CN103646792B - A kind of preparation method of metal/metal oxide nano composite material - Google Patents
A kind of preparation method of metal/metal oxide nano composite material Download PDFInfo
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- CN103646792B CN103646792B CN201310705152.7A CN201310705152A CN103646792B CN 103646792 B CN103646792 B CN 103646792B CN 201310705152 A CN201310705152 A CN 201310705152A CN 103646792 B CN103646792 B CN 103646792B
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Abstract
The invention belongs to technical field of nanometer material preparation, relate to the preparation method of a kind of metal/metal oxide nano composite material.Feature of present invention is: is first according to the concentration preparation oxalic acid solution of 0.01～1.5mol/L, prepares electrolyte；Again flat metal or foam metal are placed in prepared electrolyte, carry out anodized with constant-voltage method or constant flow method；The extent of reaction is controlled, the most controlled metal/metal oxide nano composite material preparing different-shape, thickness, composition by controlling reaction condition such as response voltage or electric current, response time and reaction temperature etc..The metal/metal oxide nano composite material prepared by the method, it is 50 nanometers～the metal oxide layer of 100 microns including flat board or the metallic substrates of foam form and thickness, metal-oxide directly generates in metal surface, in petal-shaped or graininess, a size of 50～500 nanometers.The present invention is simple, the cycle is short, strong adaptability, low cost, beneficially business application.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, relate to a kind of nano combined material of metal/metal oxide
The preparation method of material.
Background technology
Metal-oxide is as the common electrode material of ultracapacitor, and it has the electric capacity higher than carbon electrode material
Advantage with the electrochemical stability higher than macromolecular material.The preparation method of metal-oxide is a lot, leads at present
Electrochemical deposition method to be had, sol-gal process, template and hydro-thermal method etc., operate complex, to experiment behaviour
It is required higher and wastes time and energy.Additionally, as a kind of electrode material, metal-oxide often need to be supported on gold
To support and to strengthen electric conductivity on Shuing.Common method, a kind of is that the mealy metallic oxide of preparation is coated in bubble
On foam metal；One is in-situ preparation on metal.Both approaches, the first lack of homogeneity, loose contact
Being easily caused poor stability, the second operation is relatively complicated, wayward.
Hu Junqing, Xu Kaibing etc. reported one hydro-thermal method in 2013 and prepare electrode material for super capacitor
The method of nickel oxide, the method time-consumingly long, complex steps (Hu Junqing, Xu Kaibing " a kind of super capacitor electrode
The preparation method of pole material oxidation nickel " CN201210438935, on January 16th, 2013).Song dynasty's literary composition, pipe
Road peaces etc. reported the preparation method of a kind of nano nickel oxide composite electrode in 2011, were to pass through calcined powder
The nano oxidized nickel material of shape and a certain amount of metallic element and make the composite that slurry obtains, the method needs point
Step operation, it is impossible to disposably prepare metal/nickel oxide composite material, and with the material made to be the most also
Active substance conventional method makes electrode (Song dynasty's literary composition, the pipeline peace " nano-nickel oxide for ultracapacitor
Combination electrode and preparation method thereof " CN201010265362.5, on January 19th, 2011).
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of easy and simple to handle, controlled easy, suitable
The preparation method of the metal/metal oxide nano composite material of Ying Xingguang.The method is at flat board and foam metal
(ferrum, cobalt, copper, nickel, manganese etc.) upper directly preparation has the metal-oxide of even structure, Ke Yiti
High metallic substrates and the contact of metal-oxide, enhance the stability of electrode material, electric conductivity, significantly carry
The utilization rate of high metal-oxide, and simplify operating procedure.
The present invention is achieved in the following ways:
The preparation method of a kind of metal/metal oxide nano composite material, is characterized in that comprising the following steps:
(1) prepare oxalic acid solution according to the concentration of 0.01～1.5mol/L, prepare electrolyte；
(2) by flat metal or foam metal, it is placed in the electrolyte prepared by step (1), metal used
For the one in ferrum, cobalt, copper, nickel, manganese；Anodized is carried out with constant-voltage method or constant flow method；Constant-voltage method
Reaction condition be: reaction potential 1～100 volts, 10 seconds response time～1 hour, reaction temperature-10～
90 degrees Celsius；The reaction condition of constant flow method is: kinetic current 10 milliamperes～30 peaces, 10 seconds response time～1
Hour, reaction temperature-10～90 degrees Celsius；Prepare corresponding metal/metal oxide nano composite material.
The preparation method of above-mentioned a kind of metal/metal oxide nano composite material, is characterized in that working as flat metal
Or foam metal is when being nickel, need the composite prepared in step (2) to carry out at 325～400 degrees Celsius
Annealing, obtains nickel/nickel oxide nano composite.
The preparation method of above-mentioned a kind of metal/metal oxide nano composite material, it is characterized in that preparation metal/
Metal oxide nano composite material includes that base metal and thickness are 50 nanometers～the burning of 100 microns
Nitride layer；Metal-oxide is petal-shaped or graininess, a size of 50～500 nanometers；Metal oxide layer is base
The oxide of substrate also directly generates in base metal surfaces, and uniform fold is in base metal surfaces.
Embodiment of the present invention be preparation oxalic acid solution, with anodised method metal (ferrum, cobalt, copper,
Nickel, manganese etc.) oxide of Surface Creation metal, by changing concentration and volume, proportioning and the reaction of solution
The parameters such as temperature, voltage (electric current), time, electrode spacing, regulation generates the structure of oxide.The present invention
The thickness of prepared metal/metal oxide nano composite material is adjustable, structure-controllable, the electric conductivity of material,
Uniformity, stability etc. are all effectively improved.The metal/metal oxide nano composite material of preparation can be answered
It is used in aspects such as preparing sensor, chemical catalysis, lithium ion battery and ultracapacitor.
The invention have the advantages that
(1) gold preparing different-shape, thickness, composition that preparation method of the present invention can be the most controlled
Genus/metal oxide nano composite material, the method low cost, controlled easy, applied widely, beneficially business
Industry is applied；
(2) metal/metal oxide nano composite material of the present invention, it is not necessary to binding agent, metal oxygen
Compound directly generates in metal surface, has been provided simultaneously with metal-oxide high-specific surface area and metal high conductivity
Feature, the metal-oxide obtained is in the side such as sensor, chemical catalysis, lithium ion battery and ultracapacitor
There is application in face.
Detailed description of the invention
Two ten one specific embodiments of the present invention are given below, but institute of the present invention protection domain is not limited to this.
Embodiment 1
The preparation method of a kind of nickel foam/nickel oxide nano composite is as follows:
(1) oxalic acid solution of preparation 0.01mol/L is standby；
(2) by 2 cm x 2 centimetres, the nickel foam of 2 millimeters thick is placed in the electrolyte described in (1), connects
Wire, nickel foam does positive pole, and flat board nickel sheet does negative pole；
(3) under subzero 70 volts of voltages of 5 degrees Celsius of constant potentials, nickel foam is carried out anodized, reaction
40 minutes, prepare nickel foam/bis-oxalic acid hydrate nickel nano composite material.
In resulting materials, two oxalic acid hydrate nickel are that block is reunited, on the ligament being deposited in nickel foam straggly, and block
Diamondwise, the length of side at 500 ran, has space, it has micropore between block, pore size is received several
Rice, further increases specific surface area, and these gaps and the diffusion that micropore is electrolyte leave big quantity space, have
It is beneficial to the mass transfer in charge and discharge process.
Above-mentioned material is annealed under 400 degrees Celsius and is obtained nickel foam/nickel oxide nano composite, nickel oxide shape
Shape is close to cauliflower, the bottom surface length of side 200 ran, and top gathering is connected in nickel foam, it has many receive
Rice grain pattern road, space becomes big, advantageously in the diffusion transport of electrolyte.
Embodiment 2
The preparation method of a kind of nickel foam/bis-oxalic acid hydrate nickel nano composite material is as follows:
(1) oxalic acid solution of preparation 0.5mol/L is standby；
(2) by 2 cm x 2 centimetres, the nickel foam of 2 millimeters thick is placed in the electrolyte described in (1), connects
Wire, nickel foam does positive pole, and flat board nickel sheet does negative pole；
(3) under subzero 50 volts of voltages of 10 degrees Celsius of constant potentials, nickel foam is carried out anodized, reaction
5 minutes, prepare nickel foam/bis-oxalic acid hydrate nickel nano composite material.
Embodiment 3
The preparation method of a kind of nickel foam/bis-oxalic acid hydrate nickel nano composite material is as follows:
(1) oxalic acid solution of preparation 1.5mol/L is standby；
(2) by 2 cm x 2 centimetres, the nickel foam of 2 millimeters thick is placed in the electrolyte described in (1), connects
Wire, nickel foam does positive pole, and flat board nickel sheet does negative pole；
Under 20 volts of voltages of (3) 30 degrees Celsius of constant potentials, nickel foam is carried out anodized, reacts 10 points
Clock, prepares nickel foam/bis-oxalic acid hydrate nickel nano composite material.
Embodiment 4
The preparation method of a kind of nickel foam/bis-oxalic acid hydrate nickel nano composite material is as follows:
(1) oxalic acid solution of preparation 0.5mol/L is standby；
(2) by 2 cm x 2 centimetres, the nickel foam of 2 millimeters thick is placed in the electrolyte described in (1), connects
Wire, nickel foam does positive pole, and flat board nickel sheet does negative pole；
(3) under subzero 5 degrees Celsius of constant currents 3 peace, nickel foam is carried out anodized, reacts 10 minutes,
Prepare nickel foam/bis-oxalic acid hydrate nickel nano composite material.
Embodiment 5
The preparation method of a kind of nickel foam two oxalic acid hydrate nickel nano composite material is as follows:
(1) oxalic acid solution of preparation 0.1mol/L is standby；
(2) by 2 cm x 2 centimetres, the nickel foam of 2 millimeters thick is placed in the electrolyte described in (1), connects
Wire, nickel foam does positive pole, and flat board nickel sheet does negative pole；
Under 40 volts of voltages of (3) 25 degrees Celsius of constant potentials, nickel foam is carried out anodized, reacts 10 points
Clock, prepares nickel foam/bis-oxalic acid hydrate nickel nano composite material.
Embodiment 6
The preparation method of a kind of flat board nickel/bis-oxalic acid hydrate nickel nano composite material is as follows:
(1) oxalic acid solution of preparation 0.05mol/L is standby；
(2) by 2 cm x 2 centimetres, 100 microns of thick flat board nickel are placed in the electrolyte described in (1), even
Connecing wire, positive and negative pole material is all flat board nickel；
(3) under subzero 60 volts of voltages of 5 degrees Celsius of constant potentials, flat board nickel is carried out anodized, reaction
45 minutes, prepare flat board nickel/bis-oxalic acid hydrate nickel nano composite material.
Embodiment 7
The preparation method of a kind of flat board nickel/bis-oxalic acid hydrate nickel nano composite material is as follows:
(1) oxalic acid solution of configuration 0.3mol/L is standby；
(2) by 2 cm x 2 centimetres, 100 microns of thick flat board nickel are placed in the electrolyte described in (1), even
Connecing wire, positive and negative pole material is all flat board nickel；
(3) under subzero 40 volts of voltages of 5 degrees Celsius of constant potentials, flat board nickel is carried out anodized, reaction
20 minutes, prepare flat board nickel/bis-oxalic acid hydrate nickel nano composite material.
Embodiment 8
The preparation method of a kind of flat board nickel/bis-oxalic acid hydrate nickel nano composite material is as follows:
(1) oxalic acid solution of preparation 1mol/L is standby；
(2) by 2 cm x 2 centimetres, 100 microns of thick flat board nickel are placed in the electrolyte described in (1), even
Connecing wire, positive and negative pole material is all flat board nickel；
(3) under subzero 30 volts of voltages of 5 degrees Celsius of constant potentials, flat board nickel is carried out anodized, reaction
10 minutes, prepare flat board nickel/bis-oxalic acid hydrate nickel nano composite material.
Embodiment 9
The preparation method of a kind of flat board nickel/bis-oxalic acid hydrate nickel nano composite material is as follows:
(1) oxalic acid solution of configuration 0.1mol/L is standby；
(2) by 2 cm x 2 centimetres, 100 microns of thick flat board nickel are placed in the electrolyte described in (1), even
Connecing wire, positive and negative pole material is all flat board nickel；
(3) subzero 5 degrees Celsius of constant currents 5 are pacified and flat board nickel are carried out anodized, react 10 minutes,
Prepare flat board nickel/bis-oxalic acid hydrate nickel nano composite material.
Embodiment 10
The preparation method of a kind of flat board cobalt/cobalt oxide nano composite material is as follows:
(1) oxalic acid solution of configuration 0.3mol/L is standby；
(2) by 2 cm x 2 centimetres, 100 microns of thick flat board cobalts are placed in the electrolyte described in (1), even
Connecing wire, positive and negative pole material is all flat board cobalt；
(3) under subzero 50 volts of voltages of 5 degrees Celsius of constant potentials, flat board cobalt is carried out anodized, reaction
15 minutes, prepare flat board cobalt/cobalt oxide nano composite material.
Embodiment 11
The preparation method of a kind of flat board cobalt/cobalt oxide nano composite material is as follows:
(1) oxalic acid solution of configuration 1mol/L is standby；
(2) by 2 cm x 2 centimetres, 100 microns of thick flat board cobalts are placed in the electrolyte described in (1), even
Connecing wire, positive and negative pole material is all flat board cobalt；
Under 40 volts of voltages of (3) 10 degrees Celsius of constant potentials, flat board cobalt is carried out anodized, reacts 15 points
Clock, prepares flat board cobalt/cobalt oxide nano composite material.
Embodiment 12
The preparation method of a kind of flat board cobalt/cobalt oxide nano composite material is as follows:
(1) oxalic acid solution of configuration 1.2mol/L is standby；
(2) by 2 cm x 2 centimetres, 100 microns of thick flat board cobalts are placed in the electrolyte described in (1), even
Connecing wire, positive and negative pole material is all flat board cobalt；
Under (3) 20 degrees Celsius of constant current 2 peaces, flat board cobalt is carried out anodized, reacts 15 minutes,
Prepare flat board cobalt/cobalt oxide nano composite material.
Embodiment 13
The preparation method of a kind of ferrum/ferric oxide nano composite, metal used is ferrum, and remaining is with embodiment 2.
Embodiment 14
The preparation method of a kind of ferrum/ferric oxide nano composite, metal used is ferrum, and remaining is with embodiment 3.
Embodiment 15
The preparation method of a kind of ferrum/ferric oxide nano composite, metal used is ferrum, and remaining is with embodiment 4.
Embodiment 16
The preparation method of a kind of copper/cupric oxide nano composite, metal used is copper, and remaining is with embodiment 2.
Embodiment 17
The preparation method of a kind of copper/cupric oxide nano composite, metal used is copper, and remaining is with embodiment 3.
Embodiment 18
The preparation method of a kind of copper/cupric oxide nano composite, metal used is copper, and remaining is with embodiment 4.
Embodiment 19
The preparation method of a kind of manganese/manganese oxide nano composite material, metal used is manganese, and remaining is with embodiment 2.
Embodiment 20
The preparation method of a kind of manganese/manganese oxide nano composite material, metal used is manganese, and remaining is with embodiment 3.
Embodiment 21
The preparation method of a kind of manganese/manganese oxide nano composite material, metal used is manganese, and remaining is with embodiment 4.
Claims (2)
1. a preparation method for metal/metal oxide nano composite material, is characterized in that comprising the following steps:
(1) prepare oxalic acid solution according to the concentration of 0.01～1.5mol/L, prepare electrolyte；
(2) flat board nickel or nickel foam are placed in the electrolyte prepared by step (1), with constant-voltage method or constant current
Method carries out anodized；The reaction condition of constant-voltage method is: reaction potential 1～100 volts, response time 10
Second～1 hour, reaction temperature-10～90 degrees Celsius；The reaction condition of constant flow method is: kinetic current 10 milliamperes～
30 peaces, 10 seconds response time～1 hour, reaction temperature-10～90 degrees Celsius；
(3) nickel/bis-oxalic acid hydrate nickel nano composite material that will prepare in step (2), takes the photograph in 325～400
Family name's degree makes annealing treatment, and obtains nickel/nickel oxide nano composite.
The preparation method of a kind of metal/metal oxide nano composite material the most according to claim 1,
It is characterized in that the metal/metal oxide nano composite material of preparation includes that base metal and thickness are 50 nanometers
The metal oxide layer of-100 microns；Metal-oxide is petal-shaped or graininess, a size of 50-500 nanometer；
Metal oxide layer is the oxide of base metal and directly generates in base metal surfaces, and uniform fold is at metal
On surface.
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| CN105097297B (en) * | 2014-05-08 | 2018-04-03 | 同济大学 | The method for preparing high activity electrode material for super capacitor nano cupric oxide |
| CN104120480A (en) * | 2014-08-13 | 2014-10-29 | 南京大学（苏州）高新技术研究院 | Method for preparing nickel oxide buffer layer for high temperature superconducting coated conductors |
| CN105118691B (en) * | 2015-09-14 | 2018-01-23 | 南京大学 | Nickel foam supports ferrous sub-micron tube electrode material of cobalt acid and preparation method thereof |
| CN106531464B (en) * | 2016-11-28 | 2018-10-16 | 东佳电子（郴州）有限公司 | A kind of preparation method of high-performance symmetric form ultracapacitor |
| US11559791B2 (en) * | 2020-01-22 | 2023-01-24 | The Regents Of The University Of California | Carbon-doped nickel oxide catalyst and methods for making and using thereof |
| CN113394030B (en) * | 2021-06-26 | 2022-09-09 | 南昌师范学院 | Nickel-based electrode material and preparation method and application thereof |
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| US4391668A (en) * | 1980-09-02 | 1983-07-05 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of National Defence | Mixed oxide oxygen electrode |
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| US4391668A (en) * | 1980-09-02 | 1983-07-05 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of National Defence | Mixed oxide oxygen electrode |
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| Growth of Different Nanostructures of Cu2O (Nanothreads, Nanowires, and Nanocubes) by Simple Electrolysis Based Oxidation of Copper;Dinesh Pratap Singh等;《J. Phys. Chem. C》;20070401;摘要及实验部分 * |
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