 60mL deionized water ultrasonic 2.5mmol graphene oxide, then add 1.6mmol dodecylTrimethylammonium bromide cationic surfactant, and fully stir, then add successively 0.76g (6.25mmol) L-half Guang ammoniaAcid and 0.3g (1.25mmol) sodium molybdate (Na2MoO42H2O), and constantly stir and make Cys and sodium molybdate completely moltenSeparate, adjust volume to about 80mL by deionized water, obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100mL, willThis reactor is put in constant temperature oven, after hydro-thermal reaction 24h, allows it naturally cool to room temperature at 230 DEG C, receives with centrifugationCollection solid product, and fully washing by deionized water, vacuum drying at 100 DEG C, by the hydro-thermal solid product obtaining nitrogen/In hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, in mist, hydrogen volume mark is 10%, prepares MoS2NanometerThe nano composite material of sheet/Graphene, MoS in composite nano materials2With the ratio of the amount of substance of Graphene be 1:2. With XRD,SEM and TEM are to finally preparing MoS2The nano composite material of nanometer sheet/Graphene characterizes, and XRD analysis result showsMoS in composite nano materials2For layer structure, its average number of plies is 7 layers, and TEM and HRTEM photo (seeing accompanying drawing 5) have shown negativeBe loaded in the MoS on Graphene2For nanometer sheet pattern, its thickness and plane sizes are not so good as MoS above2Nanometer watt evenly, MoS2The number of plies of nanometer sheet is at 4-9 layer, and the average number of plies is 7 layers, consistent with XRD analysis.
With prepared MoS2Nanometer sheet/Graphene composite nano materials is electrochemistry storage magnesium active material, by above-mentioned stepRapid 3) process is prepared MoS2Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode, and survey by aforementioned identical electrochemistry storage magnesiumMethod for testing is tested its electrochemistry storage magnesium performance. Result shows: MoS2Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode electrochemistryThe initial reversible capacity of storage magnesium is that 182mAh/g(charging and discharging currents is 50mA/g), after 50 circulations, reversible capacity is 176MAh/g; In the time of high current charge-discharge (charging and discharging currents is 800mA/g), its capacity is 115mAh/g.
Claims (2)
1. capacity electrochemistry high and stable circulation is store a magnesium combination electrode, it is characterized in that the electrochemistry storage of combination electrodeMagnesium active material is MoS2The composite nano materials of nanometer watt/Graphene, MoS in composite nano materials2Nanometer watt and GrapheneThe ratio of amount of substance is 1:1-1:3, described MoS2The nanometer watt layer structure for few number of plies, the component of combination electrode and quality thereofDegree is: MoS2Nanometer watt/Graphene composite nano materials 80%, acetylene black 10%, carboxymethyl cellulose 5%, poly-Vinylidene 5%, described method for preparing composite electrode comprises the following steps:
(1) be dispersed in deionized water ultrasonic graphene oxide, add Gemini surface active agent N-dodecyl propylidene twoTwo ammonium bromides of amine, and fully stirring, then add Cys and sodium molybdate successively, and constantly stir make Cys andSodium molybdate dissolves completely, and the ratio of the amount of substance of Cys and sodium molybdate consumption is 5:1, sodium molybdate and graphene oxideThe ratio of amount of substance is at 1:1-1:3;
(2) mixed dispersion step (1) being obtained is transferred in hydrothermal reaction kettle, and adds deionized water to adjust volume extremely80% of hydrothermal reaction kettle nominal volume, the concentration of the two ammonium bromides of Gemini surface active agent N-dodecyl trimethylene diamine is0.01-0.02mol/L, the content of graphene oxide is 30-65mmol/L, this reactor is put in constant temperature oven, at 230-At 250 DEG C, after hydro-thermal reaction 24h, allow it naturally cool to room temperature, with centrifugation collection hydro-thermal reaction solid product, and spendIonized water fully washs, vacuum drying at 100 DEG C, by the hydro-thermal reaction solid product obtaining at nitrogen/hydrogen mixed gas atmosphereIn at 800 DEG C heat treatment 2h, in mist, hydrogen volume mark is 10%, finally prepares MoS2Nanometer watt/graphiteThe composite nano materials of alkene;
(3) by the MoS of above-mentioned preparation2Nanometer watt/Graphene composite nano materials is lived as the electrochemistry storage magnesium of preparing combination electrodeProperty material, is stirring with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%Mix the uniform pastel of lower abundant mixing furnishing, this pastel is coated onto equably on the foam copper of collector, in 110 DEG CLower vacuum drying, roll extrusion obtains MoS2Nanometer watt/Graphene electrochemistry storage magnesium combination electrode.
2. capacity according to claim 1 electrochemistry high and stable circulation is store magnesium combination electrode, it is characterized in that, described inMoS2The average number of plies of nanometer watt is 4-5 layer.
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