CN107658145A - A kind of three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide and preparation method and application - Google Patents
A kind of three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide and preparation method and application Download PDFInfo
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- CN107658145A CN107658145A CN201710909263.8A CN201710909263A CN107658145A CN 107658145 A CN107658145 A CN 107658145A CN 201710909263 A CN201710909263 A CN 201710909263A CN 107658145 A CN107658145 A CN 107658145A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide, it is to use using conducting bracket material as electrode and support, in its superficial growth metal composite oxide presoma, then by being heat-treated and nitrogenizing, the method for the composition metal nitrogen/oxide formed on load conducting bracket material is made；Composition metal nitrogen/the oxide is that the composite metal nitride nanoparticle connected on conducting bracket material with metal composite oxide nanometer sheet forms three-dimensional " nanometer pearl-decorated curtain " shape, wherein metal composite oxide nanometer chip size is 100~500nm, a diameter of 5~the 50nm of composite metal nitride nanoparticle, composition metal nitrogen/load capacity of the oxide on conducting bracket are 0.1~0.5mg/cm2.Operating procedure of the present invention is simple, and relatively low cost and higher capacitive property cause the energy storage aspect that is incorporated in of composition metal nitrogen/oxide to have broad application prospects.
Description
Technical field
The present invention relates to a kind of three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide and preparation method thereof with preparing electricity
Application in container electrode material.
Background technology
Ultracapacitor and electrochemical capacitor are received much concern with advantages such as its high-energy-density and power densities in recent years.
The key of acquirement high-energy-density and power density is largely dependent upon the selection and preparation of electrode material.Except traditional
Outside double layer capacitor, the capacitor of fake capacitance also gets most of the attention.Traditional fake capacitance capacitor electrode material is mainly Mn,
The mixing of the metal oxides such as Ni, Co, hydroxide or both.But such electrode material causes electricity due to the problems such as electric conductivity
It is poor high rate performance to be present in container, the more low drawback of capacitive property.
To improve disadvantages mentioned above, by metal oxide hetero atom or Heteroatom doping to introduce abundant functional group with reality
Now improve the performance of fake capacitance capacitor.Metal nitride causes the discussion interest of numerous scientific research personnel at present.Metal nitride
There is many advantageous characteristics, such as high reaction activity, excellent electronic characteristic and good catalysis effect compared with metal oxide
Fruit etc..Additionally due to the price of metal nitride is relatively low, therefore it also has larger potential in energy storage field, is ideal
Anode material.Traditional metal nitride is CoN, CrN, VN or nitrided iron etc., but such nitride is because of its stability and synthesis
Complex process etc., when being used as electrode material, capacitor high rate performance is low, and cyclical stability is poor, it is still necessary to further improves.Therefore
There is an urgent need to develop new nitride material as high-performance fake capacitance material, the defects of to solve current material and technology.Through
Retrieval, about three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide and preparation method thereof and preparing capacitor electrode material
In application have not been reported.
The content of the invention
Carried for the deficiency of current fake capacitance material property, and the preparation of nitride material and performance limitation, the present invention
Supply one kind that there is three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide of high-performance fake capacitance and preparation method thereof with preparing
Application in capacitor electrode material.
To obtain above-mentioned three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide material with high-performance fake capacitance, this
Inventing the technical scheme used and reaction mechanism is：Using constant voltage electrochemical deposition method, prepared in conductive substrates point
The uniform metal composite oxide presoma of cloth, metal composite oxide is obtained by calcining, then by corresponding atmosphere
Further heat treatment, the nitridation process of metal composite oxide is realized, so as to obtain target composition metal nitrogen/oxide.Pass through
Realize that there are the three-dimensional " nano-beads of high-performance fake capacitance with reference to the stability of metal oxide and the high reaction activity of metal nitride
The preparation of curtain shape " composition metal nitrogen/oxide.
Specifically, three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide of the present invention, is used with conducting bracket
Material is electrode and support, in its superficial growth metal composite oxide presoma, then by being heat-treated and nitrogenizing, is formed negative
The method for carrying composition metal nitrogen/oxide on conducting bracket material is made；It is characterized in that：The three-dimensional " nanometer pearl-decorated curtain shape "
Composition metal nitrogen/oxide is the composite metal nitride connected on conducting bracket material with metal composite oxide nanometer sheet
Nanoparticle forms three-dimensional " nanometer pearl-decorated curtain " shape, and wherein metal composite oxide nanometer chip size is 100~500nm, compound gold
Category nitride nano microsphere diameter be 5~50nm, composition metal nitrogen/load capacity of the oxide on conducting bracket for 0.1~
0.5mg/cm2；Metal composite oxide is that the two-dimentional cobalt acid nickel that nanometer sheet is representative is received in the composition metal nitrogen/oxide structure
Rice piece, composite metal nitride are that nanoparticle is the three-dimensional nickel cobalt nitrogen represented and/or is two-dimentional nickel of the nano particle as representative
Cobalt nitrogen；The conducting bracket material is porous metal material, selects one kind in nickel foam, titanium foam, foam copper, conducting bracket material
The size of material is 1 × 4cm2~4 × 8cm2, depositional area is 1 × 1cm2~1 × 4cm2。
In above-mentioned three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide：The metal composite oxide nanometer sheet chi
Very little is preferably 200~400nm, and composite metal nitride nanoparticle diameter is preferably 10~30nm, composition metal nitrogen/oxide
Load capacity on conducting bracket is 0.2~0.4mg/cm2, the conducting bracket material preferred foams nickel, it is preferably dimensioned to be 1
×4cm2~1 × 6cm2, depositional area is preferably 1 × 1cm2~1 × 3cm2。
The preparation method of three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide of the present invention, step are：
(1) electrochemical deposition of metal composite oxide presoma；
(2) calcining of electrochemical deposition thing, prepares metal composite oxide；
(3) nitridation of metal composite oxide, three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide is made；
It is characterized in that：
The method of the electrochemical deposition of step (1) the metal composite oxide presoma is：According to mol ratio 1:1~5:
1 is dissolved in water two kinds of salt in manganese nitrate, cobalt nitrate, nickel nitrate or ferric nitrate, is stirred continuously complete to dissolving；Measure 10
The mixed solution that~50mL is prepared is placed in electrolytic cell, is 1 × 4cm by size2~4 × 8cm2Conducting bracket material suspend leaching
In mixing salt solution, 2~20min is deposited with -0.2~-1V with constant voltage electrochemical deposition method, depositional area is 1 × 1~1
×4cm2；Product after electrochemical deposition is cleaned up with deionized water, is placed in vacuum drying chamber, at 50~100 DEG C
Dry 5~24h；
The method that the calcining of step (2) the electrochemical deposition thing prepares metal composite oxide is：By dried electricity
Chemical sediment is placed in silica crucible, then crucible is placed in tube furnace, under nitrogen and/or argon gas atmosphere protection, with 1~
10 DEG C/min heating rates are warming up to 300~350 DEG C, calcine 1~5h；Air velocity is 50~100scc；It is cooled to room temperature
Obtained product is metal composite oxide afterwards；
Step (3) it is described by metal composite oxide nitridation method be：Metal composite oxide will be obtained in step (2)
It is placed in silica crucible, then crucible is placed in tube furnace, then passes to nitrogen, ammonia, nitrogen/hydrogen or Nitrogen, Ammonia,
300~800 DEG C are warming up to 1~10 DEG C/min, calcines 1~5h；Air velocity is 20~100scc；It is cooled to institute after room temperature
The product obtained is three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide.
In the preparation method of above-mentioned three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide：Step (1) described conducting bracket
One kind in material preferred foams nickel, titanium foam, foam copper, conducting bracket material are preferably dimensioned to be 1 × 4cm2~1 × 6cm2,
Depositional area is preferably 1 × 1cm2~1 × 3cm2, with constant voltage electrochemical deposition method preferably with -0.8~-1V deposition 10~
12min。
In the preparation method of above-mentioned three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide：Step (2) preferable embodiment party
Formula is under nitrogen or argon gas atmosphere protection, is warming up to 320 DEG C with 1~2 DEG C/min heating rates, calcines 2~4h.
In the preparation method of above-mentioned three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide：Step (3) preferable embodiment party
Formula is under ammonia or Nitrogen, Ammonia atmosphere protection, is warming up to 400 DEG C with 1~2 DEG C/min heating rates, calcines 2~4h.
Three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide answering in capacitor electrode material is prepared of the present invention
With.
The present invention can overcome self-supporting electrode material conduction base from matrix of the metal composite oxide as nitridation
The shortcomings that combination degree is poor between electrode material, electric conductivity is low, the part of simultaneous oxidation thing, which retains, can effectively improve electrode material
Stability；The formation of nitride can provide more reactivity sites, improve the compatibility of compound and electrolyte, reduce electricity
The resistivity of pole material improves the high rate performance and cyclical stability of pseudocapacitors simultaneously.Experiment confirms：The three-dimensional of the present invention " is received
Measle curtain shape " composition metal nitrogen/oxide has good electric conductivity and chemical property (see Fig. 4~Fig. 6), its higher electricity
Capacitive can cause the energy storage aspect that is incorporated in of composition metal nitrogen/oxide to be widely used, and indicate that it is preparing capacitor electricity
Had broad application prospects in the material of pole.
The present invention has the advantage that:
(1) present invention is to synthesize metal composite oxide presoma using electrochemical deposition method one-step method, and with
Collector does substrate, without adding binding agent.Technique is easy and effective, cost-effective, avoid shadow of the binding agent to capacitor performance
Ring.
(2) present invention is nitrogenized using metal composite oxide, can be participated in more compared with single metallization compound first
More redox reactions provides higher fake capacitance, and the secondly introducing of nitrogen causes complex metal compound metal oxide
Overcome the defects of multiplying power is low, resistivity is high and cyclical stability is poor, metal composite oxide part is left composition metal nitrogen
Compound provides bigger reference area and provides more avtive spots, while composition metal nitrogen/higher chemical stability of oxide
Be advantageous to the capacitive property of capacitor.
Brief description of the drawings
Fig. 1 is the front and rear XPS spectrum figure (a) and XRD (b) of metal composite oxide nitridation.
Fig. 2 be different amplification under metal composite oxide (a) to (c), metal composite oxide nitridation after (d) extremely
(f) SEM schemes.
Fig. 3 be different amplification under metal composite oxide (a), (b), metal composite oxide nitridation after (c),
(d) TEM schemes.
Fig. 4 is the impedance operator spectrogram before composition metal nitrogen/oxide nitride and after nitridation.
Fig. 5 is the cyclic voltammetry curve of (a) and (b) after nitridation before composition metal nitrogen/oxide nitride.
Fig. 6 is the charging and discharging curve of (a) and (b) after nitridation before composition metal nitrogen/oxide nitride.
Embodiment
With reference to specific embodiment and accompanying drawing, the invention will be further elaborated, but embodiments of the present invention are not
This is only limitted to, in addition to any combination between each embodiment.Routine techniques is can refer to for unreceipted technological parameter
Carry out.
Embodiment 1
The preparation method of three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide, step are：
(1) it is 2 according to mol ratio by cobalt nitrate and nickel nitrate:1 ratio mixed dissolution is stirred continuously to mixing in water
Completely.
(2) mixed solution for measuring 40mL preparations is placed in electrolytic cell, cuts 1 × 5cm2Nickel foam be suspended in mixing it is molten
In liquid, the wetted area of nickel foam is 1 × 1cm2.Circuit is connected in a manner of three-electrode system, is sunk using constant voltage electrochemistry
Area method, deposition voltage are -1V, deposit 10min.Post-depositional nickel foam is cleaned to remove surface attachment repeatedly with deionized water
Thing and the ion of attachment.Nickel foam after cleaning is placed in vacuum drying chamber, and 24h is dried at 50 DEG C.
(3) dried nickel foam is placed in silica crucible, be placed in tube furnace under argon atmosphere with 1
DEG C/min is warming up to 320 DEG C, it is incubated 2h.Nickel foam after calcining is placed again into tube furnace, with 1 DEG C/min in ammonia atmosphere
Programming rate is warming up to 400 DEG C, is incubated 2h.Air velocity control is 50scc.The product for being cooled to gained after room temperature is multiple
Close metal nitrogen/oxide.
By the composition metal obtained in above-described embodiment nitrogen/oxide PHI 5000X X-ray photoelectron spectroscopy Xs (XPS) and
BrukerD8X x ray diffractions (XRD) (Fig. 1) analysis sample finds the obvious increase of nitrogen element content in the product after nitridation and oxygen is first
Cellulose content reduces substantially, and most of oxygen element successfully substitutes to form Ni by nitrogen in metal composite oxide after calcining3N and
CoN, and retain NiCo2O4。
With HTACHI S-4800 Flied emission Scanning Electron microscopes (Fig. 2) and Japanese JEOL companies JEM2100 types transmission electricity
It is equally distributed porous NiCo that sub- microscope (Fig. 3), which carries out the metal composite oxide that observation finds to obtain,2O4Nanometer sheet.Nitrogen
Porous nano-sheet is changed into the nanoparticle that the size using a small amount of nanometer sheet as connection is about 5-10nm after change.Wherein a small amount of nanometer
Piece is metal composite oxide NiCo2O4, nanoparticle is the product Ni after nitridation3N and CoN, nanometer sheet serve connection nanometer
Wire effect between microballoon.
Composition metal chemical combination before and after testing nitridation with the CHI600E electrochemical workstations of Shanghai Chen Hua Instrument Ltd.
The impedance characteristic and cyclic voltammetry curve of thing, it is found that the complex metal compound after nitridation has good electric conductivity and electricity
Chemical property (Fig. 4~Fig. 6).Indicate that it has a wide range of applications in capacitor electrode material is prepared.
To sum up, the composition metal nitrogen/oxide obtained in above-described embodiment be three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/
Oxide, it is the composite metal nitride nanoparticle connected on conducting bracket material with metal composite oxide nanometer sheet
Form three-dimensional " nanometer pearl-decorated curtain " shape, wherein metal composite oxide nanometer chip size is 100~500nm, composite metal nitride
A diameter of 5~the 50nm of nanoparticle, composition metal nitrogen/load capacity of the oxide on conducting bracket are 0.1~0.5mg/cm2；
Metal composite oxide is the two-dimentional cobalt acid nickel nano film that nanometer sheet is representative in the composition metal nitrogen/oxide structure, compound
Metal nitride is that nanoparticle is the three-dimensional nickel cobalt nitrogen represented and/or is two-dimentional nickel cobalt nitrogen of the nano particle as representative, described
Conducting bracket material is nickel foam.
Embodiment 2
(1) it is 1 according to mol ratio by cobalt nitrate and nickel nitrate:1 ratio mixed dissolution is stirred continuously to mixing in water
Completely.
(2) mixed solution for measuring 40mL preparations is placed in electrolytic cell, cuts 1 × 4cm2Nickel foam be suspended in mixing it is molten
In liquid, the wetted area of nickel foam is 1 × 2cm2.Circuit is connected in a manner of three-electrode system, is sunk using constant voltage electrochemistry
Area method, deposition voltage are -0.8V, deposit 5min.Post-depositional nickel foam is cleaned with deionized water repeatedly attached to remove surface
Thing and the ion of attachment.Nickel foam after cleaning is placed in vacuum drying chamber, and 20h is dried at 60 DEG C.
(3) dried nickel foam is placed in silica crucible, be placed in tube furnace under argon atmosphere with 2
DEG C/min is warming up to 300 DEG C, it is incubated 2h.Nickel foam after calcining is placed again into tube furnace, in ammonia and nitrogen with 4:1 it is mixed
Close in gas and be warming up to 300 DEG C with 1 DEG C/min programming rates, be incubated 2h.Air velocity control is 50scc.It is cooled to room temperature
The product of gained is three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide afterwards.
Embodiment 3
(1) it is 4 according to mol ratio by cobalt nitrate and nickel nitrate:1 ratio mixed dissolution is stirred continuously to mixing in water
Completely.
(2) mixed solution for measuring 50mL preparations is placed in electrolytic cell, cuts 1 × 8cm2Nickel foam be suspended in mixing it is molten
In liquid, the wetted area of nickel foam is 1 × 3cm2.Circuit is connected in a manner of three-electrode system, is sunk using constant voltage electrochemistry
Area method, deposition voltage are -1V, deposit 15min.Post-depositional nickel foam is cleaned to remove surface attachment repeatedly with deionized water
Thing and the ion of attachment.Nickel foam after cleaning is placed in vacuum drying chamber, and 10h is dried at 80 DEG C.
(3) dried nickel foam is placed in silica crucible, be placed in tube furnace under argon atmosphere with 2
DEG C/min is warming up to 350 DEG C, it is incubated 3h.Nickel foam after calcining is placed again into tube furnace, in ammonia and nitrogen mixed proportion
For 3:500 DEG C are warming up to 1 DEG C/min programming rates in 1 gaseous mixture, is incubated 2h.Air velocity control is 50scc.It is to be cooled
The product of gained is three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide after to room temperature.
Claims (7)
1. a kind of three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide, is used using conducting bracket material as electrode and support,
In its superficial growth metal composite oxide presoma, then by being heat-treated and nitrogenizing, formed on load conducting bracket material
The method of composition metal nitrogen/oxide be made；It is characterized in that：Described three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxidation
Thing is to form three on conducting bracket material with the composite metal nitride nanoparticle of metal composite oxide nanometer sheet connection
" nanometer pearl-decorated curtain " shape is tieed up, wherein metal composite oxide nanometer chip size is 100~500nm, and composite metal nitride nanometer is micro-
Bulb diameter is 5~50nm, and composition metal nitrogen/load capacity of the oxide on conducting bracket is 0.1~0.5mg/cm2；This is compound
In metal nitrogen/oxide structure metal composite oxide be nanometer sheet be representative two-dimentional cobalt acid nickel nano film, composition metal nitrogen
Compound is that nanoparticle is the three-dimensional nickel cobalt nitrogen represented and/or is two-dimentional nickel cobalt nitrogen of the nano particle as representative；The conductive branch
Frame material is porous metal material, selects one kind in nickel foam, titanium foam, foam copper, the size of conducting bracket material for 1 ×
4cm2~4 × 8cm2, depositional area is 1 × 1cm2~1 × 4cm2。
2. three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide according to claim 1, it is characterised in that：It is described multiple
It is 200~400nm to close metal oxide nano-sheet size, composite metal nitride nanoparticle a diameter of 10~30nm, compound
Load capacity of the metal nitrogen/oxide on conducting bracket is 0.2~0.4mg/cm2, the conducting bracket material is nickel foam, its
Size is 1 × 4cm2~1 × 6cm2, depositional area is 1 × 1cm2~1 × 3cm2。
3. a kind of preparation method of three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide, step are：
(1) electrochemical deposition of metal composite oxide presoma；
(2) calcining of electrochemical deposition thing, prepares metal composite oxide；
(3) nitridation of metal composite oxide, three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide is made；
It is characterized in that：
The method of the electrochemical deposition of step (1) the metal composite oxide presoma is：According to mol ratio 1:1~5:1 will
Two kinds of salt in manganese nitrate, cobalt nitrate, nickel nitrate or ferric nitrate are dissolved in water, and are stirred continuously complete to dissolving；Measure 10~
The mixed solution that 50mL is prepared is placed in electrolytic cell, is 1 × 4cm by size2~4 × 8cm2Conducting bracket material suspend be immersed in
In mixing salt solution, with constant voltage electrochemical deposition method with -0.2~-1V deposit 2~20min, depositional area be 1 × 1~1 ×
4cm2；Product after electrochemical deposition is cleaned up with deionized water, is placed in vacuum drying chamber, is done at 50~100 DEG C
Dry 5~24h；
The method that the calcining of step (2) the electrochemical deposition thing prepares metal composite oxide is：By dried electrochemistry
Deposit is placed in silica crucible, then crucible is placed in tube furnace, under nitrogen and/or argon gas atmosphere protection, with 1~10
DEG C/min heating rates are warming up to 300~350 DEG C, calcine 1~5h；Air velocity is 50~100scc；After being cooled to room temperature
Obtained product is metal composite oxide；
Step (3) it is described by metal composite oxide nitridation method be：It is placed in metal composite oxide is obtained in step (2)
In silica crucible, then crucible is placed in tube furnace, then passes to nitrogen, ammonia, nitrogen/hydrogen or Nitrogen, Ammonia, with 1~
10 DEG C/min is warming up to 300~800 DEG C, calcines 1~5h；Air velocity is 20~100scc；It is cooled to gained after room temperature
Product is three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide.
4. the preparation method of three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide, its feature exist according to claim 3
In：Step (1) the conducting bracket material is one kind in nickel foam, titanium foam, foam copper, and the size of conducting bracket material is
1×4cm2~1 × 6cm2, depositional area is 1 × 1cm2~1 × 3cm2, sunk with constant voltage electrochemical deposition method with -0.8~-1V
10~12min of product.
5. the preparation method of three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide, its feature exist according to claim 3
In：Step (2) is described under nitrogen or argon gas atmosphere protection, and 320 DEG C are warming up to 1~2 DEG C/min heating rates, and calcining 2~
4h。
6. the preparation method of three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide, its feature exist according to claim 3
In：Step (3) is described under ammonia or Nitrogen, Ammonia atmosphere protection, is warming up to 400 DEG C with 1~2 DEG C/min heating rates, forges
Burn 2~4h.
7. three-dimensional " nanometer pearl-decorated curtain shape " composition metal nitrogen/oxide is preparing capacitor electrode material according to claim 1
In application.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111179440A (en) * | 2020-01-02 | 2020-05-19 | 哈尔滨工业大学 | Three-dimensional object model retrieval method oriented to natural scene |
| CN114551120A (en) * | 2022-01-13 | 2022-05-27 | 河北科技大学 | Preparation method of metal oxide nanosheet |
| CN114974937A (en) * | 2022-06-29 | 2022-08-30 | 哈尔滨理工大学 | Preparation method and application of iron-doped cobaltosic oxide/cobalt nitride heterostructure nanowire electrode material |
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| CN111179440A (en) * | 2020-01-02 | 2020-05-19 | 哈尔滨工业大学 | Three-dimensional object model retrieval method oriented to natural scene |
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| CN114551120B (en) * | 2022-01-13 | 2023-12-19 | 河北科技大学 | Preparation method of metal oxide nanosheets |
| CN114974937A (en) * | 2022-06-29 | 2022-08-30 | 哈尔滨理工大学 | Preparation method and application of iron-doped cobaltosic oxide/cobalt nitride heterostructure nanowire electrode material |
| CN114974937B (en) * | 2022-06-29 | 2022-11-25 | 哈尔滨理工大学 | Preparation method and application of iron-doped cobaltosic oxide/cobalt nitride heterostructure nanowire electrode material |
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