CN105655152A - Ni-Mn layered double hydroxide@nickel foam@carbon three-dimensional hierarchically-structured electrode material and preparation method thereof - Google Patents
Ni-Mn layered double hydroxide@nickel foam@carbon three-dimensional hierarchically-structured electrode material and preparation method thereof Download PDFInfo
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- CN105655152A CN105655152A CN201511026865.6A CN201511026865A CN105655152A CN 105655152 A CN105655152 A CN 105655152A CN 201511026865 A CN201511026865 A CN 201511026865A CN 105655152 A CN105655152 A CN 105655152A
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- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 61
- 239000006260 foam Substances 0.000 title claims abstract description 58
- 239000007772 electrode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 21
- 229910003286 Ni-Mn Inorganic materials 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 118
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 20
- 239000008103 glucose Substances 0.000 claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 16
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 10
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 10
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 10
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 10
- 239000011565 manganese chloride Substances 0.000 claims abstract description 10
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 229960001031 glucose Drugs 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229960004756 ethanol Drugs 0.000 description 10
- 238000013019 agitation Methods 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229950000845 politef Drugs 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion 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
Classifications
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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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- 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
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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
- H01G11/32—Carbon-based
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a Ni-Mn layered double hydroxide@nickel foam@carbon three-dimensional hierarchically-structured electrode material and a preparation method thereof. The preparation method comprises the following steps: firstly carrying out one-step hydrothermal treatment by respectively taking nickel chloride hexahydrate, anhydrous manganese chloride and nickel foam as a nickel source, a manganese source and a substrate, so as to obtain Ni-Mn LDH@NF; and coating Ni-Mn LDH@NF by virtue of glucose or graphene as a carbon source, and carrying out hydrothermal treatment, so as to obtain Ni-Mn LDH@NF@C. According to the preparation method, by virtue of a stepwise hydrothermal-drying method, the preparation process and the required equipment are simple, raw material sources are rich, the reaction temperature is relatively low, the high temperature carbonization is not needed, and the large-scale production is easy to realize; and the Ni-Mn LDH@NF@C composite material is good in thermal stability, high in crystalline degree, large in specific surface area and strong in shape controllability and is one of ideal energy source materials.
Description
Technical field
The invention belongs to materialogy technical field, relate to a kind of three-dimensional hierarchical structure combination electrode material, specifically three-dimensional hierarchical structure electrode material of a kind of Ni-Mn layered double-hydroxide nickel foam carbon (Ni-MnLDHNFC) and preparation method thereof.
Background technology
The progress of human social development, the increase of energy demand, cause that the deterioration of supply and demand crisis and environment occurs in traditional fossil energy, the environmental issue such as the acid rain of initiation, greenhouse gases becomes increasingly conspicuous, and constantly seeks new clean energy resource in the urgent need to people. The appearance of ultracapacitor and lithium electricity, has complied with people's demand to Novel clean regenerative resource (such as solar energy, wind energy, biomass energy, geothermal energy and tide energy etc.). It is increasingly subject to pay attention to because of it has extended cycle life, the discharge and recharge time is short, energy density, power density are high and wider range of operating temperature, good reliability etc. are excellent performance and being widely applied property, substitute traditional nickel hydrogen battery, ickel-cadmium cell and lead-acid accumulator gradually, it is widely used in the various electronic equipments of information age today, such as mobile phone, digital camera, video camera and digital processor etc. In recent years, lithium ion battery application in a new generation's hybrid vehicle (hybridelectricalvehicle, HEV) and pure electric automobile (electricalvehicle, HEV) is also increasingly subject to pay close attention to.
Current most business-like electrode material is mainly the material with carbon element of Large ratio surface, but its energy density is relatively low, and restriction is large-scale to be used. And transition metal oxide is different from material with carbon element with hydroxide storage electric charge, by surface faraday's redox reaction, there is the energy density higher than material with carbon element, and its layer structure can provide well-proportioned dispersion liquid for transition metal ion so that has good application prospect in electrochemistry. But the layered double hydroxide that laboratory is studied at present also has certain defect: (1) LDH electric conductivity is bad, and running voltage is not high; (2) along with very big change in volume can occur in the increase of discharge and recharge number of times, this can be substantially reduced the cyclical stability of electrode; (3) must be first bonded in conductive substrates with PTFE etc. when applying as electrode material, complicated operation;If one layer of carbon can be coated with on LDH, and allow LDH electrode active material be grown directly upon in conductive substrates as electrode material, its performance will be greatly improved, reduce production technology.
Summary of the invention
For above-mentioned technical problem, it is an object of the invention to provide a kind of Ni-Mn layered double-hydroxide nickel foam carbon three-dimensional hierarchical structure electrode material and preparation method thereof. The method can solve that layered double hydroxide LDH electric conductivity of the prior art is bad, the shortcoming of adhesive etc. when using, and will not environment be worked the mischief simultaneously.
The present invention is respectively with Nickel dichloride hexahydrate and anhydrous Manganese chloride for nickel source and manganese source, and nickel foam is substrate, obtains Ni-MnLDHNF after a step hydro-thermal; Then with glucose or Graphene for carbon source, it is coated with Ni-MnLDHNF, then the hydrothermal treatment consists carrying out second step obtains Ni-MnLDHNFC. Adopt substep hydro-thermal-seasoning, by controlling the concentration of Ni-Mn mol ratio, hydro-thermal reaction time and temperature, glucose, prepare the Ni-MnLDHNFC of three-dimensional hierarchical structure. The concrete technical scheme of the present invention is described below.
The preparation method that the present invention provides a kind of Ni-Mn layered double-hydroxide nickel foam carbon three-dimensional hierarchical structure electrode material, specifically comprises the following steps that
(1) nickel foam is carried out pretreatment
(2) Ni-MnLDHNF is prepared
First, at room temperature, by Nickel dichloride hexahydrate, anhydrous Manganese chloride, urotropine and deionized water mix homogeneously in container; Then, above-mentioned mixed solution is moved in autoclave, and is added thereto to the nickel foam that step (1) pretreatment obtains, carry out hydro-thermal reaction; Reaction naturally cools to room temperature, washing foam nickel after terminating; Wherein: the mol ratio of Nickel dichloride hexahydrate, anhydrous Manganese chloride, urotropine and deionized water is (8-11): 2:10:5;
(3) Ni-MnLDHNFC is prepared
First, under room temperature condition, glucose or Graphene and deionized water and stirring are dissolved and make solution; Then above-mentioned solution is moved in autoclave, and is added thereto to the nickel foam that step (2) obtains, carry out hydro-thermal reaction; Reaction naturally cools to room temperature, washing foam nickel, vacuum drying, obtains Ni-Mn layered double-hydroxide nickel foam carbon three-dimensional hierarchical structure electrode material after terminating.
In above-mentioned steps (1), the method that nickel foam carries out pretreatment is as follows: first cutting nickel foam, then successively with deionized water, acetone, ethanol, deionized water supersound washing, last vacuum drying.
In above-mentioned steps (2), hydrothermal temperature is 85-95 DEG C, and the response time is 5-7 hour.
In above-mentioned steps (3), hydrothermal temperature is 175-185 DEG C, and the time is 11-13 hour.
In above-mentioned steps (3), glucose be D-(+)-glucose, Graphene is to obtain by reducing the graphene oxide prepared of hummer method.
In the solution that in above-mentioned steps (3), glucose or Graphene and deionized water are made, the concentration of glucose is 10-20mg/mL, and the concentration of Graphene is 3-10mg/mL.
The present invention also provides for a kind of Ni-Mn layered double-hydroxide nickel foam carbon three-dimensional hierarchical structure electrode material that above-mentioned preparation method obtains.
The beneficial effects of the present invention is:
1, the preparation technology of the present invention and equipment needed thereby are simple, and it is relatively low that base foam nickel has good flexility, abundant raw material source, reaction temperature, it is not necessary to high temperature cabonization, it is easy to accomplish large-scale production.
2, the Ni-MnLDHNFC composite obtained by the method for the present invention takes full advantage of the synergism of layered metal double-hydroxide, nickel foam and carbon, overcome the shortcoming that electric conductivity and the cycle performance material with carbon element energy density poor, independent of simple LDH is low, not only Heat stability is good, crystallization degree are high, specific surface area is big, good cycling stability, and morphology controllable is strong, has higher ratio electric capacity, is one of desirable energy and material.
Accompanying drawing explanation
Fig. 1 is the Ni-MnLDH of embodiment 1 gained scanning electron microscope (SEM) photograph under the multiplying power of 10000.
Fig. 2 is the Ni-MnLDHNF of embodiment 1 gained scanning electron microscope (SEM) photograph under the multiplying power of 7000.
Fig. 3 is the Ni-MnLDH of embodiment 2 gained scanning electron microscope (SEM) photograph under the multiplying power of 20000.
Fig. 4 is the Ni-MnLDHNF of embodiment 2 gained scanning electron microscope (SEM) photograph under the multiplying power of 5000.
Fig. 5 is the Ni-MnLDHNFC of embodiment 3 gained scanning electron microscope (SEM) photograph under the multiplying power of 10000.
Fig. 6 is the Ni-MnLDHNFC of embodiment 3 gained transmission electron microscope picture under high-resolution
Fig. 7 is the Ni-MnLDH electrochemical property test figure of embodiment 3 gained.
Fig. 8 is the Ni-MnLDHNF of embodiment 4 gained scanning electron microscope (SEM) photograph under the multiplying power of 2300.
Fig. 9 is the XRD figure of Ni-MnLDH and the Ni-MnLDHC powder of embodiment 4 gained.
Figure 10 is the Ni-MnLDHNFC of embodiment 4 gained scanning electron microscope (SEM) photograph under the multiplying power of 2000.
Detailed description of the invention
Below by specific embodiment and in conjunction with accompanying drawing, the present invention is expanded on further, but is not limiting as the present invention.
Embodiment 1
The preparation method of a kind of Ni-MnLDHNFC three-dimensional hierarchical structure electrode material, comprises the steps:
(1) pre-treatment step of nickel foam, nickel foam is cut into the shape of 1cm �� 3cm �� 1cm, successively with deionized water, acetone, ethanol, each 15min of deionized water supersound washing, then with deionized water wash 2 times, then vacuum drying 12h under 60 DEG C of conditions; Concrete, the mass percent concentration of described acetone is 60��98%, and ethanol is dehydrated alcohol.
(2) steps preparing Ni-MnLDH, at room temperature, it is 9:2:10:5 according to mol ratio, Nickel dichloride hexahydrate, anhydrous Manganese chloride, urotropine, deionized water are joined in a container, magnetic agitation 30-40min to mixing completely uniformly, moves in polytetrafluoroethyllining lining rustless steel autoclave; Then by step 1) nickel foam that obtains of pretreatment tiltedly puts in a kettle., puts into 85 DEG C of baking boxs reaction 6h after tightening; Naturally cool to room temperature afterwards, with deionized water and ethanol washing foam nickel 3-4 time successively;
(3) step of Ni-MnLDHNFC is prepared, at ambient temperature a certain amount of glucose, deionized water are joined in a container, magnetic agitation 10-20 minute to being completely dissolved, obtain the glucose solution that concentration is 10mg/ml, then move it in politef autoclave; By step 2) nickel foam that obtains tiltedly puts in a kettle., is placed on 12h in 185 DEG C of baking boxs, naturally cools to room temperature afterwards after tightening, successively with deionized water and washing with alcohol nickel foam 3-4 time, vacuum drying 12h under 60 DEG C of conditions.
Adopt field emission scanning electron microscope (Germany Zeissultra55) instrument, under the multiplying power of 10000, the Ni-MnLDH powder of above-mentioned gained is scanned, the scanning electron microscope (SEM) photograph of gained is as shown in Figure 1, as can be seen from Figure 1 the petal-like structures of composite, has been indicated above successfully preparing Ni-MnLDH; Under the multiplying power of 7000, the Ni-MnLDHNF three-dimensional material of above-mentioned gained is scanned, the scanning electron microscope (SEM) photograph of gained as in figure 2 it is shown, as can be seen from Figure 2 Ni-MnLDH be uprightly evenly distributed in nickel foam surface, be indicated above successfully preparing Ni-MnLDHNF three-dimensional hierarchical structure material.
Embodiment 2
A kind of preparation method of Ni-MnLDHNFC three-dimensional hierarchical structure electrode material, comprise the steps: the pre-treatment step of (1) nickel foam, nickel foam is cut into the shape of 1cm �� 3cm �� 1cm, successively with deionized water, acetone, ethanol, each 15min of deionized water supersound washing, use deionized water wash 2 times again, then vacuum drying 12h under 60 DEG C of conditions;
(2) steps preparing Ni-MnLDH, at room temperature, according to mol ratio 8:2:10:5, Nickel dichloride hexahydrate, anhydrous Manganese chloride, urotropine and deionized water are joined in a container, magnetic agitation 30-40min to mixing completely uniformly, moves in polytetrafluoroethyllining lining rustless steel autoclave; Then by step 1) nickel foam that obtains of pretreatment tiltedly puts in a kettle., puts into 95 DEG C of baking boxs reaction 6h after tightening; Room temperature is naturally cooled to, with deionized water and ethanol washing foam nickel 3-4 time successively after taking-up;
(3) step of Ni-MnLDHNFC is prepared, at ambient temperature a certain amount of glucose, deionized water are joined in a container, magnetic agitation 10-20 minute to being completely dissolved, obtain the glucose solution that concentration is 13mg/ml, then move it in politef autoclave; By step 2) nickel foam that obtains tiltedly puts in a kettle., is placed on 12h in 175 DEG C of baking boxs, naturally cools to room temperature after taking-up after tightening, successively with deionized water and washing with alcohol nickel foam 3-4 time, vacuum drying 12h under 60 DEG C of conditions.
Adopt field emission scanning electron microscope (Germany Zeissultra55) instrument, under the multiplying power of 20000, the Ni-MnLDH powder of above-mentioned gained is scanned, the scanning electron microscope (SEM) photograph of gained is as shown in Figure 3, as can be seen from Figure 3 the petal-like structures of composite, has been indicated above successfully preparing Ni-MnLDH; Under the multiplying power of 5000, the Ni-MnLDHNF three-dimensional material of above-mentioned gained is scanned, the scanning electron microscope (SEM) photograph of gained is as shown in Figure 4, as can be seen from Figure 4 Ni-MnLDH is deposited in nickel foam surface, skewness, but it can be seen that is successfully prepared out Ni-MnLDHNF three-dimensional hierarchical structure material.
Embodiment 3
The preparation method of a kind of Ni-MnLDHNFC three-dimensional hierarchical structure electrode material, comprises the steps:
(1) pre-treatment step of nickel foam, nickel foam is cut into the shape of 1cm �� 3cm �� 1cm, successively with deionized water, acetone, ethanol, each 15min of deionized water supersound washing, then with deionized water wash 2 times, then vacuum drying 12h under 60 DEG C of conditions;
(2) steps preparing Ni-MnLDH, at room temperature, according to mol ratio 10:2:10:5, it is that 10:2:10:5 joins in a container by Nickel dichloride hexahydrate, anhydrous Manganese chloride, urotropine, deionized water according to mol ratio, magnetic agitation 30-40min to mixing completely uniformly, moves in polytetrafluoroethyllining lining rustless steel autoclave; Then by step 1) nickel foam that obtains of pretreatment tiltedly puts in a kettle., puts into 85 DEG C of baking boxs reaction 6h after tightening; Room temperature is naturally cooled to, with deionized water and ethanol washing foam nickel 3-4 time successively after taking-up;
(3) step of Ni-MnLDHNFC is prepared, at ambient temperature a certain amount of Graphene, deionized water are joined in a container, within magnetic agitation 10-20 minute, to being completely dissolved, obtain the graphene solution that concentration is 5mg/ml, then move it in politef autoclave; By step 2) nickel foam that obtains tiltedly puts in a kettle., is placed on 12h in 185 DEG C of baking boxs, naturally cools to room temperature after taking-up after tightening, successively with deionized water and washing with alcohol nickel foam 3-4 time, vacuum drying 12h under 60 DEG C of conditions.
Fig. 5 is the Ni-MnLDHNFC of gained scanning electron microscope (SEM) photograph under the multiplying power of 10000. As can be seen from Figure 5 Graphene is successfully coated on above Ni-MnLDHNF, and the petal of lamellar is in the state being coated with by carbon, but still can find out the structure of lamellar clearly;Fig. 6 is the transmission electron microscope picture under the high-resolution of gained, it can be seen that very regular lattice structure; Fig. 7 is Ni-MnLDH electrochemical property test figure, it can be seen that the three-dimensional stratum combination electrode material of the present invention all has a pair obvious oxidoreduction peak under different scanning speeds from Fig. 7 cyclic voltammogram, thus demonstrating redox reaction.
Embodiment 4
The preparation method of a kind of Ni-MnLDHNFC three-dimensional hierarchical structure electrode material, comprises the steps:
(1) pre-treatment step of nickel foam, nickel foam is cut into the shape of 1cm �� 3cm �� 1cm, successively with deionized water, acetone, ethanol, each 15min of deionized water supersound washing, then with deionized water wash 2 times, then vacuum drying 12h under 60 DEG C of conditions;
(2) steps preparing Ni-MnLDH, at room temperature, according to mol ratio 11:2:10:5, Nickel dichloride hexahydrate, anhydrous Manganese chloride, urotropine, deionized water are joined in a container, magnetic agitation 30-40min to mixing completely uniformly, moves in polytetrafluoroethyllining lining rustless steel autoclave; Then by step 1) nickel foam that obtains of pretreatment tiltedly puts in a kettle., puts into 90 DEG C of baking boxs reaction 6h after tightening; Room temperature is naturally cooled to, with deionized water and ethanol washing foam nickel 3-4 time successively after taking-up;
(3) step of Ni-MnLDHNFC is prepared, at ambient temperature a certain amount of glucose, deionized water are joined in a container, magnetic agitation 10-20 minute to being completely dissolved, obtain the glucose solution that concentration is 20mg/ml, then move it in politef autoclave; By step 2) nickel foam that obtains tiltedly puts in a kettle., is placed on 12h in 175 DEG C of baking boxs, naturally cools to room temperature after taking-up after tightening, successively with deionized water and washing with alcohol nickel foam 3-4 time, vacuum drying 12h under 60 DEG C of conditions.
Under the multiplying power of 2300, the Ni-MnLDHNF three-dimensional material of above-mentioned gained is scanned, the scanning electron microscope (SEM) photograph of gained is as shown in Figure 8, as can be seen from Figure 8 Ni-MnLDH is evenly distributed in nickel foam surface, it is indicated above successfully preparing Ni-MnLDHNF three-dimensional hierarchical structure material, but the petal piled up above is too many. Fig. 9 is the XRD figure spectrum of Ni-MnLDH and the Ni-MnLDHC powder scraped nickel foam. As can be seen from Figure 9 prepared by the success of this composite, and has good degree of crystallinity. Figure 10 is the Ni-MnLDHNFC of gained scanning electron microscope (SEM) photograph under the multiplying power of 2000. But as can be seen from Figure 10 glucose is successfully coated on above Ni-MnLDHNF. Ni-MnLDH is covered by glucose completely.
In sum, a kind of Ni-MnLDHNFC of the different-shape of the preparation method gained of the Ni-MnLDHNFC three-dimensional hierarchical structure electrode material of the present invention, thus the chemical property affecting them is different, under 1mol/LKOH electrolyte conditions, with the three-electrode system chemical property at electrochemical workstation and indigo plant electricity system test material, the best Ni-MnLDHNF electrode of prepared chemical property is at 500mAg-1There is during constant current charge-discharge 1100mAhg-1, but owing to, in charge and discharge process, its volume has obvious change, after circulation 2090 times, specific capacity substantially reduces, and under high current density, high rate performance declines clearly; And it is coated with the Ni-MnLDHNFC three-dimensional hierarchical structure electrode material after a certain amount of glucose or Graphene at 500mAg-1There is during constant current charge-discharge 1900mAhg-1, and after circulation 2090 times, remain in that the specific capacity of nearly 80%, there is good cyclical stability, at 10Ag-1High current density under, remain in that the electric capacity of nearly 70%, having good high rate performance, take full advantage of the synergism with the nickel foam of the netted high surface area of 3 D stereo, material with carbon element and transition metal layered double-hydroxide, the homogenous material simultaneously overcome is as the defect of electrode.
Foregoing is only specifically enumerating of embodiments of the present invention, and according to any equivalent transformation that technical scheme is made, all should belong to protection scope of the present invention.
Claims (7)
1. the preparation method of a Ni-Mn layered double-hydroxide nickel foam carbon three-dimensional hierarchical structure electrode material, it is characterised in that specifically comprise the following steps that
(1) nickel foam is carried out pretreatment;
(2) Ni-MnLDHNF is prepared
First, at room temperature, by Nickel dichloride hexahydrate, anhydrous Manganese chloride, urotropine and deionized water mix homogeneously in container; Then, above-mentioned mixed solution is moved in autoclave, and is added thereto to the nickel foam that step (1) pretreatment obtains, carry out hydro-thermal reaction; Reaction naturally cools to room temperature, washing foam nickel after terminating; Wherein: the mol ratio of Nickel dichloride hexahydrate, anhydrous Manganese chloride, urotropine and deionized water is (8-11): 2:10:5;
(3) Ni-MnLDHNFC is prepared
First, under room temperature condition, glucose or Graphene and deionized water and stirring are dissolved and make solution; Then above-mentioned solution is moved in autoclave, and is added thereto to the nickel foam that step (2) obtains, carry out hydro-thermal reaction; Reaction naturally cools to room temperature, washing foam nickel, vacuum drying, obtains Ni-Mn layered double-hydroxide nickel foam carbon three-dimensional hierarchical structure electrode material after terminating.
2. preparation method as claimed in claim 1, it is characterized in that, in step (1), the method that nickel foam carries out pretreatment is as follows: first cutting nickel foam is in blocks, then successively with deionized water, acetone, ethanol, deionized water supersound washing, last vacuum drying.
3. preparation method as claimed in claim 1, it is characterised in that in step (3), hydrothermal temperature is 85-95 DEG C, and the response time is 5-7 hour.
4. preparation method as claimed in claim 1, it is characterised in that in step (3), hydrothermal temperature is 175-185 DEG C, and the time is 11-13 hour.
5. preparation method as claimed in claim 1, it is characterised in that in step (3), glucose be D-(+)-glucose, Graphene is to obtain by reducing graphene oxide prepared by hummer method.
6. preparation method as claimed in claim 1, it is characterised in that: in step (3), in the solution that glucose or Graphene and deionized water are made, the concentration of glucose is 10-20mg/mL, and the concentration of Graphene is 3-10mg/mL.
7. the Ni-Mn layered double-hydroxide nickel foam carbon three-dimensional hierarchical structure electrode material that preparation method as described in one of claim 1-6 obtains.
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