CN109950056A - A kind of preparation of hollow NiO@N-C nanometer tube combination electrode material - Google Patents
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Abstract
A kind of preparation of hollow NiO@N-C nanometer tube combination electrode material, the invention belongs to supercapacitor technologies field, purpose is primarily to solve the problems such as existing carbon-based electrode material specific capacitance is not high, high rate performance is low and fake capacitance electrode material cyclical stability is poor and poorly conductive.This product is with MoO3For template, carbon matrix precursor of the polypyrrole as N doping, continuous cladding process is prepared for hollow NiO@N-C nanometer tube combination electrode material.The electrode material as working electrode and is shown into higher specific capacitance, excellent multiplying power property and good cyclical stability, while this method can be used to synthesize other kinds of hollow structure composite material.
Description
Technical field
The invention belongs to supercapacitor technologies fields, and in particular to a kind of hollow NiO@N-C nanometer tube combination electrode material
The preparation of material.
Background technique
Supercapacitor is a kind of novel energy storage device between traditional capacitor and battery, in recent years by
To the concern of vast researcher.Due to its specific capacitance with superelevation, power density is high, has extended cycle life, charging rate
It the advantages that fast and green safe, is widely used in recent years in the high frontier such as electronics industry, new energy, it has also become generation
One of the hot spot of various countries, boundary new energy field research.Increasingly exhaustion and supercapacitor applications field with resources such as petroleum
It constantly widens, developing has practical value and the electrode material that has excellent performance is with extremely profound significance.
It is different according to ultracapacitor energy storage mechanism, it can substantially be divided into double layer capacitor and fake capacitance supercapacitor
Two classes.Double layer capacitor uses the electrode material of high-specific surface area, utilizes the double electricity in the interface formed between electrode and electrolyte
Layer stores energy, and carbon material is as typical double layer capacitor, due to its specific surface area with higher and controllable
Pro-gaze of the pore structure increasingly by various countries researcher；Fake capacitance capacitor is also known as Faradic pseudo-capacitor, electrode material master
It to be transition metal oxide and two kinds of conducting polymer, the process of storage charge not only includes the storage of double layer capacitor
Mode, and including electrolyte intermediate ion stored by redox reaction process in electrode active material.With tradition
Double layer capacitor compare, fake capacitance capacitor can store more charges, therefore have higher specific capacitance.
Polypyrrole (PPy) is a kind of C, N five-ring heterocycles molecule as a kind of common conducting polymer, for biology, from
Sub- detection, electrochemical capacitance, the modified electrode of antistatic material and photoelectrochemical cell, battery electrode material.Since it contains
Nitrogen-atoms abundant has obtained a kind of porous nitrogenous carbon material by carrying out high temperature cabonization to polypyrrole material in recent years, miscellaneous
It is atom doped effectively to provide fake capacitance for whole system while the diffusion admittance of ion being provided, it is super preparing carbon material
When capacitor, introducing containing a large amount of heteroatomic polymer precursors is a very practical method.For this purpose, we urgently develop
A kind of carbon material that appearance structure is extremely similar with traditional carbon nanotube, makes it not only remain high electric conductivity and nanometer interpenetrating
Network structure, moreover it is possible to obtain the specific surface area and Heteroatom doping of superelevation.Nanostructure is directly prepared using self assembling process
Material is new method developed in recent years and is expected to solve the above problems.
Transition metal oxide with its good conductivity, thermal stability is high, electronic structure is unique the advantages that, have as one kind
Representative fake capacitance super capacitor material, especially metal nickel cobalt oxide, cause in electrochemical energy storage and catalyst
Extensive research.The redox that Rapid reversible can occur for nickel oxide (NiO) should provide more energy in turn, NiO with
By means of the theoretical specific capacitance (2584Fg of superelevation-1), lower price and excellent chemical/thermal stability, be widely used in super
Capacitor electrode material.Due to the factors such as NiO poorly conductive, stock utilization be low, NiO based super capacitor and it is theoretical at present
There are also biggish gaps for specific capacitance.
Summary of the invention
The invention belongs to supercapacitor technologies field, purpose is primarily to solve existing carbon-based electrode material ratio
The problems such as capacitor is not high, high rate performance is low and fake capacitance electrode material cyclical stability is poor and poorly conductive, the present invention provides
A kind of safe preparation process is nontoxic, composite material morphological rules and the good hybrid super capacitor electrode material of electric conductivity,
Designed electrode material have good cyclical stability and superelevation specific capacitance, while material safe preparation process it is nontoxic and
It is low in cost to be easy to industrialization.
A kind of preparation of hollow NiO N-C nanometer tube combination electrode material of the present invention, it is characterised in that Yi Zhongkong
The preparation of heart NiO@N-C nanometer tube combination electrode material is with the MoO of morphological rules3Nanotube is template, and the template removal side
Method is simple to operate, while using carbon matrix precursor of the polypyrrole as N doping, forms bivalve layer using continuous cladding process
Hollow nanotube；
The template that the hollow NiO@N-C nanometer tube combination electrode material uses is the MoO of morphological rules3Nanotube；
For the hollow NiO@N-C nanometer tube combination electrode material using PPy as the carbon matrix precursor material of N doping, PPy is logical
Cross anionic polymerization preparation；
The hollow NiO@N-C nanometer tube combination electrode material uses continuous growth method, is prepared by chemical bath deposition
Ni(OH)2Film；
The hollow NiO@N-C nanometer tube combination electrode material is with NiSO4For nickel source, high-temperature calcination prepares NiO；
The hollow NiO@N-C nanometer tube combination electrode material removes MoO by being soaked in NaOH solution3Template；
Beneficial effects of the present invention:
Compared with existing electrode material for super capacitor, hollow NiO@N-C nanometer tube combination electrode synthesized by the present invention
Material solves that current existing carbon-based electrode material specific capacitance is low, poorly reversible and transition metal oxide electrode material circulation
The problems such as stability is poor, furthermore prepared hollow NiO@N-C nanometer tube combination electrode material have simultaneously safe operation it is nontoxic,
Electrochemical reversibility is good, the features such as haveing excellent performance.
Detailed description of the invention
Fig. 1 is the Fourier of hollow NiO@N-C nanometer tube combination electrode material and independent PPy that verification test (one) obtains
Infrared spectrum comparison diagram；
Fig. 2 is the scanning electron microscope (SEM) photograph of hollow NiO@N-C nanometer tube combination electrode material obtained in verification test (one).
Fig. 3 is the transmission electron microscope picture of hollow NiO@N-C nanometer tube combination electrode material obtained in verification test (one).
Fig. 4 is hollow NiO N-C nanometer tube combination electrode material following under the conditions of difference sweeps speed in verification test (two)
Ring volt-ampere curve (CV)；
Fig. 5 is the hollow NiO@N-C nanometer tube combination electrode material of synthesis in verification test (three) in different current densities
Under constant current charge discharge figure；
Fig. 6 is the hollow NiO@N-C nanometer tube combination electrode material synthesized in verification test (four) and PPy hollow nanotube
Electrode material AC impedance comparison diagram；
Fig. 7 is the stable circulation figure of the hollow NiO@N-C nanometer tube combination electrode material synthesized in verification test (four).
Specific embodiment
Specific embodiment 1: present embodiment is the nanotube-shaped MoO prepared with hydro-thermal method3For template, NiSO4As
Nickel source, carbon matrix precursor of the polypyrrole as N doping, polypyrrole are prepared by anionic polymerization.
Specific embodiment 2: a kind of preparation method of hollow NiO@N-C nanometer tube combination electrode material is according to the following steps
It carries out:
One, nanotube-shaped MoO3Preparation:
1. the ammonium molybdate for accurately weighing 2.8g first be dissolved in 80mL containing nitric acid and deionized water (nitric acid: deionized water=1:
5) in solution, magnetic agitation 25~30 minutes, clear transparent solutions A is formed；
2. solution A is transferred in the autoclave of 100mL polytetrafluoroethyllining lining, 200 DEG C of hydrothermal condition reactions
20h, the centrifuge washing after naturally cooling to room temperature are washed to neutrality, and the revolution of centrifuge is set as 5000r/min~6000r/
Sample grinding dress sample after drying is formed white powder A by min, dry 48h under the conditions of 60 DEG C；
Step 1 1. described in solution A the quality of cobalt acetate and the volume ratio of mixed solution be 2.8g: 80mL；
Two, PPy film coated MoO3(PPy@MoO3) preparation:
1. accurately weighing the MoO of 0.5g3With the p-methyl benzenesulfonic acid of 0.415g~0.42g, it is dissolved in the anhydrous second of 30mL
In alcohol, after being ultrasonically treated 30min, it is placed in 5~10min of stirring in ice-water bath, forms solution A；
2. the pyrrole monomer of 0.2mL is then added dropwise in solution A, the ammonium persulfate of 0.23g~0.25g and 20mL go from
Sub- water, magnetic agitation 30s~60s form solution B；
3. solution B is placed in dark condition lower 4 hours, respectively washed three times with deionized water and ethyl alcohol, vacuum under the conditions of 60 DEG C
Drying forms powders A；
Step 2 1. described in MoO3Mass ratio with p-methyl benzenesulfonic acid is 0.5g: 0.415g~0.42g；
Step 2 1. described in MoO3Quality and dehydrated alcohol volume ratio be 0.5g: 30mL；
Step 2 1. described in p-methyl benzenesulfonic acid quality and dehydrated alcohol volume ratio be 0.415g~0.42g: 30mL；
Step 2 2. described in pyrrole monomer and solution B volume ratio be 0.2: 50；
Three, Ni (OH)2Coat PPy hollow nanotube (Ni (OH)2@PPy) preparation:
1. by the PPy@MoO of above-mentioned preparation3It is immersed in the NaOH solution of 2mol/L and takes 60mL, 85 DEG C are reacted 12 hours,
Centrifugation washing, centrifuge revolution are set as 5000r/min~6000r/min, and dry 12h under the conditions of 60 DEG C forms powders A；
2. accurately weighing the NiSO of 1g4Solid is dissolved in the deionized water of 10mL, forms solution A, 0.33g potassium peroxydisulfate
6mL deionized water, which is dissolved in, with 0.5g powders A forms solution B；
3. solution A is added in solution B, 5~8min is stirred, the ammonium hydroxide that 2mL is added forms solution C, and centrifugation washing is more
Time, dry 12h, forms powder B under the conditions of 60 DEG C；
Step 3 2. described in NiSO in solution A4Quality and deionized water volume ratio be 1g: 10mL；
Step 3 2. described in solution B potassium peroxydisulfate and the mass ratio of powders A be 0.33: 0.5；
Four, hollow tubular NiO coats the preparation of nitrogen-doped carbon nanometer pipe (NiO@N-C) composite material:
1. by the Ni (OH) of above-mentioned preparation2@PPy composite material is in N2Under atmosphere, 2h, heating rate are calcined under the conditions of 700 DEG C
For 5 DEG C/min, grinding dress sample forms black powder A after being cooled to room temperature；
Five, the preparation method of the electrochemical working electrode based on hollow NiO@N-C nanometer tube combination electrode material:
1. accurately weigh 0.01g preparation active material hollow tubular NiO@N-C composite material, 0.0018g acetylene black and
0.0006g polytetrafluoroethylene (PTFE) (PTFE), by it, ultrasonic mixing is uniform in the ethyl alcohol of 4~6mL, forms paste A；
2. 1. paste A that step obtains is coated in a piece of 1cm × 1cm × 0.1cm nickel foam, 60 DEG C of conditions are dried
Dry 6~8h, obtains substance B；
Step 5 1. described in paste A in NiO@N-C composite material, acetylene black and the mass ratio of PTFE three be 80
:15:5；
Step 5 1. described in paste A quality and ethyl alcohol volume ratio be 0.0124g: 4mL~6mL；
Specific embodiment 3: present embodiment is unlike specific embodiment one to two: step 1 1. described in
The quality of ammonium molybdate be 2.8g, be dissolved in 80mL containing nitric acid and deionized water (nitric acid: deionized water=1: in solution 5), magnetic
Power stirs 30 minutes, forms clear transparent solutions A.Other steps and parameter are identical as one of specific embodiment one to two.
Specific embodiment 4: present embodiment is unlike specific embodiment one to three: step 1 2. described in
The revolution of centrifuge be set as 6000r/min, dry 48h under the conditions of 60 DEG C forms the sample grinding dress sample after drying white
Color powders A.Other steps and parameter are identical as one of specific embodiment one to three.
Specific embodiment 5: present embodiment is unlike specific embodiment one to four: step 2 1. described in
MoO3Quality be 0.5g, the quality of p-methyl benzenesulfonic acid is 0.416g, is dissolved in the dehydrated alcohol of 30mL, is ultrasonically treated
It after 30min, is placed in ice-water bath and stirs 10min, form solution A.Other steps and parameter and specific embodiment one to four it
One is identical.
Specific embodiment 6: present embodiment is unlike specific embodiment one to five: step 2 2. described in
Solution A in the pyrrole monomer of 0.2mL, the ammonium persulfate of 0.24g and the deionized water of 20mL is added dropwise, magnetic agitation 60s is formed
Solution B.Other steps and parameter are identical as one of specific embodiment one to five.
Specific embodiment 7: present embodiment is unlike specific embodiment one to six: step 3 1. described in
Centrifuge revolution be set as 6000r/min, dry 12h, forms powders A under the conditions of 60 DEG C.Other steps and parameter and specific
One of embodiment one to six is identical.
Specific embodiment 8: present embodiment is unlike specific embodiment one to seven: step 3 3. described in
Solution A be added in solution B, stir 5min, the ammonium hydroxide that 2mL is added forms solution C, centrifugation washing multipass, under the conditions of 60 DEG C
Dry 12h, forms powder B.Other steps and parameter are identical as one of specific embodiment one to seven.
Specific embodiment 9: present embodiment is unlike specific embodiment one to eight: step 5 1. described in
0.01g preparation active material hollow tubular NiO@N-C composite material, 0.0018g acetylene black and 0.0006g polytetrafluoroethylene (PTFE)
(PTFE), by it, ultrasonic mixing is uniform in the ethyl alcohol of 5mL, forms paste A.Other steps and parameter and specific embodiment
One of one to eight is identical.
Specific embodiment 10: present embodiment is unlike specific embodiment one to nine: step 5 2. described in
The paste A for 1. obtaining step be coated in a piece of 1cm × 1cm × 0.1cm nickel foam, 60 DEG C of conditions dry 6h, obtain
To substance B.Other steps and parameter are identical as one of specific embodiment one to nine.
Effect of the invention is verified with following tests
Test one, a kind of preparation method of hollow NiO@N-C nanometer tube combination electrode material sequentially include the following steps:
One, nanotube-shaped MoO3Preparation:
1. the ammonium molybdate for accurately weighing 2.8g first be dissolved in 80mL containing nitric acid and deionized water (nitric acid: deionized water=1:
5) in solution, magnetic agitation 30 minutes, clear transparent solutions A is formed；
2. solution A is transferred in the autoclave of 100mL polytetrafluoroethyllining lining, 200 DEG C of hydrothermal condition reactions
20h, the centrifuge washing after naturally cooling to room temperature are washed to neutrality, and the revolution of centrifuge is set as 6000r/min, 60 DEG C of items
Sample grinding dress sample after drying is formed white powder A by dry 48h under part；
Two, PPy film coated MoO3(PPy@MoO3) preparation:
1. accurately weighing the MoO of 0.5g3It with the p-methyl benzenesulfonic acid of 0.416g, is dissolved in the dehydrated alcohol of 30mL, surpasses
It after sonication 30min, is placed in ice-water bath and stirs 10min, form solution A；
2. the pyrrole monomer of 0.2mL, the ammonium persulfate of 0.24g and the deionized water of 20mL, magnetic are then added dropwise in solution A
Power stirs 60s, forms solution B；
3. solution B is placed in dark condition lower 4 hours, ionized water and ethyl alcohol are respectively washed three times, and vacuum is dried under the conditions of 60 DEG C
It is dry, form powders A；
Three, Ni (OH)2Coat PPy hollow nanotube (Ni (OH)2@PPy) preparation:
1. by the PPy@MoO of above-mentioned preparation3It is immersed in the NaOH solution of 2mol/L and takes 60mL, 85 DEG C are reacted 12 hours,
Centrifugation washing, centrifuge revolution are set as 6000r/min, and dry 12h under the conditions of 60 DEG C forms powders A；
2. accurately weighing the NiSO of 1g4Solid is dissolved in the deionized water of 10mL, forms solution A, 0.33g potassium peroxydisulfate
6mL deionized water, which is dissolved in, with 0.5g powders A forms solution B；
3. solution A is added in solution B, 5min is stirred, the ammonium hydroxide that 2mL is added forms solution C, and multipass is washed in centrifugation,
Dry 12h, forms powder B under the conditions of 60 DEG C；
Four, hollow tubular NiO coats the preparation of nitrogen-doped carbon nanometer pipe (NiO@N-C) composite material:
1. by the Ni (OH) of above-mentioned preparation2@PPy composite material calcines 2h, heating speed under N2 atmosphere under the conditions of 700 DEG C
Rate is 5 DEG C/min, and grinding dress sample forms black powder A after being cooled to room temperature；
Five, the preparation method of the electrochemical working electrode based on hollow NiO@N-C nanometer tube combination electrode material:
1. accurately weigh 0.01g preparation active material hollow tubular NiO@N-C composite material, 0.0018g acetylene black and
0.0006g polytetrafluoroethylene (PTFE) (PTFE), by it, ultrasonic mixing is uniform in the ethyl alcohol of 5mL, forms paste A；
2. 1. paste A that step obtains is coated in a piece of 1cm × 1cm × 0.1cm nickel foam, 60 DEG C of conditions are dried
Dry 6h, obtains substance B；
The determination of structure and the characterization of pattern are carried out to the hollow tubular NiO N-C composite material that test one obtains:
(1) FTIR-650 type infrared spectrometer, S-4300 type scanning electron microscope (SEM) and JEM-2010 type are utilized
Transmission electron microscope (TEM) carries out the determination and shape of structure to the obtained hollow tubular NiO N-C composite material of test one
The characterization of looks obtains the FTIR spectrum of hollow tubular NiO@N-C composite material as shown in Figure 1, Fig. 2 is hollow NiO@
Scanning electron microscope diagram, Fig. 3 of N-C nanometer tube combination electrode material are hollow NiO@N-C nanometer tube combination electrode material
Transmission electron microscope figure.
It will be seen from figure 1 that PPy hollow nanotube and hollow NiO@N-C nanometer tube combination electrode material are successfully made
It is standby.The characteristic peak of pyrrole ring is located at 1576cm-1And 1450cm-1Place is the antisymmetric stretching vibration of pyrrole ring respectively and is symmetrically stretched
Contracting vibration peak.Peak value 1576cm-1For-C=C- stretching vibration peak, peak value 1314cm-1Place is C-N stretching vibration peak.In 895cm-1
And 801cm-1The peak value at place is divided into C-H in-plane bending vibration peak and out-of-plane bending vibration peak.By comparison PPy hollow nanotube and
The peak position of hollow tubular NiO@N-C composite material can be seen that the characteristic peak of PPy significantly reduces, and show that PPy is carbonized completely, bone
Frame collapses, while 459cm-1For the characteristic peak of NiO metal oxygen key, show Ni (OH)2Successful conversion is NiO after high temperature.
Fig. 2 is the scanning electron microscope diagram of hollow NiO@N-C nanometer tube combination electrode material, is as can be seen from the figure closed
At composite material microscopic appearance be even size distribution nanotube, NiO@N-C nanotube size is 350nm or so, and is made
It is porous that standby nanotube surface is bulk.
Fig. 3 is the transmission electron microscope figure of hollow NiO@N-C nanometer tube combination electrode material, and a figure is it can be seen that NiO@
N-C nanotube is hollow structure, and b figure is the enlarged drawing of NiO@N-C nanotube, its hollow structure, carbon-coating can be clearly seen
With a thickness of 65nm or so.
(2) electrochemical behavior for the hollow NiO@N-C nanometer tube combination electrode material that verifying the application test one obtains.
One, the preparation of supercapacitor
Hollow NiO@N-C nanometer tube combination electrode material, acetylene black and the PTFE mixing shape obtained with the application test one
At electrode active material, to coat the nickel foam of the active material as working electrode, saturation calomel is reference electrode, platinized platinum electricity
Extremely to electrode, the three-electrode system of composition is supercapacitor.
Two, using hollow NiO@N-C nanometer tube combination electrode material prepared by step 1 as working electrode, prepared is super
Grade capacitor has obtained hollow NiO@N-C under the conditions of sweeping speed and being respectively 5mV/s, 10mV/s, 20mV/s, 30mV/s, 50mV/s
Nanometer tube combination electrode material cyclic voltammetry curve.
Conclusion: obtaining hollow NiO@N-C nanometer tube combination electrode material as shown in Figure 4 sweeping speed is 5mV/s-50mV/s
Obtained cyclic voltammetry curve, from can be to occur a pair of apparent redox peaks from 0.463V and 0.252V in figure, this be
Reversible redox reaction has occurred between NiO and NiOOH, it was demonstrated that the fake capacitance performance of material.With sweep speed by
The cumulative added-time, CV curvilinear motion is unobvious, illustrates that NiO@N-C electrode material has good electrochemical stability.In addition, CV is bent
The area and peak current value that line is enclosed are gradually increased, and illustrate that NiO@N-C electrode material has preferable electric conductivity.Pass through
These results indicate that electro-chemical activity can be improved in hollow NiO@N-C nanometer tube combination electrode material.
(3) charge-discharge performance for the hollow NiO@N-C nanometer tube combination electrode material that verifying the application test one obtains.
The preparation of supercapacitor: with one obtained hollow NiO@N-C nanometer tube combination electrode material of the application test and
Acetylene black, PTFE mixing constitute electrode active material, and the nickel foam to coat the active material is saturated calomel as working electrode
As reference electrode, platinum plate electrode is used as to electrode, and the three-electrode system of composition constitutes supercapacitor.
Using constant current charge-discharge method, to be added hollow NiO@N-C nanometer tube combination electrode material 0.5A/g, 1A/g,
Under the current density of 2A/g, 3A/g, 5A/g, potential window tests its charge-discharge performance under the conditions of being 0-0.4V, obtains such as Fig. 5 institute
The charging and discharging curve of the hollow NiO@N-C nanometer tube combination electrode material shown, as can be seen from the figure the ratio in 0.5A/g is electric
Hold and is up to 782Fg-1, in 5A/g, still there is 101Fg-1Capacitance.
(4) verifying the application tests the electric conductivity for the hollow NiO@N-C nanometer tube combination electrode material that one obtains and follows
Ring stability.
The preparation of supercapacitor: with one obtained hollow NiO@N-C nanometer tube combination electrode material of the application test and
Acetylene black, PTFE mixing constitute electrode active material, coat the nickel foam of the active material as working electrode, being saturated calomel is
Reference electrode, platinum plate electrode are to electrode, and the three-electrode system of composition is supercapacitor.
The friendship of hollow NiO@N-C nanometer tube combination electrode material and PPy hollow nanotube is tested by electrochemical workstation
Flow impedance map, frequency range are 0.05~105Hz, obtained nyquist plot consist of two parts, respectively high frequency region
Semi-circular portions and low frequency range straight line portion.Pass through comparison nyquist plot discovery, it is clear that in high frequency region hollow NiO@N-C
Half circular diameter of nanometer tube combination electrode material is less than PPy hollow nanotube, and charge transfer resistance is smaller, this is because hollow
Charge transfer process between NiO@N-C nanometer tube combination electrode material and electrolyte is very fast, to show porous porous layer of charcoal
Electric conductivity with higher.In low frequency part, it is empty that the linear gradient of hollow NiO@N-C nanometer tube combination electrode material is higher than PPy
Heart nanotube illustrates that hollow NiO@N-C nanometer tube combination electrode material has lesser Particle diffusion resistance.Simultaneously by following
It calculates its capacity retention ring 4,000 times, still keeps the 89.8% of its initial capacitance after 2,000 circle of circulation, it was demonstrated that synthesized
Electrode material has good conductive property and cyclical stability.
In conclusion a kind of hollow NiO@N-C nanometer tube combination electrode material is successfully prepared, prepared composite wood
Expect with specific capacitance value height, good cycling stability, safe preparation process is nontoxic low in cost and electrode material electric conductivity is good
The advantages that.
Claims (6)
1. a kind of preparation of hollow NiO@N-C nanometer tube combination electrode material, it is characterised in that a kind of hollow NiO@N-C nanotube
The preparation of combination electrode material is with the MoO of morphological rules3Nanotube is template, and the template minimizing technology is simple to operate,
Carbon matrix precursor of the polypyrrole as N doping is used simultaneously, forms the hollow nanotube of bivalve layer using continuous cladding process.
2. according to claim 1, it is characterised in that a kind of preparation of hollow NiO@N-C nanometer tube combination electrode material,
The template is the MoO of morphological rules3Nanotube.
3. according to claim 1, it is characterised in that a kind of preparation of hollow NiO@N-C nanometer tube combination electrode material,
For the hollow NiO@N-C nanometer tube combination electrode material using PPy as the carbon matrix precursor material of N doping, PPy passes through anion
Polymerization preparation.
4. according to claim 1, it is characterised in that a kind of preparation of hollow NiO@N-C nanometer tube combination electrode material,
The hollow NiO@N-C nanometer tube combination electrode material uses continuous growth method, prepares Ni (OH) by chemical bath deposition2It is thin
Film.
5. according to claim 1, it is characterised in that a kind of preparation of hollow NiO@N-C nanometer tube combination electrode material,
The hollow NiO@N-C nanometer tube combination electrode material is with NiSO4For nickel source, high-temperature calcination prepares NiO.
6. according to claim 1, it is characterised in that a kind of preparation of hollow NiO@N-C nanometer tube combination electrode material,
The PPy@MoO3MoO is removed by being soaked in NaOH solution3Template.
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