CN108878168A - The modified electrode material in surface and the processing method modified to electrode material surface - Google Patents
The modified electrode material in surface and the processing method modified to electrode material surface Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 77
- 238000003672 processing method Methods 0.000 title claims abstract description 12
- 239000002070 nanowire Substances 0.000 claims abstract description 76
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 239000006260 foam Substances 0.000 claims abstract description 29
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000010936 titanium Substances 0.000 claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000000151 deposition Methods 0.000 claims abstract description 13
- 230000008021 deposition Effects 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 4
- 238000009826 distribution Methods 0.000 claims abstract description 3
- 230000004087 circulation Effects 0.000 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- CZAYMIVAIKGLOR-UHFFFAOYSA-N [Ni].[Co]=O Chemical compound [Ni].[Co]=O CZAYMIVAIKGLOR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 43
- 239000010408 film Substances 0.000 description 21
- 229910003266 NiCo Inorganic materials 0.000 description 14
- 239000010410 layer Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- 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, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a kind of modified electrode materials in surface and the processing method modified to electrode material surface, which includes nickel cobalt oxide nano wire and titanium deoxid film；Nickel cobalt oxide nano wire includes foam nickel base, the nickel cobalt oxygen nano wire of array distribution in foam nickel base；The nickel cobalt oxide nano wire is heat-treated by nickel cobalt oxide nanowire precursor；Titanium deoxid film recycles Multiple depositions to the outer surface of the nickel cobalt oxide nanowire precursor by technique for atomic layer deposition.Nickel cobalt oxide nano wire is obtained eventually by heat treatment technics and the titanium dioxide membrane electrode provided material present invention improves the chemical property of nickel cobalt oxide, keeps its stability.
Description
Technical field
The present invention relates to electrode technology fields, more particularly to a kind of modified electrode material in surface and to electrode material table
The modified processing method in face.
Background technique
In numerous electrode materials, the cobalt oxide and nickel cobalt oxide of spinel structure are due to its outstanding redox energy
Power and high theoretical specific capacity (> 3000F/g), become one of electrode material most potential in supercapacitor.In conjunction with mesh
From the point of view of preceding research, simple using nickel cobalt oxide as the supercapacitor of electrode material, there are also very high capacity boost spaces.
But when supercapacitor is in high capacity working condition for a long time, because quickly, non-fully reversible redox
The influence to its initial configuration is reacted, causes nanostructure that will be destroyed, and then reduce cycle life, and then affect
The cyclical stability of electrode material.Therefore, how modified electrode material is to improve the chemical property of electrode material, and keeps it
Stability becomes the problem of those skilled in the art's urgent need to resolve.
Summary of the invention
The object of the present invention is to provide a kind of modified electrode materials in surface and the processing side modified to electrode material surface
Method keeps its stability to improve the chemical property of nickel cobalt oxide.
To achieve the above object, the electrode material modified the present invention provides a kind of surface, including nickel cobalt oxide nanometer
Line and the titanium deoxid film coated in the outer surface of the nickel cobalt oxide nano wire；
The nickel cobalt oxide nano wire includes foam nickel base, the nickel cobalt oxide synthesized in the foam nickel base
Nano wire；The nickel cobalt oxide nano wire is heat-treated by nickel cobalt oxide nanowire precursor；
The titanium deoxid film recycles Multiple depositions to the nickel cobalt oxide nano wire by technique for atomic layer deposition
The outer surface of presoma.Nickel cobalt oxide nano wire and titanium dioxide electrodes material are obtained eventually by heat treatment technics.
Optionally, the titanium deoxid film is brockite structure.
The optional titanium deoxid film with a thickness of 1nm.
The present invention also provides the modified processing methods of a kind of pair of electrode material surface, including：
Nickel cobalt oxide nano wire is synthesized in foam nickel base, obtains nickel cobalt oxide nanowire precursor；
Using technique for atomic layer deposition the nickel cobalt oxide nanowire precursor surface circulation deposition of titanium oxide,
Layer of titanium dioxide film is formed on the surface of the nickel cobalt oxide nanowire precursor, before obtaining nickel cobalt oxide nano wire
Drive body and composite titania material；
By the composite material be put into atmospheric environment carry out temperature be 300 DEG C of times be 2h annealing, obtain table
The modified nickel cobalt oxide in face and titanium dioxide membrane electrode provided material.
Optionally, described that nickel cobalt oxide nano wire is synthesized in foam nickel base, before obtaining nickel cobalt oxide nano wire
Body is driven, is specifically included：
The foam nickel base being sized is taken up in order of priority to be placed in acetone soln and ethanol solution and carries out ultrasonic cleaning
5min,
Foam nickel base after cleaning is put into air dry oven, 3h is dried with 80 DEG C of drying temperature, obtains standard bubble
Foam nickel substrate；
0.58g cobalt nitrate, 0.18g ammonium fluoride and 1.2g urea are dissolved in 35ml deionized water, uniform powder is formed
Color solution；
It is in the reaction kettle of 50ml that by the pink colour solution and the standard foam nickel substrate, to put temperature into, which be 120 DEG C of capacity,
6h is reacted, after cooled to room temperature, opens the reaction kettle, takes out nickel cobalt oxide nano wire obtained；
By nickel cobalt oxide nano wire deionized water repeated flushing 5min, then put into drying box with 80 DEG C of baking
Dry temperature dries 3h, obtains nickel cobalt oxide nanowire precursor.
Optionally, the titanium deoxid film is brockite structure.
Optionally, the titanium deoxid film with a thickness of 1nm.
Optionally, described heavy in the surface circulation of the nickel cobalt oxide nanowire precursor using technique for atomic layer deposition
The number of product titanium dioxide is 40-60 times.
Optionally, the foam nickel base is sized as 1cm*2cm.
The specific embodiment provided according to the present invention, the invention discloses following technical effects：
1, the present invention does not destroy original structure：Before and after atomic layer deposition titanium deoxid film, the pattern of electrode material does not have
There is change, stability while remaining biggish specific surface area for structure provides protection.
2, high conformality, precision are high：Due to the unique depositional mode of technique for atomic layer deposition, so technique for atomic layer deposition
With high conformality；Since technique for atomic layer deposition can be with the deposition of monoatomic layer in layer, so having precision Gao Te
Point.
3, chemical property significantly improves：It can be seen that NiCo by cyclic voltammetry result and charging and discharging curve2O4/
TiO2Electrode material has apparent fake capacitance characteristic, and the specific capacity of the material after atomic layer deposition is modified has obviously
It improves.It can be seen that the NiCo after handling by atomic layer deposition by multiplying power test curve2O4/TiO2Nano line electrode material
Material is in 2,4,5,10,15,20,25,30mA/cm2Current density under specific capacity be respectively 2.94,2.88,2.86,2.62,
2.57、2.49、2.32、2.25、2.1F/cm2, compared to NiCo2O4The specific capacity 1.1 of nano line electrode material, 1.1,1.08,
1.04、1.0、0.98、0.85、0.8F/cm2There is apparent raising.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, without any creative labor, can also be according to these attached drawings
Obtain other attached drawings.
Fig. 1 is the electrode material and treated electrode material X ray diffracting spectrum before surface modification treatment；
A is NiCo in Fig. 22O4The scanning electron microscope image of electrode material；B is NiCo2O4/TiO2The scanning electron microscope of electrode material
Image；C is NiCo2O4The images of transmissive electron microscope of electrode material；D is NiCo2O4/TiO2The images of transmissive electron microscope of electrode material；
A and b is NiCo in Fig. 32O4/TiO2Electrode material high-resolution-ration transmission electric-lens image；C is NiCo2O4/TiO2Electrode material
Expect high angle annular dark field image and NiCo2O4/TiO2Electrode material EDS energy spectrum analysis figure；
Fig. 4 is NiCo2O4/TiO2XPS map, wherein a be Co2p map；B is Ni2p map；C is Ti2p map；D is
O1s map；
A is NiCo in Fig. 52O4/TiO2Electrode material difference potential sweeps cyclic voltammetry result figure under speed；B is NiCo2O4
And NiCo2O4/TiO2Electrode material 2mA/cm2Charging and discharging curve under current density；C is NiCo2O4And NiCo2O4/TiO2Electrode material
Expect constant current density charge-discharge test result figure；D is NiCo2O4And NiCo2O4/TiO2Electrode material impedance test results figure；E is
NiCo2O4And NiCo2O4/TiO2Electrode material 10mA/cm2Cyclic voltammetry result figure under current density；
A is NiCo in Fig. 62O4Images of transmissive electron microscope after electrode material circulation；B is NiCo2O4/TiO2After electrode material circulation
Images of transmissive electron microscope.
Specific embodiment
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 description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The object of the present invention is to provide a kind of modified electrode materials in surface and the processing side modified to electrode material surface
Method keeps its stability to improve the electric conductivity of nickel cobalt oxide.
In optimization using the cobalt oxide of spinel structure or nickel cobalt oxide as the electrochemistry of the supercapacitor of electrode material
When performance, maximum problem is to improve its specific capacity to greatest extent in the case where not influencing the characteristics such as its structure and cycle life,
So that its meet demand.In the experimental method of structural stability optimization and Material cladding, technique for atomic layer deposition (ALD)
Major advantage is that have during the deposition process from restricted and high conformality, it will not both destroy the structure and morphology of primary sample,
Protective film can be accurately plated on nanoscale again.Based on the above result of study, in order to improve nickel cobalt oxide
Electric conductivity, keep its stability, it is heavy on the nickel cobalt oxide nano wire surface layer being grown in foam nickel base by ALD technique
The brockite structure Ti O of a layer thickness about 1nm in product2, obtained the nanocomposite NiCo of excellent electrochemical performance2O4/
TiO2。
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing and specific real
Applying mode, the present invention is described in further detail.
The modified electrode material in surface provided by the invention includes nickel cobalt oxide nanowire precursor and in the nickel cobalt
The titanium deoxid film of the outer surface cladding of oxide nano thread presoma.
Wherein, the nickel cobalt oxide nano wire includes foam nickel base, the array distribution in the foam nickel base
Nickel cobalt oxygen nano wire.The nickel cobalt oxygen nano wire is dioxy described in that is obtained as nickel cobalt oxygen nanowire precursor through Overheating Treatment
Change titanium film and Multiple depositions are recycled to the outer surface of the nickel cobalt oxide nanowire precursor by technique for atomic layer deposition.Most
It is obtained in nickel cobalt oxygen nano wire and titanium dioxide membrane electrode provided material the present embodiment by heat treatment technics eventually, titanium dioxide is thin
Film be brockite structure, titanium deoxid film with a thickness of 1nm.
The modified electrode material in corresponding above-mentioned surface, the present invention also provides the modified places of a kind of pair of electrode material surface
Reason method, use prepare raw material be foam nickel base, ammonium fluoride, cobalt nitrate, urea, deionized water, titanium source, dehydrated alcohol,
Acetone, all drugs are by any processing.The equipment used be magnetic stirring apparatus, three-electrode system, stainless steel cauldron,
CHI660C electrochemical workstation, LAND battery test system, constant temperature electric heating air dry oven, CVD furnace, atomic layer deposition apparatus
(ALD)。
To electrode material surface, modified processing method includes：
Step 1：Nickel cobalt oxide nano wire is synthesized in foam nickel base, obtains nickel cobalt oxide nanowire precursor.
The step 1 specifically includes following steps：
The foam nickel base for 1cm*2cm will be sized and be taken up in order of priority to be placed in acetone soln and ethanol solution and surpassed
Sound wave cleans 5min,
Foam nickel base after cleaning is put into air dry oven, 3h is dried with 80 DEG C of drying temperature, obtains standard bubble
Foam nickel substrate；
0.58g cobalt nitrate, 0.18g ammonium fluoride and 1.2g urea are dissolved in 35ml deionized water, uniform powder is formed
Color solution；
It is in the reaction kettle of 50ml that by the pink colour solution and the standard foam nickel substrate, to put temperature into, which be 120 DEG C of capacity,
6h is reacted, after cooled to room temperature, opens the reaction kettle, takes out nickel cobalt oxide nano wire obtained；
By nickel cobalt oxide nano wire deionized water repeated flushing 5min, then put into drying box with 80 DEG C of baking
Dry temperature dries 3h, obtains nickel cobalt oxide nanowire precursor.
Step 2：Using technique for atomic layer deposition the nickel cobalt oxide nanowire precursor surface circulation deposition of thick
Degree is the titanium dioxide of the brockite structure of 1nm, forms one layer of dioxy on the surface of the nickel cobalt oxide nanowire precursor
Change titanium film, obtains nickel cobalt oxide nanowire precursor and composite titania material.Using technique for atomic layer deposition in institute
The number for stating the surface circulation deposition of titanium oxide of nickel cobalt oxide nanowire precursor is 40-60 times, specifically be can be 50 times.
Step 3：By the composite material be put into atmospheric environment carry out temperature be 300 DEG C of times be 2h annealing,
Obtain the modified electrode material in surface.
Comparison by electrode material and each performance parameter of treated electrode material before surface modification treatment is such as
Under：
1、NiCo2O4And NiCo2O4/TiO2The pattern and contrastive Analysis of Structures of composite nano-line electrode material
Fig. 1 is the electrode material and treated electrode material X ray diffracting spectrum, i.e. NiCo before surface modification treatment2O4
And NiCo2O4/TiO2XRD spectrum, square mark represents the diffraction maximum of Ni substrate in figure.It can be found that 4 apparent from figure
Characteristic peak respectively appears in 2 θ=31.1 °, 36.6 °, 59.1 ° and 64.9 °.The NiCo at all these peaks and spinel structure2O4's
(220), (311), (511) and (440) crystal face correspond.Due to the TiO using technique for atomic layer deposition deposition2Film thickness
Only about 1nm, so being difficult to observe and detect TiO in XRD spectrum2Film.
Fig. 2 a is NiCo2O4Shape appearance figure under scanning electron microscope, as can be seen from the figure every nanometer sheet top is all dispersed into number
Root nano wire, this structure provide biggish specific surface area for electrochemical reaction, and the infiltration and ion for being conducive to electrolyte pass
It is defeated.Fig. 2 b is NiCo2O4/TiO2Shape appearance figure under scanning electron microscope, by the comparisons of two width figures it can be concluded that, in atomic layer deposition
TiO2Before and after film, the pattern of sample is mentioned there is no changing while remaining biggish specific surface area for the stability of structure
Protection is supplied.Fig. 2 c, 2d are NiCo respectively2O4And NiCo2O4/TiO2The shape appearance figure of single nano-wire under transmission electron microscope, can see
Also there is no change for the pattern of single nano-wire out.In conjunction with Fig. 1, due to the TiO using technique for atomic layer deposition deposition2Film
Thickness only has about 1nm, so being difficult to observe and detect TiO in SEM (scanning electron microscope (SEM) photograph) and XRD spectrum2Film.But
Exactly because being the TiO of also deposition2It is very thin, the transmission of ion will not be hindered, it can be in the premise for guaranteeing electrode material capacity
Lower its stability of raising.
Fig. 3 gives NiCo2O4/TiO2The more careful structure feature image of nano wire.Fig. 3 a and Fig. 3 b are NiCo2O4/
TiO2Nano wire high-resolution-ration transmission electric-lens image.It can be seen that NiCo from Fig. 3 a2O4/TiO2Nano wire is by many very small
Nanoparticle composition, is typical meso-hole structure.It is mainly since phase transition in precursor thermal decomposition process and lattice are dehydrated
It is caused.Such an arrangement provides biggish specific surface areas, are conducive to contact of the electrolyte with electrode material, to improve electrode
The chemical property of material.It in fig 3b, is 0.468nm and 0.203nm, difference by the interplanar distance that measurement obtains the crystal face
With NiCo2O4(111) (400) crystal face it is consistent, it was demonstrated that NiCo2O4/TiO2Nano wire has good crystallinity.Fig. 3 c is
NiCo2O4/TiO2Nano wire high angle annular dark field image and EDS energy spectrum analysis can therefrom be observed directly in nano wire table
There is the TiO that a layer thickness is about 1nm in face2Film, and can be seen that Ni, Co, O and Ti element are uniformly distributed in nano wire
In, further prove that this experiment successfully coats ultra-thin TiO in electrode material surface2Film.
Fig. 4 gives NiCo2O4And NiCo2O4/TiO2The X-ray photoelectron spectroscopic analysis map of each element of nano wire.
Fig. 4 a is the open score figure of Co2p, corresponds to Co in conjunction with the peak that can be located at 781 and 794.7eV2+, in conjunction with 779.6 and 796eV can be located at
Peak correspond to Co3+.Fig. 4 b is the open score figure of Ni2p, it can be seen that Ni element is mainly Ni2+And Ni3+Two kinds of valence state forms are deposited
Electron binding energy is located at the 874.6eV of the 856.4eV and 2p1/2 of 2p2/3, and the result is consistent with XRD test result.Fig. 4 c
It is the open score figure of Ti2p, it can be seen that electron binding energy is located at the 464.3eV of the 457eV and 2p1/2 of 2p3/2, is a typical case
Ti4+The peak position of-O key is distributed[72].Fig. 4 d is the open score figure of O1s, and four peak positions therein are respectively labeled as O1, O2, O3
And O4.In conjunction with the bond energy that positioned at the O1 of 539.4eV can be a typical metal oxide.In conjunction with can positioned at 530eV O2 with
Hydroxyl groups are related.The appearance of O3 shows NiCo2O4/TiO2The aerobic vacancy defect of nanowire surface, typically appears in mesoporous material
In, it is consistent with the result of TEM (images of transmissive electron microscope).The appearance of O4 is attributed to the physical/chemical adsorption effect of nanowire surface.
These elements can provide very high specific capacitance, it is made to show outstanding chemical property by different Valence changes.
2、NiCo2O4And NiCo2O4/TiO2The chemical property comparative analysis of composite nano-line
In order to which the chemical property to two kinds of electrode materials has one more fully to understand, pass through cyclic voltammetry, constant current
Charge-discharge test, ac impedance measurement is respectively to the capacitance of electrode material, and multiplying power, cyclical stability and impedance etc. are surveyed
Examination.NiCo2O4/TiO2It is as shown in Figure 5 a that electrode material difference potential sweeps cyclic voltammetry result under speed.It can from figure
Out, electrode material has apparent fake capacitance characteristic.Fig. 5 b is NiCo respectively2O4And NiCo2O4/TiO2Nano material is as electrode
The constant current charge-discharge curve of material, it can be seen that apparent charge and discharge platform, illustrates that oxygen has occurred herein in charging and discharging curve
Change reduction reaction, match with the result of CV curve, and it can be seen from the figure that material after atomic layer deposition is modified
The specific capacity of material is significantly improved.In fig. 5 c, the NiCo after being handled by atomic layer deposition2O4/TiO2Nano line electrode
Material is in 2,4,5,10,15,20,25,30mA/cm2Current density under specific capacity be respectively 2.94,2.88,2.86,
2.62、2.57、2.49、2.32、2.25、2.1F/cm2, compared to NiCo2O4The specific capacity of nano line electrode material has obviously
Raising.Fig. 5 d is ac resistance analysis image, by image as can be seen that in initial reaction stage, NiCo2O4Electrode material it is interior
Resistance is less than NiCo2O4/TiO2Electrode material.But after recycling a period of time, NiCo2O4/TiO2The internal resistance of electrode material is less than
NiCo2O4Electrode material, this may be with as circulation carries out, and electrode material surface generates nickel cobalt oxide particle shell, and introduces
Activation process occurs for a small amount of Lacking oxygen and carbon and oxygen functional group related.In the stable circulation linearity curve of Fig. 5 e, it can be seen that
NiCo2O4/TiO2Under the premise of greatly improving electric conductivity, compared to research before, cyclical stability has electrode material
Apparent improvement is still higher than NiCo in 4000 circulations with the specific capacity of rear electrode material2O4The specific capacity of electrode material,
Conservation rate is 63%.
Such as Fig. 6,4000 later transmission electron microscope pictures are recycled by two kinds of electrode materials, it can be seen that NiCo2O4Electricity
Apparent change, nano wire distortion bending has occurred in nano wire shape characteristic after the material circulation of pole, and has a large amount of reaction
Product is attached to nanowire surface, affects reaction and carries out, this also explains NiCo2O4Electrode material is under high specific capacity
Its cycle performance declines very fast reason.And NiCo2O4/TiO2Electrode material is due to there is ultra-thin TiO2The protective effect of layer, is being followed
There is no too big changes for its nano wire pattern after ring, and only less reaction product is attached to nanowire surface, thus higher
It is recycled under specific capacity state repeatedly still preferable with rear stability.
To sum up, the present invention is in atomic layer deposition TiO2Before and after film, the pattern of electrode material does not change, and does not destroy original
There is structure, stability while remaining biggish specific surface area for structure provides protection.The electrode material that the present invention obtains
Material has high conformality, and chemical property significantly improves.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.
Used herein a specific example illustrates the principle and implementation of the invention, and above embodiments are said
It is bright to be merely used to help understand method and its core concept of the invention；At the same time, for those skilled in the art, foundation
Thought of the invention, there will be changes in the specific implementation manner and application range.In conclusion the content of the present specification is not
It is interpreted as limitation of the present invention.
Claims (9)
1. a kind of modified electrode material in surface, which is characterized in that aoxidized including nickel cobalt oxide nano wire and in the nickel cobalt
The titanium deoxid film of the outer surface cladding of object nano wire；
The nickel cobalt oxide nano wire includes foam nickel base, the nickel cobalt oxide nano of array distribution in the foam nickel base
Line；The nickel cobalt oxide nano wire is heat-treated by nickel cobalt oxide nanowire precursor；
The titanium deoxid film recycles Multiple depositions to the nickel cobalt oxide nano wire forerunner by technique for atomic layer deposition
The outer surface of body.
2. the modified electrode material in surface according to claim 1, which is characterized in that the titanium deoxid film is plate titanium
Mine structure.
3. the modified electrode material in surface according to claim 1, which is characterized in that the thickness of the titanium deoxid film
For 1nm.
4. the modified processing method of a kind of pair of electrode material surface, which is characterized in that including：
Nickel cobalt oxide nano wire is synthesized in foam nickel base, obtains nickel cobalt oxide nanowire precursor；
Using technique for atomic layer deposition the nickel cobalt oxide nanowire precursor surface circulation deposition of titanium oxide, in institute
The surface for stating nickel cobalt oxide nanowire precursor forms layer of titanium dioxide film, obtains nickel cobalt oxide nanowire precursor
And composite titania material；
By the composite material be put into atmospheric environment carry out temperature be 300 DEG C of times be 2h annealing, obtain to surface and change
Nickel cobalt oxide and titanium dioxide membrane electrode provided material after property.
5. processing method according to claim 4, which is characterized in that described to synthesize nickel cobalt oxide in foam nickel base
Nano wire obtains nickel cobalt oxide nanowire precursor, specifically includes：
The foam nickel base being sized is taken up in order of priority and is placed on progress ultrasonic cleaning 5min in acetone soln and ethanol solution,
Foam nickel base after cleaning is put into air dry oven, 3h is dried with 80 DEG C of drying temperature, obtains standard foam nickel
Substrate；
0.58g cobalt nitrate, 0.18g ammonium fluoride and 1.2g urea are dissolved in 35ml deionized water, it is molten to form uniform pink colour
Liquid；
It is to react in the reaction kettle of 50ml that by the pink colour solution and the standard foam nickel substrate, to put temperature into, which be 120 DEG C of capacity,
6h after cooled to room temperature, opens the reaction kettle, takes out nickel cobalt oxide nano wire obtained；
By nickel cobalt oxide nano wire deionized water repeated flushing 5min, then put into drying box with 80 DEG C of drying temperature
Degree drying 3h, obtains nickel cobalt oxide nanowire precursor.
6. processing method according to claim 4, which is characterized in that the titanium deoxid film is brockite structure.
7. processing method according to claim 4, which is characterized in that the titanium deoxid film with a thickness of 1nm.
8. processing method according to claim 4, which is characterized in that described to utilize technique for atomic layer deposition in the nickel cobalt
The number of the surface circulation deposition of titanium oxide of oxide nano thread presoma is 40-60 times.
9. processing method according to claim 4, which is characterized in that the foam nickel base is sized as 1cm*
2cm。
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| CN112162439A (en) * | 2020-10-14 | 2021-01-01 | 中国科学技术大学 | Method for enhancing optical regulation and control capability of titanium dioxide electrode |
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