CN109243847B - A kind of NiMoO4/ redox graphene nanocomposite and preparation method thereof - Google Patents
A kind of NiMoO4/ redox graphene nanocomposite and preparation method thereof Download PDFInfo
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- CN109243847B CN109243847B CN201811249162.3A CN201811249162A CN109243847B CN 109243847 B CN109243847 B CN 109243847B CN 201811249162 A CN201811249162 A CN 201811249162A CN 109243847 B CN109243847 B CN 109243847B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of three-dimensional ordered macroporous carbon-coated NiMoO4/ redox graphene nanocomposite and preparation method thereof.Present invention introduces crosslinking agent PVA, pass through ice template method first for (NH3)4(NiMo6O24H6)/GO two-dimensional slice is built into three-dimensional ordered macroporous structure, is then heat-treated under an inert gas, so that package (NH3)4(NiMo6O24H6The PVA of)/GO is converted into carbon shell, meanwhile, (NH3)4(NiMo6O24H6) it is converted into NiMoO4, GO is reduced into redox graphene, and then obtains target nanocomposite.Preparation method of the present invention is simple, and obtained material has a bigger specific surface area, when electrode material as supercapacitor, shows excellent chemical property, is one of ideal energy storage material.
Description
Technical field
The present invention relates to a kind of three-dimensional ordered macroporous carbon-coated NiMoO4/ redox graphene nanocomposite and
Preparation method belongs to technical field of nano material.
Background technique
With the fast development of global economy, the mankind have inevitably fallen into fossil energy increasingly exhausted and environmental pollution
The awkward situation got worse.In face of nowadays serious environment and energy problem, the exploitation of new cleaning fuel seems especially urgent.Such as
What, which seeks and develop pollution-free, the own warp of circulation new energy, becomes one of the problem of nowadays social sustainable development necessarily faces.?
In many form of energy (such as fossil energy, wind energy, solar energy, electric energy and nuclear energy), electric energy is as a kind of clean energy resource in day
It is often most widely used in life and using more convenient, but its energy storage problem is always the bottleneck for restricting its development.It therefore can
Become the focus of attention with the energy storage of recycling and conversion equipment, such as: fuel cell, supercapacitor and lithium battery.
It is the one-shot battery of representative, plumbic acid, ni-Cd, ni-mh, lithium with alkali manganese, silver-colored zinc, lithium electricity etc. by taking common cell system in the market as an example
The secondary cells such as ion, poly-lithium battery have been widely used for automobile, electronics, communication, aerospace, military affairs, medical treatment, postal
Political affairs, food and processing and other fields.Although these traditional battery energy densities are relatively large, answering for most of occasion can satisfy
It, the defects of power density is relatively low, cannot in some high energy pulse applications with demand, but long there are the charging time
Meet the maximum peak power of system needs.On the other hand, the traditional electrostatic capacitance famous with quick charge and discharge, high power
Device, such as alminium electrolytic condenser, tantalum electrolytic capacitor, although there are also certain to answer in fields such as electric system, computer, electronic circuits
With market, but since its energy storage density is too low, it can not meet the requirements, be currently under the diminution process using depth and range
In.Therefore, it being continued to develop with economical, the improvement of people's living standards, the reinforcement of environmental consciousness, new opplication field is opened up,
With high-energy density, high power density, novel green energy storage component urgently development and production and the application of long-life.
A kind of energy storage device of the supercapacitor as electrical energy form, has that power density is high, has extended cycle life and safety
The features such as environmentally friendly, becomes whole world focus of attention.Supercapacitor is a kind of storage between traditional capacitor and battery
Energy element, can be widely applied to the fields such as national defense industry, mobile communication and electric car.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of three-dimensional ordered macroporous carbon-coated
NiMoO4/ redox graphene nanocomposite and preparation method thereof；The present invention is used through ice~separation~induction certainly
Dress, the i.e. method of ice template, and carbonized under inert atmosphere (nitrogen, argon gas etc.), cellular nanocomposite is obtained, it should
Composite material large specific surface area, for presenting excellent chemical property in terms of supercapacitor.
Present invention introduces crosslinking agent PVA, by ice template method by (NH3)4(NiMo6O24H6)/GO two-dimensional slice is built into three
Ordered big hole structure is tieed up, is then heat-treated under an inert gas, so that package (NH3)4(NiMo6O24H6The PVA of)/GO is converted into
Carbon shell, meanwhile, (NH3)4(NiMo6O24H6) it is converted into NiMoO4, GO is reduced into redox graphene, and then obtains three-dimensional
The carbon-coated NiMoO of orderly macropore4/ redox graphene nanocomposite.Technical solution of the present invention is specifically introduced
It is as follows.
The present invention provides a kind of three-dimensional ordered macroporous carbon-coated NiMoO4/ redox graphene nanocomposite
Preparation method includes the following steps:
1) graphene oxide GO is added in deionized water, ultrasound is evenly dispersed, and Anderson type is then added
(NH3)4(NiMo6O24H6), ultrasonic dissolution；
2) dispersion liquid for obtaining step 1) is heated to flowing back, heating temperature be 105~120 DEG C, return time be 12~
24h；
3) it after reaction, is down to room temperature, for several times with deionized water centrifuge washing, discards supernatant liquid, then by lower part
GO/(NH3)4(NiMo6O24H6) concentration；
It 4) is that the aqueous solution of PVA is added to the GO/ (NH after being concentrated in step 3) by 1:1 according to volume ratio3)4
(NiMo6O24H6) in, it is transferred in disposable needle tubing, is freezed under liquid nitrogen atmosphere after mixing；
5) sample for obtaining step 4) is transferred to freeze drier freeze-drying, forms a complete block；
6) the block sample in step 5) is calcined in an inert atmosphere, is obtained three-dimensional ordered macroporous carbon-coated
NiMoO4/ redox graphene nanocomposite.
In the present invention, in step 1), GO and (NH3)4(NiMo6O24H6) mass ratio be 1:2~1:10, when ultrasonic dissolution
Between be 15~30min.
In the present invention, in step 3), GO/ (NH3)4(NiMo6O24H6) concentration concentration control in 10~50mg/mL.
In the present invention, in step 4), the mass concentration of the aqueous solution of PVA is 10~50mg/mL；It is freezed under liquid nitrogen atmosphere
Time be 5~for 24 hours.
In the present invention, in step 5), freeze-drying temperature is -48~-80 DEG C, and sublimation drying is 24~72h.
In the present invention, in step 6), calcination procedure is as follows: being that 5~10 DEG C/min is heated to 500~800 with heating rate
DEG C, continue 1~5h of heat preservation.
The present invention further provides three-dimensional ordered macroporous carbon-coated NiMoO made from a kind of above-mentioned preparation method4/ also
Former stannic oxide/graphene nano composite material.
Compared to the prior art, the beneficial effects of the present invention are:
The cellular three-dimensional ordered macroporous carbon-coated NiMoO that the present invention is obtained by above-mentioned preparation method4/ oxygen reduction
Graphite alkene nanocomposite, has a bigger specific surface area, when electrode material as supercapacitor, shows excellent
Different chemical property, specific capacitance reach 1080F g-1, it is ideal that after circulation 5000 is enclosed, specific capacitance conservation rate, which is 97.6%,
One of energy storage material.
Detailed description of the invention
Fig. 1 is three-dimensional ordered macroporous carbon-coated NiMoO prepared by embodiment 14The nano combined material of/redox graphene
The scanning electron microscope (SEM) photograph of material.
Fig. 2 is three-dimensional ordered macroporous carbon-coated NiMoO prepared by embodiment 24The nano combined material of/redox graphene
The scanning electron microscope (SEM) photograph of material.
Fig. 3 is three-dimensional ordered macroporous carbon-coated NiMoO prepared by embodiment 34The nano combined material of/redox graphene
The XRD diagram of material.
Fig. 4 is three-dimensional ordered macroporous carbon-coated NiMoO prepared by embodiment 44The nano combined material of/redox graphene
Expect the charge and discharge electrograph in electro-chemical test.
Specific embodiment
The present invention is further described below by specific embodiment and in conjunction with attached drawing, but the present invention is not by following implementation
The limitation of mode, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination,
Simplify, should be equivalent substitute mode, be included within the scope of the present invention.
In embodiment, (the NH of Anderson type3)4(NiMo6O24H6) obtained by following preparation method, preparation process is such as
Under:
By (NH4)6Mo7O24﹒ 4H2O aqueous solution is heated to boiling, and the aqueous solution dissolved with nickel salt is added thereto, and mixed liquor exists
It evaporates, while hot filtering heat solution, is cooled to room temperature in steam bath, it is allowed to precipitate crystal naturally, it is miscellaneous more to obtain Ni-Anderson
Acid.
Embodiment 1
1) GO of 30mg is pipetted in deionized water, and ultrasonic 30min keeps GO evenly dispersed.Then 0.15g is added
(the NH of Anderson type3)4(NiMo6O24H6), ultrasonic 15min dissolution.
2) above-mentioned dispersion liquid is transferred to 100mL eggplant type bottle, heating stirring under the conditions of 105 DEG C, reflux condensation mode 12h.
3) reaction solution after reaction, is down to room temperature, and three times with deionized water centrifuge washing, discards supernatant liquid, it will
GO/(NH3)4(NiMo6O24H6) concentration concentration be 15mg/mL.
4) it is 1:1 according to volume ratio, the PVA solution of 50mg/mL is added to GO/ (NH in 3)3)4(NiMo6O24H6) in,
Then it is uniformly mixed and is transferred in the disposable needle tubing of 1mL, freeze 8h under liquid nitrogen atmosphere.
5) 4) sample obtained in is transferred to freeze drier freeze-drying 72h, drying temperature is -72 DEG C, forms one
A complete block.
6) under nitrogen atmosphere by the block sample in 5), with the rate of heat addition it is that 5 DEG C/min is heated to 500 DEG C, then 500
2h is calcined under conditions of DEG C, finally obtains product C-NiMoO4/ redox graphene -1.
Pass through this embodiment step 1)~6) obtained three-dimensional ordered macroporous C-NiMoO4- 1 nanometer of/redox graphene
Composite material, scanning electron microscope are shown in Fig. 1, are presented honeycomb structure, the large specific surface area of material, when being prepared into super capacitor electrode
When pole, the chemical property that is excellent in.
Embodiment 2
Illustrate: step 1)~5) it is identical as example 1, it repeats no more.
6) it under nitrogen atmosphere by the sample in step 5), calcines under the conditions of 600 DEG C, finally obtains product C-NiMoO4/
Redox graphene -2.
The three-dimensional ordered macroporous C-NiMoO being prepared by this embodiment4The nano combined material of/redox graphene -2
Material, scanning electron microscope are shown in Fig. 2, honeycomb structure are presented, and compared with Example 1 compared with lamella is thicker, illustrates PVA degree of carbonization
Increase, is conducive to the increase of conductivity, when being prepared into electrode of super capacitor, the chemical property that is excellent in.
Embodiment 3
Illustrate: step 1)~5) it is identical as example 2, it repeats no more.
6) it under nitrogen atmosphere by the sample in step 5), calcines under the conditions of 700 DEG C, finally obtains product C-NiMoO4/
Redox graphene -3.
The three-dimensional ordered macroporous C-NiMoO being prepared by this embodiment4The nano combined material of/redox graphene -3
Material, XRD diagram are shown in Fig. 3, and it is the apparent characteristic peak of carbon material that 2 θ, which are 20~30 °, which has a big broad peak, 14.3 °, 21.7 °,
25.3 °, 29.7 °, 32.6 °, 43.9 ° are NiMoO4Characteristic diffraction peak, the C-NiMoO of preparation4/ redox graphene -3 is received
Nano composite material shows good crystal form.
Embodiment 4
Illustrate: step 1)~5) it is identical as example 3, it repeats no more.
6) it under nitrogen atmosphere by the sample in step 5), calcines under the conditions of 800 DEG C, finally obtains product C-NiMoO4/
Redox graphene -4.
Pass through this embodiment step 1)~6) obtained three-dimensional ordered macroporous C-NiMoO4- 4 nanometers of/redox graphene
Composite material, gap is more, large specific surface area；When being prepared into electrode of super capacitor, electrochemical workstation, three electrodes are utilized
System, KOH test its chemical property as reference electrode as electrolyte, Ag/AgCl.
Fig. 4 is three-dimensional ordered macroporous carbon-coated NiMoO prepared by embodiment 44The nano combined material of/redox graphene
Expect the charge and discharge electrograph in electro-chemical test.It is 0.5A g in current density-1, 1A g-1, 2A g-1, 5A g-1, 10A g-1When,
Specific capacitance respectively reaches 1080F g-1, 900F g-1, 800F g-1, 715F g-1, 635F g-1。
Claims (7)
1. a kind of NiMoO4The preparation method of/redox graphene nanocomposite, which comprises the steps of:
1) graphene oxide GO is added in deionized water, ultrasound is evenly dispersed, and (the NH of Anderson type is then added3)4
(NiMo6O24H6), ultrasonic dissolution；
2) dispersion liquid for obtaining step 1) is heated to flowing back, heating temperature be 105~120 DEG C, return time be 12~for 24 hours；
3) it after reaction, is down to room temperature, for several times with deionized water centrifuge washing, discards supernatant liquid, then by the GO/ of lower part
(NH3)4(NiMo6O24H6) concentration；
It 4) is that the aqueous solution of PVA is added to the GO/ (NH after being concentrated in step 3) by 1:1 according to volume ratio3)4(NiMo6O24H6)
In, it is transferred in disposable needle tubing, is freezed under liquid nitrogen atmosphere after mixing；
5) sample for obtaining step 4) is transferred to freeze drier freeze-drying, forms a complete block；
6) the block sample in step 5) is calcined in an inert atmosphere, obtains three-dimensional ordered macroporous carbon-coated NiMoO4/ graphite
Alkene nanocomposite.
2. preparation method according to claim 1, it is characterised in that: in step 1), GO and (NH3)4(NiMo6O24H6)
Mass ratio is 1:2~1:10, and the ultrasonic dissolution time is 15~30min.
3. preparation method according to claim 1, it is characterised in that: in step 3), GO/ (NH3)4(NiMo6O24H6) concentration
Control is in 10~50mg/mL.
4. preparation method according to claim 1, it is characterised in that: in step 4), the mass concentration of the aqueous solution of PVA is
10~50mg/mL；Under liquid nitrogen atmosphere cooling time be 5~for 24 hours.
5. preparation method according to claim 1, it is characterised in that: in step 5), freeze-drying temperature is -48~-80
DEG C, sublimation drying is 24~72h.
6. preparation method according to claim 1, it is characterised in that: in step 6), calcination procedure is as follows: with heating rate
500~800 DEG C are heated to for 5~10 DEG C/min, continues 1~5h of heat preservation.
7. it is a kind of according to claim 1~one of 6 described in three-dimensional ordered macroporous carbon-coated NiMoO made from preparation method4/
Redox graphene nanocomposite.
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| CN103346301B (en) * | 2013-06-25 | 2016-01-13 | 上海交通大学 | The preparation method of the graphene-based metal oxide composite of three-dimensional structure and application thereof |
| CN104752067A (en) * | 2015-03-27 | 2015-07-01 | 新疆大学 | Microwave-assisted method of nickel molybdate graphene composite material used for capacitor |
| CN105244182B (en) * | 2015-09-29 | 2019-02-15 | 重庆大学 | Capacitor electrode material β-NiMoO4Preparation method and supercapacitor |
| CN108123110B (en) * | 2016-11-28 | 2020-09-04 | 中国科学院大连化学物理研究所 | Preparation method and application of nitrogen-containing large-pore-volume porous carbon material |
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