CN106298287B - A kind of composite material and preparation method and its ultracapacitor of application of multi-layer graphene and iron cobalt layered double hydroxide - Google Patents
A kind of composite material and preparation method and its ultracapacitor of application of multi-layer graphene and iron cobalt layered double hydroxide Download PDFInfo
- Publication number
- CN106298287B CN106298287B CN201610920428.7A CN201610920428A CN106298287B CN 106298287 B CN106298287 B CN 106298287B CN 201610920428 A CN201610920428 A CN 201610920428A CN 106298287 B CN106298287 B CN 106298287B
- Authority
- CN
- China
- Prior art keywords
- layer graphene
- layered double
- double hydroxide
- composite material
- iron cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention belongs to super capacitance electrode material technical field, the composite material and preparation method for disclosing a kind of multi-layer graphene and iron cobalt layered double hydroxide includes the following steps with its ultracapacitor, wherein preparation method is applied：S10, expanded graphite generates multi-layer graphene solution after ultrasound, S20, it is generated close to parallel graphene at graphene surface and in the iron cobalt layered double hydroxide of the vertical graphene of outer surface using hydrothermal synthesis method, the composite material of multi-layer graphene and iron cobalt layered double hydroxide is obtained, to increase the contact with electrolyte.The invention preparation method is simple, and the composite material of preparation has excellent super capacitor performance.
Description
Technical field
The invention belongs to super capacitance electrode material technical fields, and in particular to a kind of multi-layer graphene is double with iron cobalt layers shape
For the composite material and preparation method of metal hydroxides with using its ultracapacitor, composite material is by multi-layer graphene
It is formed perpendicular to the iron cobalt layered double hydroxide of graphene surface with after its surface is first parallel, the composite material of preparation
With high capacitance characteristic, electrode material for super capacitor can be applied to.
Background technology
Ultracapacitor is a kind of energy storage device between ordinary capacitor and chemical cell, has both the excellent of the two
Point, such as power density is high, energy density is high, have extended cycle life, can fast charging and discharging, and with instantaneous high-current discharge and to ring
The characteristics such as border is pollution-free, before the fields such as hybrid-power electric vehicle, pulse power system and emergency power supply have a wide range of applications
Scape.
Super capacitor material mainly has carbon-based electrode material, metal (hydrogen) oxide material and conducting polymer base electricity
Pole material.For Carbon-based supercapacitor, mainly the specific capacitance of capacitor is improved by increasing the specific surface area of material.Root
According to double electrode layer theory, the electric double layer capacitance of electrode surface is about 25 μ F/cm2If specific surface area is 1000m2/ g, then electric double layer is electric
The specific capacity of container is 200F/g, and this higher theoretical value makes people produce greatly the carbon material of high-specific surface area
Interest.
The metal oxide ultracapacitor of original research is mainly with RuO2Equal noble metals are electrode material.Due to RuO2's
Big two orders of magnitude of Conductivity Ratio carbon material, and electrode is stablized in sulfuric acid solution, so obtaining very high specific capacity, prepares
Capacitor than carbon electrode capacitor have better performance.But Precious Metals Resources are limited, and it is expensive, this is greatly
Limit the large-scale application of this kind of electrode material.In order to reduce cost, present researcher is inquiring into other metal oxygens
Compound replaces RuO2Electrode material as ultracapacitor.Some cheap metal oxides such as NiO, MnO2、Co3O4、SnO2、
V2O5Deng they are suffered from and RuO2Similar property, and it is resourceful, cheap, receive the wide of domestic and international researcher
General concern.
Application of the hydroxide on ultracapacitor has similitude with oxide, moreover, layered double hydroxide
Peculiar layer structure, the double effect with large specific surface area and faraday's reaction, therefore Many researchers study its conduct
Electrode material, facts proved that, above there is good foreground in the application of electrochemistry.But its low conductivity is interior when it being made singly to obtain use
Resistance is too big, to make its application be restricted.Double-metal hydroxide and compound the grinding as current ultracapacitor of graphene
Study carefully hot spot.Wherein graphene has good conductive property, and provides substrate for the growth of double-metal hydroxide.Currently, layer
The preparation of shape double-metal hydroxide on the surface of graphene mainly uses graphene oxide (GO), adds two metal ion species and sinks
Product agent carries out chemical deposition, and carries out crystallization and grow into layered hydroxide.But this kind of preparation method complexity, the stratiform of preparation
Double-metal hydroxide is unevenly distributed on the surface of graphene.
For above deficiency, the embodiment of the present invention is self-assembled into sheet under hydrothermal conditions using one-step method, makes sheet
Ferro-cobalt bimetallic is uniformly distributed on the surface of graphene, this kind of preparation method makes iron cobalt layered double hydroxide close to graphene
It is parallel graphene at surface, and in the vertical graphene of outer surface, to increase the contact with electrolyte.The invention preparation side
Method is simple, and the composite material of preparation has excellent super capacitor performance.
Invention content
The technical problem to be solved in the present invention is to provide a kind of multi-layer graphenes and iron cobalt layered double hydroxide
Composite material and preparation method and its ultracapacitor of application.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A kind of preparation method of multi-layer graphene and the composite material of iron cobalt layered double hydroxide, including following step
Suddenly：
S10, expanded graphite generate multi-layer graphene solution after ultrasound,
S20 is generated using hydrothermal synthesis method close to parallel graphene at graphene surface and in the vertical stone of outer surface
The iron cobalt layered double hydroxide of black alkene, obtains the composite wood of multi-layer graphene and iron cobalt layered double hydroxide
Material.
Preferably, S10 specifically includes following steps：
The in the mixed solvent of S101, DMF and distilled water is added expanded graphite and carries out, and mixed solvent is used as after mixing；
S102, in the mixed solvent are added after expanded graphite carries out ultrasonic vibration and obtain multi-layer graphene solution.
Preferably, S20 specifically includes following steps：
Four water frerrous chloride (FeCl are added in S201 in multi-layer graphene mixed solution2·4H2O), cobalt acetate (Co
(CH3COO)2·4H2) and anhydrous sodium acetate (CH O3COONa), it is put into magnetic stirring apparatus and is stirred with 500 rpms of rotating speed
3-7 minutes；
Solution after stirring is poured into the stainless steel hydrothermal reaction kettle of polytetrafluoroethylene (PTFE) by S202, in 100~120 DEG C of temperature
Lower heat preservation obtains reaction production object for 0.5~3 hour after postcooling to room temperature, take out reaction product；
S203, reaction product alcohol and each 3 times of water eccentric cleaning, 60 DEG C of dryings 24 hours, obtain in drying box
The composite material of multi-layer graphene and iron cobalt layered double hydroxide.
Preferably, in S101, the volume ratio of DMF and distilled water is 9:1~6:4.
Preferably, in S102, expanded graphite is 0.2mg/ml~1.0mg/ml relative to mixed solvent volume.
Preferably, FeCl2·4H2O is 30mmol/L~80mmol/L relative to the molar ratio of mixed solvent.
Preferably, Co (CH3COO)2·4H2Cobalt atom in O and FeCl2·4H2The molar ratio of iron atom in O is 2:1
~1:1.
Preferably, CH3A concentration of 0.08mol/L~0.25mol/L of COONa.
A kind of composite material of multi-layer graphene and iron cobalt layered double hydroxide, using above-mentioned preparation method system
, by multi-layer graphene and vertical-growth in multi-layer graphene upper surface and the parallel iron cobalt for being grown on multi-layer graphene upper surface
Layered double hydroxide forms, and the thickness of obtained iron cobalt layered double hydroxide is less than 25nm, uniform in size.
A kind of ultracapacitor uses answering for a kind of above-mentioned multi-layer graphene and iron cobalt layered double hydroxide
Condensation material.
There is following advantageous effect using the present invention：
1, multi-layer graphene is obtained by the in the mixed solvent supersonic expansion graphite formed in organic and inorganic, preparation method
Simply, it is made of Multi-layer graphite layer, surface does not introduce oxygen-containing functional group, thus its chemism is low.Multi-layer graphene has
There are good electric conductivity and big surface area, it is advantageous to improve the surface area of material as the substrate of layered hydroxide, and improve
The conductivity of material.
2, layered double hydroxide is prepared on multi-layer graphene surface using hydrothermal synthesis method, one-step method may be implemented
It prepares, the composite material being prepared is uniform, realizes whole coverings of graphene surface.The method and process of the present invention is simple, holds
It is easy to control, it is at low cost, it is suitble to industrialized production, it is efficient to prepare composite material, and stock utilization is high, is made of the material super
Grade condenser capacity is high.
3, the thickness of the layered double hydroxide obtained is less than 25nm, uniform in size.Thin stratiform is conducive to improve
Surface area.Layered double hydroxide is parallel to graphene on the layer close to graphene and arranges, and subsequent one layer
It is perpendicular to the arrangement of graphene direction.The active force of hydroxide and graphene can be enhanced by being parallel to the arrangement of graphene, make layer
Shape is not easy to fall off from the right surface of graphite.And the layered metal hydroxides of outer layer are to be arranged perpendicular to substrate, can be increased compound
The surface area of material, so as to improve the contact area with electrolyte, to increase capacitive character.Meanwhile charge is reduced compound
Diffusion length in material, to improve the power-performance of capacitance.
Description of the drawings
Fig. 1 is that the multi-layer graphene of the embodiment of the present invention is flowed with the step of iron cobalt layered double hydroxide composite material
Cheng Tu；
The scanning electron microscope (SEM) photograph of the multi-layer graphene of Fig. 2 embodiment of the present invention；
Fig. 3 is the low power of the multi-layer graphene and iron cobalt layered double hydroxide composite material of the embodiment of the present invention 1
Scanning electron microscope (SEM) photograph；
Fig. 4 is the high power of the multi-layer graphene and iron cobalt layered double hydroxide composite material of the embodiment of the present invention 1
Scanning electron microscope (SEM) photograph；
Fig. 5 is the low power of the multi-layer graphene and iron cobalt layered double hydroxide composite material of the embodiment of the present invention 1
Transmission electron microscope picture；
Fig. 6 is the high power of the multi-layer graphene and iron cobalt layered double hydroxide composite material of the embodiment of the present invention 1
Transmission electron microscope picture；
Fig. 7 is that the multi-layer graphene of the embodiment of the present invention 1 is once filled with iron cobalt layered double hydroxide composite material
Discharge curve, capacity 1187F.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are some of the embodiments of the present invention, instead of all the embodiments.Based on this hair
Embodiment in bright, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
Referring to Fig. 1, it show the multi-layer graphene and iron cobalt layered double hydroxide composite wood of the embodiment of the present invention
The step flow chart of material comprising following steps：
S10, expanded graphite generate multi-layer graphene solution after ultrasound；
Specifically, S10 includes the following steps：
The in the mixed solvent of S101, DMF and distilled water is added expanded graphite and carries out, and mixed solvent is used as after mixing；It is preferred that
The volume ratio of ground, DMF and distilled water is 9:1~6:4
S102, in the mixed solvent are added after expanded graphite carries out ultrasonic vibration and obtain multi-layer graphene solution.Preferably,
In S102, expanded graphite is 0.2mg/ml~1.0mg/ml relative to mixed solvent volume.
S20 is generated using hydrothermal synthesis method close to parallel graphene at graphene surface and in the vertical stone of outer surface
The iron cobalt layered double hydroxide of black alkene, obtains the composite wood of multi-layer graphene and iron cobalt layered double hydroxide
Material.
Specifically, S20 includes the following steps：
Four water frerrous chloride (FeCl are added in S201 in multi-layer graphene mixed solution2·4H2O), cobalt acetate (Co
(CH3COO)2·4H2) and anhydrous sodium acetate (CH O3COONa), it is put into magnetic stirring apparatus and is stirred with 500 rpms of rotating speed
3-7 minutes；Preferably, FeCl2·4H2O is 30mmol/L~80mmol/L relative to the molar ratio of mixed solvent；Co
(CH3COO)2·4H2Cobalt atom in O and FeCl2·4H2The molar ratio of iron atom in O is 2:1~1:1；CH3COONa's is dense
Degree is 0.08mol/L~0.25mol/L.
Solution after stirring is poured into the stainless steel hydrothermal reaction kettle of polytetrafluoroethylene (PTFE) by S202, in 100~120 DEG C of temperature
Lower heat preservation obtains reaction production object for 0.5~3 hour after postcooling to room temperature, take out reaction product；
S203, reaction product alcohol and each 3 times of water eccentric cleaning, 60 DEG C of dryings 24 hours, obtain in drying box
The composite material of multi-layer graphene and iron cobalt layered double hydroxide.
By the composite material of the multi-layer graphene and iron cobalt layered double hydroxide of arrangement above, by Multi-layer graphite
Alkene and vertical-growth are in multi-layer graphene upper surface and the parallel iron cobalt layered bi-metal hydrogen for being grown on multi-layer graphene upper surface
Oxide forms, wherein close to parallel graphene and the iron cobalt layers shape in the vertical graphene of outer surface at graphene surface
The thickness of double-metal hydroxide, obtained iron cobalt layered double hydroxide is less than 25nm, uniform in size.
A kind of ultracapacitor uses answering for a kind of above-mentioned multi-layer graphene and iron cobalt layered double hydroxide
Condensation material, conductive capability are strong.It is obtained by the in the mixed solvent supersonic expansion graphite formed in organic and inorganic, preparation method letter
It is single, it is made of Multi-layer graphite layer, surface does not introduce oxygen-containing functional group, thus its chemism is low.Multi-layer graphene has
Good electric conductivity and big surface area, it is advantageous to improve the surface area of material as the substrate of layered hydroxide, and improve material
The conductivity of material.Layered double hydroxide is prepared on multi-layer graphene surface using hydrothermal synthesis method, a step may be implemented
Prepared by method, the composite material being prepared is uniform, realizes whole coverings of graphene surface.The method and process of the present invention is simple,
It is easy to control, it is at low cost, it is suitble to industrialized production, it is efficient to prepare composite material, and stock utilization is high.It is made of the material
Capacity of super capacitor is high, and cycle performance and stability are good.The thickness of obtained layered double hydroxide is less than 25nm,
It is uniform in size.Thin stratiform is conducive to improve surface area.Layered double hydroxide is flat on the layer close to graphene
Row is arranged in graphene, and subsequent one layer is perpendicular to the arrangement of graphene direction.Hydrogen can be enhanced by being parallel to the arrangement of graphene
The active force of oxide and graphene makes stratiform be not easy to fall off from the right surface of graphite.And the layered metal hydroxides of outer layer
To be arranged perpendicular to substrate, the surface area of composite material can be increased, so as to improve the contact area with electrolyte, to increase
Capacitive character.Meanwhile the diffusion length of charge in the composite is reduced, to improve the power-performance of capacitance.
Illustrate the implementation process of the present invention below by way of several concrete application examples.
Embodiment 1
8mlDMF and 2ml distillations water phase is mixed up for mixed solvent, adds 2mg expanded graphites toward in the mixed solvent, ultrasound is shaken
It swings 2 hours, obtains multi-layer graphene needed for the present invention, scanning electron microscope (SEM) photograph is as shown in Figure 2.Add in mixed solution
65.6mgCH3COONa, 59.7mgFeCl2·4H2O and 149.4mgCo (CH3COO)2·4H2O, FeCl2·4H2O is relative to mixing
The molar ratio of solvent is 30mmol/L, Co (CH3COO)2·4H2Cobalt atom in O and FeCl2·4H2The molar ratio of iron atom in O
It is 2：1, CH3A concentration of 0.08mol/L of COONa is put into magnetic stirring apparatus and is stirred 3 minutes with 500 rpms of rotating speed；
Solution is poured into the stainless steel hydrothermal reaction kettle of polytetrafluoroethylene (PTFE), it is 30% to make compactedness of the solution in hydrothermal reaction kettle.
1 hour postcooling is kept the temperature at a temperature of 100 DEG C to room temperature；Reactant is taken out from hydrothermal reaction kettle, uses distilled water and alcohol
Carry out each 3 times of eccentric cleaning, 60 DEG C of drying 24 hours in drying box of the solution after cleaning, obtain dry multi-layer graphene and
The composite material of iron cobalt layered double hydroxide, the wherein thickness of every layer of iron cobalt layered double hydroxide are 5nm.
Above-described multi-layer graphene is as shown in Fig. 2, the scanning of the wherein multi-layer graphene of Fig. 2 embodiment of the present invention is electric
As seen in figures 3-6, wherein Fig. 3 is the present invention to the composite material of mirror figure, multi-layer graphene and iron cobalt layered double hydroxide
The low power scanning electron microscope (SEM) photograph of the multi-layer graphene and iron cobalt layered double hydroxide composite material of embodiment 1, Fig. 4 are this hair
The high power scanning electron microscope (SEM) photograph of the multi-layer graphene and iron cobalt layered double hydroxide composite material of bright embodiment 1, Fig. 5 are this
The low power transmission electron microscope picture of the multi-layer graphene and iron cobalt layered double hydroxide composite material of inventive embodiments 1, Fig. 6 are
The high power transmission electron microscope picture of the multi-layer graphene and iron cobalt layered double hydroxide composite material of the embodiment of the present invention 1.It adopts
Performance of the supercapacitor test is carried out with performance of the supercapacitor test system, as shown in fig. 7, Fig. 7 is the embodiment of the present invention 1
Multi-layer graphene and iron cobalt layered double hydroxide charging and discharging curve figure of composite material, charging time 500s, electric discharge
Time is 470s, discharge capacity 1187F.
Embodiment 2
Measurement 8mlDMF and 2ml distillations water phase, which is mixed up, to be surpassed for mixed solvent toward in the mixed solvent addition 4mg expanded graphites
Sound oscillation 3 hours, obtains multi-layer graphene needed for the present invention.Expanded graphite is 0.4mg/ml relative to mixed solvent volume,
98.4mg CH are added in mixed solution3COONa, 79.6mg FeCl2·4H2O and 199.2mg Co (CH3COO)2·4H2O,
FeCl2·4H2O is 40mmol/L, Co (CH relative to the molar ratio of mixed solvent3COO)2·4H2Cobalt atom in O with
FeCl2·4H2The molar ratio of iron atom is 2 in O：1, CH3A concentration of 0.12mol/L of COONa, be put into magnetic stirring apparatus with
500 rpms of rotating speed stirs 4 minutes；Solution is poured into the stainless steel hydrothermal reaction kettle of polytetrafluoroethylene (PTFE), solution is made to exist
Compactedness in hydrothermal reaction kettle is 30%.1 hour postcooling is kept the temperature at a temperature of 105 DEG C to room temperature；From hydrothermal reaction kettle
Reactant is taken out, carries out eccentric cleaning each 3 times using distilled water and alcohol, solution 60 DEG C of dryings 24 in drying box after cleaning
Hour, obtain the composite material of dry multi-layer graphene and iron cobalt layered double hydroxide, the wherein double gold of iron cobalt layers shape
The thickness for belonging to every layer of hydroxide is 10nm.
Embodiment 3
Measurement 7mlDMF and 3ml distillations water phase, which is mixed up, to be surpassed for mixed solvent toward in the mixed solvent addition 6mg expanded graphites
Sound oscillation 4 hours, obtains multi-layer graphene needed for the present invention.Expanded graphite is 0.6mg/ml relative to mixed solvent volume,
131.2mg CH are added in mixed solution3COONa, 99.5mg FeCl2·4H2O and 124.5mg Co (CH3COO)2·4H2O,
FeCl2·4H2O is 50mmol/L, Co (CH relative to the molar ratio of mixed solvent3COO)2·4H2Cobalt atom in O with
FeCl2·4H2The molar ratio of iron atom is 1 in O：1, CH3A concentration of 0.16mol/L of COONa be put into magnetic stirring apparatus with
500 rpms of rotating speed stirs 6 minutes；Solution is poured into the stainless steel hydrothermal reaction kettle of polytetrafluoroethylene (PTFE), solution is made to exist
Compactedness in hydrothermal reaction kettle is 30%.2 hours postcoolings are kept the temperature at a temperature of 100 DEG C to room temperature；From hydrothermal reaction kettle
Reactant is taken out, carries out eccentric cleaning each 3 times using distilled water and alcohol, solution 60 DEG C of dryings 24 in drying box after cleaning
Hour, obtain the composite material of dry multi-layer graphene and iron cobalt layered double hydroxide, the wherein double gold of iron cobalt layers shape
The thickness for belonging to every layer of hydroxide is 15nm.
Embodiment 4
Measurement 6mlDMF and 4ml distillations water phase, which is mixed up, to be surpassed for mixed solvent toward in the mixed solvent addition 8mg expanded graphites
Sound oscillation 5 hours, obtains multi-layer graphene needed for the present invention.Expanded graphite is 0.8mg/ml relative to mixed solvent volume,
147.6mg CH are added in mixed solution3COONa, 119.4mg FeCl2·4H2O and 149.4mg Co (CH3COO)2·4H2O,
FeCl2·4H2O is 60mmol/L, Co (CH relative to the molar ratio of mixed solvent3COO)2·4H2Cobalt atom in O with
FeCl2·4H2The molar ratio of iron atom is 1 in O：1, CH3A concentration of 0.18mol/L of COONa, be put into magnetic stirring apparatus with
500 rpms of rotating speed stirs 7 minutes；Solution is poured into the stainless steel hydrothermal reaction kettle of polytetrafluoroethylene (PTFE), solution is made to exist
Compactedness in hydrothermal reaction kettle is 30%.3 hours postcoolings are kept the temperature at a temperature of 120 DEG C to room temperature；From hydrothermal reaction kettle
Reactant is taken out, carries out eccentric cleaning each 5 times using distilled water and alcohol, solution 70 DEG C of dryings 24 in drying box after cleaning
Hour, obtain the composite material of dry multi-layer graphene and iron cobalt layered double hydroxide, the wherein double gold of iron cobalt layers shape
The thickness for belonging to every layer of hydroxide is 20nm.
Embodiment 5
Measurement 9mlDMF and 1ml distillations water phase, which is mixed up, to be surpassed for mixed solvent toward in the mixed solvent addition 10mg expanded graphites
Sound oscillation 6 hours, obtains multi-layer graphene needed for the present invention.Wherein DMF：Distilled water volume ratio is 9：1, expanded graphite relative to
Mixed solvent volume is 1.0mg/ml, and 180.4mg CH are added in mixed solution3COONa, 139.3mg FeCl2·4H2O and
174.3mg Co(CH3COO)2·4H2O, FeCl2·4H2O is 70mmol/L, Co relative to the molar ratio of mixed solvent
(CH3COO)2·4H2Cobalt atom in O and FeCl2·4H2The molar ratio of iron atom is 1 in O：1, CH3COONa's is a concentration of
0.22mol/L is put into magnetic stirring apparatus and is stirred 8 minutes with 500 rpms of rotating speed；Solution is poured into polytetrafluoroethylene (PTFE)
In stainless steel hydrothermal reaction kettle, it is 30% to make compactedness of the solution in hydrothermal reaction kettle.Heat preservation 0.5 is small at a temperature of 110 DEG C
When postcooling to room temperature；Reactant is taken out from hydrothermal reaction kettle, carries out eccentric cleaning each 3 times using distilled water and alcohol, clearly
Solution after washing 70 DEG C of dryings 24 hours in drying box, obtain dry multi-layer graphene and iron cobalt laminated type bimetal hydroxide
The composite material of object, the wherein thickness of every layer of iron cobalt layered double hydroxide are 25nm.
Embodiment 6
Measurement 9mlDMF and 1ml distillations water phase, which is mixed up, to be surpassed for mixed solvent toward in the mixed solvent addition 10mg expanded graphites
Sound oscillation 7 hours, obtains multi-layer graphene needed for the present invention.Wherein DMF：Distilled water volume ratio is 9：1, expanded graphite relative to
Mixed solvent volume is 1.0mg/ml, and 205mg CH are added in mixed solution3COONa, 159.2mg FeCl2·4H2O and
199.2mg Co(CH3COO)2·4H2O, FeCl2·4H2O is 80mmol/L, Co relative to the molar ratio of mixed solvent
(CH3COO)2·4H2Cobalt atom in O and FeCl2·4H2The molar ratio of iron atom is 1 in O：1, CH3COONa's is a concentration of
0.25mol/L is put into magnetic stirring apparatus and is stirred 8 minutes with 500 rpms of rotating speed；Solution is poured into polytetrafluoroethylene (PTFE)
In stainless steel hydrothermal reaction kettle, it is 30% to make compactedness of the solution in hydrothermal reaction kettle.Heat preservation 1.5 is small at a temperature of 115 DEG C
When postcooling to room temperature；Reactant is taken out from hydrothermal reaction kettle, carries out eccentric cleaning each 3 times using distilled water and alcohol, clearly
Solution after washing 70 DEG C of dryings 24 hours in drying box, obtain dry multi-layer graphene and iron cobalt laminated type bimetal hydroxide
The composite material of object, the wherein thickness of every layer of iron cobalt layered double hydroxide are 25nm.
It should be appreciated that exemplary embodiment as described herein is illustrative and be not restrictive.Although being retouched in conjunction with attached drawing
One or more embodiments of the invention is stated, it should be understood by one skilled in the art that not departing from through appended right
In the case of the spirit and scope of the present invention defined by it is required that, the change of various forms and details can be made.
Claims (10)
1. the preparation method of a kind of multi-layer graphene and the composite material of iron cobalt layered double hydroxide, which is characterized in that
Include the following steps：
S10, expanded graphite generate multi-layer graphene solution after ultrasound,
S20 is generated using hydrothermal synthesis method close to parallel graphene at graphene surface and in the vertical graphene of outer surface
Iron cobalt layered double hydroxide, obtain the composite material of multi-layer graphene and iron cobalt layered double hydroxide.
2. the preparation side of multi-layer graphene according to claim 1 and the composite material of iron cobalt layered double hydroxide
Method, which is characterized in that S10 specifically includes following steps：
S101, DMF and distilled water mixing, are used as mixed solvent after mixing；
S102, in the mixed solvent are added after expanded graphite carries out ultrasonic vibration and obtain multi-layer graphene solution.
3. the preparation side of multi-layer graphene according to claim 1 and the composite material of iron cobalt layered double hydroxide
Method, which is characterized in that S20 specifically includes following steps：
Four water frerrous chloride (FeCl are added in S201 in multi-layer graphene mixed solution2·4H2O), cobalt acetate (Co
(CH3COO)2·4H2) and anhydrous sodium acetate (CH O3COONa), it is put into magnetic stirring apparatus and is stirred with 500 rpms of rotating speed
3-7 minutes；
Solution after stirring is poured into the stainless steel hydrothermal reaction kettle of polytetrafluoroethylene (PTFE) by S202, is protected at a temperature of 100~120 DEG C
Temperature obtains reaction product for 0.5~3 hour after postcooling to room temperature, take out reaction product；
S203, reaction product alcohol and each 3 times of water eccentric cleaning, 60 DEG C of dryings 24 hours, obtain multilayer in drying box
The composite material of graphene and iron cobalt layered double hydroxide.
4. the preparation side of multi-layer graphene according to claim 2 and the composite material of iron cobalt layered double hydroxide
Method, which is characterized in that in S101, the volume ratio of DMF and distilled water is 9: 1~6: 4.
5. the preparation side of multi-layer graphene according to claim 2 and the composite material of iron cobalt layered double hydroxide
Method, which is characterized in that in S102, expanded graphite is 0.2mg/ml~1.0mg/ml relative to mixed solvent volume.
6. the preparation side of multi-layer graphene according to claim 3 and the composite material of iron cobalt layered double hydroxide
Method, which is characterized in that FeCl2·4H2O is 30mmol/L~80mmol/L relative to the molar ratio of mixed solvent.
7. the preparation side of multi-layer graphene according to claim 3 and the composite material of iron cobalt layered double hydroxide
Method, Co (CH3COO)2·4H2Cobalt atom in O and FeCl2·4H2The molar ratio of iron atom in O is 2: 1~1: 1.
8. the preparation side of multi-layer graphene according to claim 3 and the composite material of iron cobalt layered double hydroxide
Method, CH3A concentration of 0.08mol/L~0.25mol/L of COONa.
9. the composite material of a kind of multi-layer graphene and iron cobalt layered double hydroxide, which is characterized in that wanted using right
Any preparation methods of 1-8 are asked to be made, by multi-layer graphene and vertical-growth in multi-layer graphene upper surface and parallel life
It is longer than the iron cobalt layered double hydroxide composition of multi-layer graphene upper surface, obtained iron cobalt layered double hydroxide
Thickness be less than 25nm, it is uniform in size.
10. a kind of ultracapacitor, which is characterized in that the material of a wherein at least pole is using as claimed in claim 9 a kind of
It is prepared by the composite material of multi-layer graphene and iron cobalt layered double hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610920428.7A CN106298287B (en) | 2016-10-21 | 2016-10-21 | A kind of composite material and preparation method and its ultracapacitor of application of multi-layer graphene and iron cobalt layered double hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610920428.7A CN106298287B (en) | 2016-10-21 | 2016-10-21 | A kind of composite material and preparation method and its ultracapacitor of application of multi-layer graphene and iron cobalt layered double hydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106298287A CN106298287A (en) | 2017-01-04 |
| CN106298287B true CN106298287B (en) | 2018-08-14 |
Family
ID=57718753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610920428.7A Active CN106298287B (en) | 2016-10-21 | 2016-10-21 | A kind of composite material and preparation method and its ultracapacitor of application of multi-layer graphene and iron cobalt layered double hydroxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106298287B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108364793B (en) * | 2017-12-28 | 2020-02-04 | 杭州电子科技大学 | CoNiFe-LDH/multilayer graphene high-performance composite energy storage material and preparation method thereof |
| CN111199834B (en) * | 2020-01-08 | 2021-08-17 | 杭州电子科技大学 | Cobalt sulfide/multilayer graphene composite material and preparation method thereof |
| CN113546628A (en) * | 2021-06-22 | 2021-10-26 | 南京工业大学 | Preparation method of bimetallic hydroxide-graphene aerogel electrocatalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496480A (en) * | 2011-12-16 | 2012-06-13 | 江南大学 | Preparation method of graphene/nickel-aluminum bi-metal hydroxide composite material and application thereof |
| CN104392843A (en) * | 2014-11-20 | 2015-03-04 | 上海电力学院 | Three-dimensional lamellar metal hydroxide nanosheet/graphene aerogel composite and preparation method thereof |
-
2016
- 2016-10-21 CN CN201610920428.7A patent/CN106298287B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496480A (en) * | 2011-12-16 | 2012-06-13 | 江南大学 | Preparation method of graphene/nickel-aluminum bi-metal hydroxide composite material and application thereof |
| CN104392843A (en) * | 2014-11-20 | 2015-03-04 | 上海电力学院 | Three-dimensional lamellar metal hydroxide nanosheet/graphene aerogel composite and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Precious-Metal-Free Co–Fe–O/rGO Synergetic Electrocatalysts for Oxygen Evolution Reaction by a Facile Hydrothermal Route";Jing Geng, et al.;《ChemSusChem》;20150108;第8卷;第659-664页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106298287A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | MOF-derived NiO/NiCo2O4 and NiO/NiCo2O4-rGO as highly efficient and stable electrocatalysts for oxygen evolution reaction | |
| Liu et al. | Nickel cobaltite nanostructures for photoelectric and catalytic applications | |
| Zhan et al. | Synthesis of mesoporous NiCo2O4 fibers and their electrocatalytic activity on direct oxidation of ethanol in alkaline media | |
| CN105152281B (en) | The preparation method of the classifying porous carbon material structure capacitance desalination electrode of core shell structure | |
| Lota et al. | Supercapacitors based on nickel oxide/carbon materials composites | |
| Shang et al. | Coaxial Ni x Co2 x (OH) 6 x/TiN nanotube arrays as supercapacitor electrodes | |
| US20130168611A1 (en) | Composite electrode material, manufacturing method and application thereof | |
| Reddy et al. | Highly porous metal organic framework derived NiO hollow spheres and flowers for oxygen evolution reaction and supercapacitors | |
| CN105118688B (en) | A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/graphene film material | |
| CN106315522B (en) | A kind of NiSe three-dimensional porous nano sheet materials and preparation method thereof for ultracapacitor | |
| CN109256567A (en) | A kind of preparation method of transition metal/nitrogen doped corrugated carbon nanotube | |
| CN104616915B (en) | A kind of preparation method of graphene ruthenium-oxide composite | |
| CN104021948B (en) | Nanofiber-shaped three-dimensional nickel hydroxide/carbon nanotube composite material as well as preparation method and application thereof | |
| CN108470628B (en) | A kind of combination electrode material and preparation method thereof | |
| CN105788884B (en) | A kind of preparation method of ultracapacitor manganese dioxide/carbon paper combination electrode | |
| CN108597890A (en) | A kind of polyaniline/graphene/nickel manganese hydroxide electrode material for super capacitor and preparation method thereof | |
| Lv et al. | Preparation of carbon nanosheet by molten salt route and its application in catalyzing VO2+/VO2+ redox reaction | |
| CN106298287B (en) | A kind of composite material and preparation method and its ultracapacitor of application of multi-layer graphene and iron cobalt layered double hydroxide | |
| CN107089707A (en) | Structure capacitance desalination electrode core shell structure three-dimensional graphene composite material and preparation method thereof | |
| CN102623189A (en) | Method for preparing electrode material for graphene/manganese dioxide thin-film asymmetrical supercapacitor | |
| CN110085453A (en) | The preparation method and application of the hud typed Ni-Co LDH@Ni-Mn LDH of carbon nanotube foam support | |
| Jiang et al. | Facile preparation of a novel composite Co-Ni (OH) 2/carbon sphere for high-performance supercapacitors | |
| Zeng et al. | Hierarchical 3D micro‐nanostructures based on in situ deposited bimetallic metal‐organic structures on carbon fabric for supercapacitor applications | |
| CN109473649A (en) | A kind of sodium-ion battery composite negative pole material and preparation method thereof | |
| CN103943374A (en) | Preparation method of NiO (Nickel Oxide) nanosheet/ultra-fine nanowire supercapacitor material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191129 Address after: 318000 No.2, building 17, Zhejiang Zhongde (Taizhou) industrial cooperation Park, no.558, haihao Road, Taizhou City, Zhejiang Province Patentee after: Zhejiang Boshi Technology Co., Ltd Address before: Hangzhou City, Zhejiang province 310018 Xiasha Higher Education Park No. 2 street Patentee before: Hangzhou Electronic Science and Technology Univ |