CN110379639A - NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material and preparation method and application - Google Patents
NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material and preparation method and application Download PDFInfo
- Publication number
- CN110379639A CN110379639A CN201910589388.6A CN201910589388A CN110379639A CN 110379639 A CN110379639 A CN 110379639A CN 201910589388 A CN201910589388 A CN 201910589388A CN 110379639 A CN110379639 A CN 110379639A
- Authority
- CN
- China
- Prior art keywords
- nico
- double hydroxide
- hydroxide nano
- carbon cloth
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
-
- 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
-
- 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)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material and preparation method and applications, this method comprises: by carbon cloth be placed in dissolved with nickel salt, cobalt salt, urea water in, be heat-treated；Through cooling, washs and be dried to obtain the carbon cloth containing nano wire；The carbon cloth containing nano wire is added in the aqueous solution containing nickel salt, cobalt salt and hexamethylenetetramine and is heat-treated, then is cleaned, dry, obtains NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material.The composite material has specific capacity value higher, and energy density is larger, and the good advantage of circulation discharge stability is highly suitable as electrode material.Moreover, the preparation method has a simple process, and the used time is few, and does not have to addition binder, and process is easily controllable, and preparation method has many advantages, such as green, cleans, is efficient, simple low in cost, application value with higher.
Description
Technical field
The present invention relates to electrochemical fields, specifically, and in particular, to a kind of NiCo double hydroxide nano line@NiCo
Double hydroxide nano piece composite material and preparation method and application.
Background technique
With constantly increasing to sustainable and renewable energy demand, reliable energy storage technology sets portable electronic
Standby, mixed power electric car and smart grid become more and more important.Supercapacitor (SC) is due to its high power density, out
The cycle life of color, fast charge/discharge process and safety are expected to become the most potential substitution of high-performance power supply of new generation
One of product.The performance of supercapacitor is heavily dependent on electrode material, and developing has the novel of high electrochemical performance
High quality electrode material is the striving direction of researcher from now on.
Currently, a kind of energy storage device of the supercapacitor as green, has received widespread attention in today's society, but it is super
The performance and electrode material of grade capacitor have a much relations, thus for the exploitation of electrode material and research be we all the time
Target.Further, how to obtain that specific capacity value is higher, and energy density is larger, the good electrode of circulation discharge stability is multiple
Condensation material has been a hot spot of research.
Summary of the invention
The object of the present invention is to provide a kind of NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite woods
Material and its preparation method and application, which has
Specific capacity value is higher, and energy density is larger, the good advantage of circulation discharge stability.Moreover, the preparation method has a simple process,
Used time is few, and does not have to addition binder, and process is easily controllable, and preparation method has green, cleans, is efficient, simple cost
The advantages that cheap, application value with higher.
To achieve the goals above, the present invention provides a kind of NiCo double hydroxide nano line@NiCo double-hydroxides
The preparation method of nanosheet composite material, comprising: (1) by carbon cloth be placed in dissolved with nickel salt, cobalt salt, urea aqueous solution in, into
Row heat treatment；(2) it by heat treated carbon cloth, through cooling, washs and is dried to obtain containing NiCo double hydroxide nano line
Carbon cloth；(3) carbon cloth containing NiCo double hydroxide nano line is added to containing nickel salt, cobalt salt and hexamethylenetetramine
Aqueous solution in be heat-treated, cleaned, dried after heat treatment, obtain the bis- hydrogen-oxygens of NiCo double hydroxide nano line NiCo
Compound nanosheet composite material.
The present invention also provides a kind of NiCo double hydroxide nano line@NiCo obtained according to previously described preparation method
Double hydroxide nano piece composite material.
Moreover, the present invention also provides a kind of bis- hydroxides of previously described NiCo double hydroxide nano line@NiCo
Object nanosheet composite material is as the application in electrode material.
Through the above technical solutions, the present invention is using hydrothermal method directly by NiCo double hydroxide nano line (abbreviation
NCW) material modification does not need addition binder on carbon cloth, in modification, and what is obtained contains NiCo double hydroxide nano
NiCo double hydroxide nano line in the carbon cloth of line can very securely in conjunction with carbon cloth substrate；The present invention is again to contain NiCo
The carbon cloth of double hydroxide nano line is introduced back into nickel salt, cobalt salt and hexamethylenetetramine hydro-thermal reaction as presoma, will
NiCo double hydroxide nano piece (abbreviation NCP) is compounded on the carbon cloth containing NiCo double hydroxide nano line, is obtained
NiCo double hydroxide nano line@NiCo double hydroxide nano plate electrode composite material.
The NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material that the present invention obtains has specific volume
Magnitude is higher, and energy density is larger, and the good advantage of circulation discharge stability is highly suitable as electrode material.Inventor speculates:
The present invention allows electrode material (NiCo double hydroxide nano line and NiCo double hydroxide nano using the method for growth in situ
Piece) it is grown directly upon on collector electrode (carbon cloth), reduce the resistance of charge transmission, which combines nano wire and nanometer
The multiple reaction site of piece and the stability of structure, and then improve performance of the material in terms of electrochemistry.
Moreover, the preparation method has a simple process, and the used time is few, and does not have to addition binder, and process is easily controllable, and its
Preparation method has many advantages, such as green, cleans, is efficient, simple low in cost, application value with higher.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is that sweeping for NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material is made in embodiment 2
Retouch electron microscopic (SEM) figure.
Fig. 2 is that the saturating of NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material is made in embodiment 2
Penetrate electron microscopic (TEM) figure.
Fig. 3 is that NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material is made in embodiment 2
XRD diagram.
Fig. 4 is the perseverance that NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material is made in embodiment 2
Current charging and discharging (CV) figure.
Fig. 5 is the perseverance that NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material is made in embodiment 2
Current charging and discharging (CP) figure.
Fig. 6 is that NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material is made in electricity in embodiment 2
The capacity retention rate figure of 1000 constant current charge-discharges circulation, 1000 circle of current density 10A/g.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of systems of NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material
Preparation Method, comprising: (1) by carbon cloth be placed in dissolved with nickel salt, cobalt salt, urea aqueous solution in, be heat-treated；It (2) will be at heat
The carbon cloth managed through cooling, washs and is dried to obtain the carbon cloth containing NiCo double hydroxide nano line；(3) contain by described in
The carbon cloth of NiCo double hydroxide nano line, which is added in the aqueous solution containing nickel salt, cobalt salt and hexamethylenetetramine, carries out hot place
Reason, is cleaned after heat treatment, is dried, obtain NiCo double hydroxide nano line NiCo double hydroxide nano piece composite material.
Through the above technical solutions, the present invention is using hydrothermal method directly by NiCo double hydroxide nano line (abbreviation
NCW) material modification does not need addition binder on carbon cloth, in modification, and what is obtained contains NiCo double hydroxide nano
NiCo double hydroxide nano line in the carbon cloth of line can very securely in conjunction with carbon cloth substrate；The present invention is again to contain NiCo
The carbon cloth of double hydroxide nano line is introduced back into nickel salt, cobalt salt and hexamethylenetetramine hydro-thermal reaction as presoma, will
NiCo double hydroxide nano piece (abbreviation NCP) is compounded on the carbon cloth containing NiCo double hydroxide nano line, is obtained
NiCo double hydroxide nano line@NiCo double hydroxide nano plate electrode composite material.
The NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material that the present invention obtains has specific volume
Magnitude is higher, and energy density is larger, and the good advantage of circulation discharge stability is highly suitable as electrode material.Inventor speculates:
The present invention allows electrode material (NiCo double hydroxide nano line and NiCo double hydroxide nano using the method for growth in situ
Piece) it is grown directly upon on collector electrode (carbon cloth), reduce the resistance of charge transmission, which combines nano wire and nanometer
The multiple reaction site of piece and the stability of structure, and then improve performance of the material in terms of electrochemistry.
Moreover, the preparation method has a simple process, and the used time is few, and does not have to addition binder, and process is easily controllable, and its
Preparation method has many advantages, such as green, cleans, is efficient, simple low in cost, application value with higher.
In a kind of preferred embodiment of the present invention, specific capacity value is higher in order to obtain, and energy density is larger, and circulation is put
The good electrode composite material of electrical stability, it is preferable that in step (1), nickel salt, cobalt salt and urea mol ratio are 1:1-3:1-3.
Specific capacity value is higher in order to obtain, and energy density is larger, the good electrode composite material of circulation discharge stability, more into
Preferably, in step (1), relative to the carbon cloth of 0.05g, the dosage of nickel salt is 0.002-0.006mol to one step.
According to the raw material proportioning of above-mentioned technical proposal in the present invention, electrode composite material of the invention can be obtained, and it is right
It in the concentration of each component, can be adjusted, in a kind of preferred embodiment of the present invention, compare in order to obtain in a wider range
Capacitance is higher, and energy density is larger, the good electrode composite material of circulation discharge stability, it is preferable that water-soluble in step (1)
The concentration of nickel salt is 1-3mmol/L in liquid.
In a kind of preferred embodiment of the present invention, specific capacity value is higher in order to obtain, and energy density is larger, and circulation is put
The good electrode composite material of electrical stability, it is preferable that in step (3), the molar ratio of nickel salt, cobalt salt and hexamethylenetetramine is 1:
1-3:1-3。
According to the raw material proportioning of above-mentioned technical proposal in the present invention, electrode composite material of the invention can be obtained, and it is right
It in the concentration of each component, can be adjusted, in a kind of preferred embodiment of the present invention, compare in order to obtain in a wider range
Capacitance is higher, and energy density is larger, the good electrode composite material of circulation discharge stability, it is preferable that water-soluble in step (3)
The concentration of nickel salt is 1-3mmol/L in liquid.
It for the condition being heat-treated in step (1), can be adjusted in a wider range, in a kind of preferred reality of the present invention
It applies in mode, specific capacity value is higher in order to obtain, and energy density is larger, the preferable electrode composite material of cyclical stability, preferably
Ground, it is 90-130 DEG C that the middle condition being heat-treated of step (1), which includes: temperature,.
It for the time being heat-treated in step (1), can be adjusted in a wider range, in a kind of preferred reality of the present invention
It applies in mode, specific capacity value is higher in order to obtain, and energy density is larger, the preferable electrode composite material of cyclical stability, preferably
Ground, step (1) the middle time being heat-treated is 3-15h.
It for the condition being heat-treated in step (3), can be adjusted in a wider range, in a kind of preferred reality of the present invention
It applies in mode, specific capacity value is higher in order to obtain, and energy density is larger, the preferable electrode composite material of cyclical stability, preferably
Ground, it is 90-130 DEG C that the middle condition being heat-treated of step (3), which includes: temperature,
It for the time being heat-treated in step (3), can be adjusted in a wider range, in a kind of preferred reality of the present invention
It applies in mode, specific capacity value is higher in order to obtain, and energy density is larger, the preferable electrode composite material of cyclical stability, preferably
Ground, step (3) the middle time being heat-treated is 3-20h.
And for the preparation of raw material, those skilled in the art can there are many selections, of the invention a kind of preferred
In embodiment, in order to use clean carbon cloth, it is preferable that before carrying out step (1), carried out to carbon cloth following pretreated
Step: carrying out ultrasonic cleaning 10-20min to carbon cloth with the hydrochloric acid of 1-3mol/L, then spends water and/or dehydrated alcohol is cleaned multiple times
10-15min。
Certainly, the step of the washing and drying for carbon cloth heat treated in intermediate Part (1) before carrying out step (3)
Suddenly can there are many selections, in a kind of preferred embodiment of the present invention, it is preferable that step before carrying out step (3)
(1) heat treated carbon cloth is washed with water and is dried in vacuo in 50-70 DEG C in.
In the above-mentioned technical solutions, it for nickel salt, can be selected in a wider range, as long as it can be ionized in water
Bivalent nickel ion out, in a kind of preferred embodiment of the present invention, specific capacity value is higher in order to obtain, energy density compared with
Greatly, the good electrode composite material of circulation discharge stability, it is preferable that nickel salt is Nickel dichloride hexahydrate and/or Nickelous nitrate hexahydrate.
In the above-mentioned technical solutions, it for cobalt salt, can be selected in a wider range, as long as it can be ionized in water
Divalent cobalt ion out, in a kind of preferred embodiment of the present invention, specific capacity value is higher in order to obtain, energy density compared with
Greatly, the good electrode composite material of circulation discharge stability, it is preferable that cobalt salt is cobalt chloride hexahydrate and/or four water cobalt acetates.
In the above-mentioned technical solutions, for the selection of water, routine experiment water, such as deionized water, primary steaming be can be
The present invention can be achieved in distilled water, distilled water, ultrapure water etc., different herein to enumerate.
The present invention also provides a kind of NiCo double hydroxide nano line@NiCo obtained according to previously described preparation method
Double hydroxide nano piece composite material.
The NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material that the present invention obtains has specific volume
Magnitude is higher, and energy density is larger, and the good advantage of circulation discharge stability is highly suitable as electrode material.Inventor speculates:
The present invention allows electrode material (NiCo double hydroxide nano line and NiCo double hydroxide nano using the method for growth in situ
Piece) it is grown directly upon on collector electrode (carbon cloth), reduce the resistance of charge transmission, which combines nano wire and nanometer
The multiple reaction site of piece and the stability of structure, and then improve performance of the material in terms of electrochemistry.
Moreover, the present invention also provides a kind of bis- hydroxides of previously described NiCo double hydroxide nano line@NiCo
Object nanosheet composite material is as the application in electrode material.
Further, the NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material is applicable in
In in three-electrode system be used as working electrode material.
And reference electrode in three-electrode system, the common electrode that this field can be used electrode, of the invention one
It is compound with the NiCo double hydroxide nano line@NiCo double hydroxide nano piece in the present invention in kind preferred embodiment
Material is made as reference electrode, Pt electrode to electrode as working electrode in three-electrode system, calomel electrode.
The present invention will be described in detail by way of examples below.
Embodiment 1
(1) carbon cloth pre-processes: using 3M hydrochloric ultrasonic wave 10min, deionized water, dehydrated alcohol are respectively washed 15min 3 times；
(2) by 60 DEG C of carbon cloth pretreated vacuum drying, its quality is referred to as 0.05g；
(3) NiCl is weighed2·6H2O is 0.47g, CoCl2·6H2O is 0.95, urea is 0.72g molten respectively at room temperature
It in 50mL deionized water, is transferred in autoclave and is heat-treated after scattering, temperature setting is 120 DEG C, the time
For 6h；
(4) after being heat-treated, heat treated carbon cloth is rinsed with deionized water, 60 DEG C of vacuum drying；
(5) Ni (NO is weighed3)2.6H2O is 0.58g, Co (NO3)2.6H2O is 0.58g, and hexamethylenetetramine (HMTA) is
1.1g, ultrasonic disperse are transferred in autoclave after scattering and are heat-treated in 30mL deionized water, temperature setting
It is 100 DEG C, time 5h.
(6) after being heat-treated, it to be down to room temperature to temperature of reaction kettle, rinses carbon cloth with ethyl alcohol, ultrasound removes the oxide on surface,
60 DEG C of vacuum drying.
Embodiment 2
(1) carbon cloth pre-processes: using 3M hydrochloric ultrasonic wave 10min, deionized water, dehydrated alcohol are respectively washed 15min 3 times；
(2) by 60 DEG C of carbon cloth pretreated vacuum drying, its quality is referred to as 0.05g；
(3) NiCl is weighed2·6H2O is 0.47g, CoCl2·6H2O is 0.95, urea is 0.72g molten respectively at room temperature
It in 50mL deionized water, is transferred in autoclave and is heat-treated after scattering, temperature setting is 120 DEG C, the time
For 6h；
(4) after being heat-treated, heat treated carbon cloth is rinsed with deionized water, 60 DEG C of vacuum drying；
(5) Ni (NO is weighed3)2.6H2O is 0.58g, Co (NO3)2.6H2O is 0.58g and HMTA is 1.1g, ultrasonic disperse in
It in 30mL deionized water, is transferred in autoclave and is heat-treated after scattering, temperature setting is 100 DEG C, and the time is
10h。
(6) after being heat-treated, it to be down to room temperature to temperature of reaction kettle, rinses carbon cloth with ethyl alcohol, ultrasound removes the oxide on surface,
60 DEG C of vacuum drying.
Embodiment 3
(1) carbon cloth pre-processes: using 3M hydrochloric ultrasonic wave 10min, deionized water, dehydrated alcohol are respectively washed 15min 3 times；
(2) by 60 DEG C of carbon cloth pretreated vacuum drying, its quality is referred to as 0.05g；
(3) NiCl is weighed2·6H2O is 0.47g, CoCl2·6H2O is 0.95, urea is 0.72g molten respectively at room temperature
It in 50mL deionized water, is transferred in autoclave and is heat-treated after scattering, temperature setting is 120 DEG C, the time
For 6h；
(4) after being heat-treated, heat treated carbon cloth is rinsed with deionized water, 60 DEG C of vacuum drying；
(5) Ni (NO is weighed3)2.6H2O is 0.58g, Co (NO3)2.6H2O is 0.58g and HMTA is 1.1g, ultrasonic disperse in
It in 30mL deionized water, is transferred in autoclave and is heat-treated after scattering, temperature setting is 100 DEG C, and the time is
15h。
(6) after being heat-treated, it to be down to room temperature to temperature of reaction kettle, rinses carbon cloth with ethyl alcohol, ultrasound removes the oxide on surface,
60 DEG C of vacuum drying.
Embodiment 4
(1) carbon cloth pre-processes: using 1M hydrochloric ultrasonic wave 10min, deionized water, dehydrated alcohol are respectively washed 15min 3 times；
(2) by 60 DEG C of carbon cloth pretreated vacuum drying, its quality is referred to as 0.05g；
(3) 0.001mol NiCl is taken2·6H2O, 0.001mol CoCl2·6H2O, 0.001mol urea, divide at room temperature
It not being dissolved in 20mL deionized water, is transferred in autoclave and is heat-treated after scattering, temperature setting is 90 DEG C, when
Between be 3h；
(4) after being heat-treated, heat treated carbon cloth is rinsed with deionized water, 60 DEG C of vacuum drying；
(5) 0.001mol Ni (NO is taken3)2.6H2O、0.001mol Co(NO3)2.6H2O and 0.001mol HMTA, ultrasound
It being scattered in 10mL deionized water, is transferred in autoclave and is heat-treated after scattering, temperature setting is 90 DEG C, when
Between be 3h.
(6) after being heat-treated, it to be down to room temperature to temperature of reaction kettle, rinses carbon cloth with ethyl alcohol, ultrasound removes the oxide on surface,
50 DEG C of vacuum drying.
Embodiment 5
(1) carbon cloth pre-processes: using 4M hydrochloric ultrasonic wave 10min, deionized water, dehydrated alcohol are respectively washed 15min 3 times；
(2) by 70 DEG C of carbon cloth pretreated vacuum drying, its quality is referred to as 0.05g；
(3) 0.003mol NiCl is taken2·6H2O, 0.003mol CoCl2·6H2O, 0.003mol urea, divide at room temperature
It not being dissolved in 60mL deionized water, is transferred in autoclave and is heat-treated after scattering, temperature setting is 130 DEG C,
Time is 15h；
(4) after being heat-treated, heat treated carbon cloth is rinsed with deionized water, 70 DEG C of vacuum drying；
(5) 0.003mol Ni (NO is taken3)2.6H2O、0.003mol Co(NO3)2.6H2O and 0.003molHMTA, ultrasound point
It dissipating in 40mL deionized water, is transferred in autoclave and is heat-treated after scattering, temperature setting is 130 DEG C, when
Between be 20h.
(6) after being heat-treated, it to be down to room temperature to temperature of reaction kettle, rinses carbon cloth with ethyl alcohol, ultrasound removes the oxide on surface,
70 DEG C of vacuum drying.
Comparative example 1
(1) carbon cloth pre-processes: using 3M hydrochloric ultrasonic wave 10min, deionized water, dehydrated alcohol are respectively washed 15min 3 times；
(2) by 60 DEG C of carbon cloth pretreated vacuum drying, its quality is referred to as 0.0501g；
(3) Ni (NO is weighed3)2.6H2O is 0.58g, Co (NO3)2.6H2O is 0.58g and HMTA is 1.1g, ultrasonic disperse in
It in 30mL deionized water, is transferred in autoclave and is heat-treated after scattering, temperature setting is 100 DEG C, and the time is
5h。
(4) after reaction, heat treated carbon cloth is rinsed with deionized water, 60 DEG C of vacuum drying.
Comparative example 2
(1) carbon cloth pre-processes: using 3M HCl ultrasound 10min, deionized water, dehydrated alcohol are respectively washed 15min 3 times；
(2) by 60 DEG C of carbon cloth pretreated vacuum drying, its quality is referred to as 0.05g；
(3) Ni (NO is weighed3)2.6H2O is 0.58g, Co (NO3)2.6H2O is 0.58g and HMTA is 1.1g, ultrasonic disperse in
It in 30mL deionized water, is transferred in autoclave and is heat-treated after scattering, temperature setting is 100 DEG C, and the time is
10h。
(4) after being heat-treated, heat treated carbon cloth is rinsed with deionized water, 60 DEG C of vacuum drying.
Comparative example 3
(1) carbon cloth pre-processes: using 3M hydrochloric ultrasonic wave 10min, deionized water, dehydrated alcohol are respectively washed 15min 3 times；
(2) by 60 DEG C of carbon cloth pretreated vacuum drying, its quality is referred to as 0.05g；
(3) Ni (NO is weighed3)2.6H2O is 0.58g, Co (NO3)2.6H2O is 0.58g and HMTA is 1.1g, ultrasonic disperse in
It in 30mL deionized water, is transferred in autoclave and is heat-treated after scattering, temperature setting is 100 DEG C, and the time is
15h。
(4) after being heat-treated, carbon cloth is rinsed with deionized water, 60 DEG C of vacuum drying.
Detect example
Fig. 3 is that NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material is made in embodiment 2
XRD diagram.As seen from Figure 3, the diffraction maximum occurred at 34.952,37.652,39.401,60.853 ° respectively corresponds NiCo LDH's
(012), (104), (015), (110) face, it is indicated above that successfully synthesizing the bis- hydrogen-oxygens of NiCo double hydroxide nano line@NiCo
Compound nanosheet composite material.
Fig. 1 is that sweeping for NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material is made in embodiment 2
Retouch electron microscopic (SEM) figure.As shown in Figure 1, product is NiCo double hydroxide nano line and NiCo double hydroxide nano piece
Hybrid multi-stage structure.Crosslinking nano piece uniformly increases on the skeleton of nano wire, and the flower-like structure being crosslinked isolates list
Only nanometer sheet.
Fig. 2 is that the saturating of NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material is made in embodiment 2
Penetrate electron microscopic (TEM) figure.In figure, nano wire and nanometer sheet are interweaved, and nanometer sheet is well dispersed in around nano wire, shape
At the mixing array with open free space abundant.It is presumed that the laminated structure of formation can quickly transmit charge, increase
Add reactivity site, and then improves its chemical property.
Through detecting, SEM, TEM, XRD of the composite material in embodiment 1,3-5 are similar in embodiment 2, illustrate to react
The influence of time and temperature to pattern is not very big, and nano flake shell is connected with each other and provides bigger specific surface area, generates
More active sites more effectively connect so as to shorten ion diffused line to provide between electrode material and electrolyte
Touching.
Electrochemical property test
1, using composite material obtained in embodiment and comparative example as working electrode, calomel electrode is as reference electricity
Pole, Pt electrode are used as to electrode.Electrolyte is 6mol/L KOH solution.
2, electrochemical property test: entire three-electrode system is completed with electrochemical workstation CHI660C test macro.
Fig. 4 is that following for NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material is made in embodiment 2
Ring volt-ampere (CV) figure.It can be seen that the material there are apparent redox peaks in figure, show that the material has good capacitive property.
Fig. 5 is the perseverance that NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material is made in embodiment 2
Current charging and discharging (CP) figure.As shown in figure 5, specific discharge capacity value is up to 3206F/g in current density 1A/g；When 40A/g,
Specific capacity value remains to up to 924.4F/g, can obtain the chemical property of nano wire@NiCo double hydroxide nano piece composite material
Very well,.
Fig. 6 is that NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material is made in electricity in embodiment 2
The specific capacity value retention rate figure of 1000 constant current charge-discharges circulation of current density 10A/g.As it can be seen that carrying out 600 charge and discharge
It is able to maintain the 90% of initial capacity afterwards, and 80% of initial capacity or more can also be kept after carrying out 1000 charge and discharge, says
The bright material has preferable cyclical stability.
After being tested according to the methods of cyclic voltammetry, constant current charge-discharge test and circulation, embodiment 1-5 and right
The chemical property of ratio 1-3, through detecting, the performance of embodiment 1-5 and comparative example 1-3 are as shown in table 1.
Table 1
| Number | Specific capacitance (F/g) | Power density (W/Kg) | Energy density (Wh/Kg) |
| Embodiment 1 | 1835.6 | 225 | 51.6 |
| Embodiment 2 | 3206 | 225 | 90.2 |
| Embodiment 3 | 2584.4 | 225 | 72.7 |
| Embodiment 4 | 1682.5 | 225 | 47.3 |
| Embodiment 5 | 2096.7 | 225 | 59 |
| Comparative example 1 | 1720.3 | 225 | 48.4 |
| Comparative example 2 | 1580.2 | 225 | 44.4 |
| Comparative example 3 | 1666.7 | 225 | 46.9 |
Remarks: the upper cited corresponding electrochemical data come out of table is all gained under the conditions of current density is 1A/g.
It is as shown in table 1: comparative example 1-3 do not carry out with nano wire combined processing, only obtain double hydroxide nano containing NiCo
The carbon cloth of piece, corresponding chemical property are lower compared with the composite material in embodiment 1-5, wherein specific capacity value ratio
Lower, energy density is also relatively small；Embodiment 1-3 can clearly observe that chemical property significantly improves.It invents as a result,
People speculates: the present invention allows electrode material (NiCo double hydroxide nano line and the bis- hydroxides of NiCo using the method for growth in situ
Object nanometer sheet) it is grown directly upon on collector electrode (carbon cloth), reduce the resistance of charge transmission, which combines nano wire
With the multiple reaction site of nanometer sheet and the stability of structure, and then performance of the material in terms of electrochemistry is improved.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material, feature
It is, comprising:
(1) by carbon cloth be placed in dissolved with nickel salt, cobalt salt, urea aqueous solution in, be heat-treated；
(2) it by heat treated carbon cloth, through cooling, washs and is dried to obtain the carbon cloth containing NiCo double hydroxide nano line；
(3) carbon cloth containing NiCo double hydroxide nano line is added to containing nickel salt, cobalt salt and hexamethylenetetramine
Aqueous solution in be heat-treated, cleaned, dried after heat treatment, obtain the bis- hydrogen-oxygens of NiCo double hydroxide nano line NiCo
Compound nanosheet composite material.
2. preparation method according to claim 1, wherein in step (1), nickel salt, cobalt salt and urea mol ratio are 1:1-
3:1-3；
Preferably, relative to the carbon cloth of 0.05g, the dosage of nickel salt is 0.002-0.006mol.
3. preparation method according to claim 2, wherein in step (1), the concentration of nickel salt is 1-3mmol/ in aqueous solution
L。
4. preparation method according to claim 1, wherein in step (3), nickel salt, cobalt salt and hexamethylenetetramine rub
You are than being 1:1-3:1-3.
5. preparation method according to claim 4, wherein in step (3), the concentration of nickel salt is 1- in aqueous solution
3mmol/L。
6. preparation method according to claim 1, wherein the condition being heat-treated in step (1) includes: that temperature is 90-130
℃；And/or time 3-15h；
And/or it is 90-130 DEG C that the condition being heat-treated in step (3), which includes: temperature,；And/or time 3-20h.
7. preparation method according to claim 1-6, wherein further include: before carrying out step (1), to carbon
Cloth carries out following pretreated step: ultrasonic cleaning 10-20min is carried out to carbon cloth with the hydrochloric acid of 1-3mol/L, then spend water and/
Or 10-15min is cleaned multiple times in dehydrated alcohol.
8. preparation method according to claim 1-6, wherein nickel salt is Nickel dichloride hexahydrate and/or six hydrations
Nickel nitrate；
And/or cobalt salt is cobalt chloride hexahydrate and/or four water cobalt acetates.
9. the NiCo double hydroxide nano line@NiCo that preparation method according to claim 1-8 is prepared
Double hydroxide nano piece composite material.
10. NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material as claimed in claim 9 is in conduct
Application in electrode material；
Preferably, the NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material is in three-electrode system
The middle application as in working electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910589388.6A CN110379639A (en) | 2019-07-02 | 2019-07-02 | NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910589388.6A CN110379639A (en) | 2019-07-02 | 2019-07-02 | NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material and preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110379639A true CN110379639A (en) | 2019-10-25 |
Family
ID=68251614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910589388.6A Pending CN110379639A (en) | 2019-07-02 | 2019-07-02 | NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110379639A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111439789A (en) * | 2020-03-13 | 2020-07-24 | 长春大学 | Preparation method of nickel-cobalt double hydroxide energy storage electrode material |
| CN112133570A (en) * | 2020-09-17 | 2020-12-25 | 吉林化工学院 | Co9S8Preparation method of/Ni-Co-Mo oxyhydroxide hollow core-shell electrode material |
| CN114849716A (en) * | 2022-05-18 | 2022-08-05 | 福州大学 | 1D/2D composite material based on NiZn-LDH and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107293414A (en) * | 2017-07-07 | 2017-10-24 | 安徽师范大学 | Sour nickel core-shell structure material of the isomorphism, high performance cobalt acid nickel@cobalts and its preparation method and application |
| CN108666148A (en) * | 2018-05-04 | 2018-10-16 | 上海应用技术大学 | A kind of porous C oAl double-metal hydroxides@carbon cloth combination electrode materials and preparation method thereof |
| KR101911770B1 (en) * | 2017-03-17 | 2018-10-25 | 영남대학교 산학협력단 | Preparation method of 3D hierarchical mesoporous NiCo2S4/Ni(OH)2 core-shell nanosheet arrays on 3-dimensional conductive carbon electrode and its application to high performance supercapacitors |
| CN109192535A (en) * | 2018-11-09 | 2019-01-11 | 天津工业大学 | A kind of preparation method of carbon based metal double-hydroxide electrode material for super capacitor |
-
2019
- 2019-07-02 CN CN201910589388.6A patent/CN110379639A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101911770B1 (en) * | 2017-03-17 | 2018-10-25 | 영남대학교 산학협력단 | Preparation method of 3D hierarchical mesoporous NiCo2S4/Ni(OH)2 core-shell nanosheet arrays on 3-dimensional conductive carbon electrode and its application to high performance supercapacitors |
| CN107293414A (en) * | 2017-07-07 | 2017-10-24 | 安徽师范大学 | Sour nickel core-shell structure material of the isomorphism, high performance cobalt acid nickel@cobalts and its preparation method and application |
| CN108666148A (en) * | 2018-05-04 | 2018-10-16 | 上海应用技术大学 | A kind of porous C oAl double-metal hydroxides@carbon cloth combination electrode materials and preparation method thereof |
| CN109192535A (en) * | 2018-11-09 | 2019-01-11 | 天津工业大学 | A kind of preparation method of carbon based metal double-hydroxide electrode material for super capacitor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111439789A (en) * | 2020-03-13 | 2020-07-24 | 长春大学 | Preparation method of nickel-cobalt double hydroxide energy storage electrode material |
| CN112133570A (en) * | 2020-09-17 | 2020-12-25 | 吉林化工学院 | Co9S8Preparation method of/Ni-Co-Mo oxyhydroxide hollow core-shell electrode material |
| CN114849716A (en) * | 2022-05-18 | 2022-08-05 | 福州大学 | 1D/2D composite material based on NiZn-LDH and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110379639A (en) | NiCo double hydroxide nano line@NiCo double hydroxide nano piece composite material and preparation method and application | |
| CN105097299B (en) | Cobaltosic oxide/NiCoAl double-layered hydroxides composites and preparation method thereof | |
| CN106467299A (en) | A kind of graphene-based multi-stage porous electric capacity charcoal and preparation method thereof and capacitor | |
| CN112233912B (en) | Foam nickel-loaded MnCo2O4.5Preparation method and application of/MXene composite nano material | |
| CN103440998A (en) | Zinc cobaltate nanosheet array/foamed nickel combined electrode, preparation method and application thereof | |
| CN109267047B (en) | Preparation method of flexible cloth electrode based on nickel-manganese hydroxide | |
| CN106098397B (en) | NiSe-Ni for supercapacitor3Se2Three-dimensional pine needle shape nano material and preparation method thereof | |
| CN107230560A (en) | A kind of method that microwave radiation prepares titanium dioxide/stratiform carbon composite | |
| CN110265678A (en) | A kind of preparation method and applications of the NiO@NC bifunctional electrocatalyst with core-shell structure | |
| CN109767924B (en) | LDH-based supercapacitor composite electrode material, and preparation method and application thereof | |
| CN106098414B (en) | The method of one step hydro thermal method synthesizing graphite alkene-nickel hydroxide compound electrode of super capacitor | |
| CN110233056A (en) | A kind of Co-Ni-S nanometer sheet material and the preparation method and application thereof | |
| CN107316757A (en) | A kind of Ni-based NiCo of foam2O4/MoS2Combination electrode material and preparation method thereof | |
| CN109411238A (en) | A kind of layered double-hydroxide combination electrode material and its preparation method and application | |
| CN106065180A (en) | A kind of preparation method of molybdenum trioxide polypyrrole polyaniline trielement composite material | |
| CN106340391A (en) | Graphene/nickel hydroxide composite material and preparation method thereof, and electrode material | |
| CN114628696B (en) | Preparation method of porous carbon-supported cobalt-based bifunctional oxygen catalyst | |
| CN111564324A (en) | Preparation method of carbon cloth @ sheet cobalt-aluminum hydrotalcite flexible electrode | |
| CN109119252A (en) | Vulcanize Ni-Co-Al LDH electrode composite material and preparation method thereof | |
| CN110040787A (en) | A kind of nano whiskers FeCo2O4The preparation method and application of electrode material | |
| CN109817475A (en) | The preparation method and applications of bismuth sulfide nickel positive electrode | |
| CN108281292B (en) | Preparation method and application of Ni-Co-S nanoneedle array | |
| CN106876150A (en) | A kind of porous C oAl bimetallic oxides two dimension hierarchical structure electrode material and preparation method thereof | |
| CN109872880A (en) | A kind of preparation method of humic acid synusia bimetallic MOFs composite granule | |
| CN106981369B (en) | The preparation method of bismuth molybdate/polyaniline hybrid supercapacitor electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191025 |
|
| RJ01 | Rejection of invention patent application after publication |