CN106629813B - A kind of supported porous cupric oxide nano line composite of foam copper and its preparation method and application - Google Patents
A kind of supported porous cupric oxide nano line composite of foam copper and its preparation method and application Download PDFInfo
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- CN106629813B CN106629813B CN201710021434.3A CN201710021434A CN106629813B CN 106629813 B CN106629813 B CN 106629813B CN 201710021434 A CN201710021434 A CN 201710021434A CN 106629813 B CN106629813 B CN 106629813B
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Abstract
The present invention is a kind of supported porous cupric oxide nano line composite of foam copper, and the material includes foam Copper substrate, and is supported on the cupric oxide nano line on surface；Wherein 8 ~ 12 μm of cupric oxide nano line length, wide 150 ~ 250nm, nano wire is without cracking, difficult for drop-off, microcosmic upper nano wire has loose structure, and bore dia is 2 ~ 4nm, macroscopically nano wire radially distributes, and every 60 ~ 150 nano wires form a cupric oxide micro-flowers.The composite that the present invention obtains, there is multistage loose structure, the hole of whole three-dimensional structure enriches, and is adapted to light to pass through, and also is adapted for ion transmission.The degradation efficiency that the structure is used as photocatalytically degradating organic dye can improve more than 10 times, and the capability retention as lithium ion battery negative material performance can improve more than 30%.
Description
Technical field
The present invention relates to copper oxide material technical field, specifically a kind of porous copper oxide by foam copper load is received
Rice noodles and its preparation method and application.
Background technology
Cupric oxide is a kind of p-type semiconductor material, and its energy gap is narrower, about 1.2eV, and there is good electrochemistry to live
Property, play great function in ceramics, glaze and the field such as enamel, petroleum sweetening agent, insecticide, hydrogen manufacturing, green glass, and
Photocatalytically degradating organic dye, as lithium ion battery negative material etc. show attracting application potential.
In the prior art, CN106115763A discloses a kind of preparation method of the spherical hierarchical organization material of cupric oxide, should
Product prepared by method is cupric oxide nano powder, needs to be calcined at 400~600 DEG C in its preparation process, and energy consumption is big,
Increase cost.The powder sample be used for catalytic degradation organic dyestuff before, need in dark agitating solution 30 minutes, reach material
Illumination experiment is carried out again to adsorption equilibrium, and Material handling processes are complex.Powder sample also not easily collecting after application, Yi Yin
Secondary pollution is sent out, adds the process complexity of post-processing.CN104925846A discloses a kind of preparation of nano cupric oxide
Method and its application in lithium battery, nano oxidized copper powders obtained by this method can not be directly as negative electrode of lithium ion battery material
Material and use, it is necessary to add conductive agent, binding agent and it is well mixed after, be applied on collector, reused after drying, so as to increase
Production cycle and the cost prepared.CN105514406A discloses a kind of preparation side of nanowire array of copper oxide at room temperature
Method, this method need to use the ammoniacal liquor of high concentration (28%) to participate in reaction, and in 96 hours reaction time, the process conditions are to environment
There is potential threat with workers ' health, and the process time is longer, is not suitable for rapid scale production.In addition, the patent using copper sheet as
Substrate is applied to negative electrode of lithium ion battery in copper sheet superficial growth nanowire array of copper oxide, due to copper sheet substrate sheet
Body reduces the adequacy of reaction, increases the transmission range of lithium ion and internal nanowire, and repeatedly circulate without loose structure
Afterwards, nano wire is easily roughened merging, makes cell performance decay.Paper Scientific Reports 2015,5：16115 disclose
A kind of combination anodizing and calcine technology porous metal copper superficial growth cupric oxide nano line method, first 25
DEG C, 3mol/L NaOH solutions, 10mA cm-2Current density under forged by foam copper anodic oxidation 30 minutes, then by it at 180 DEG C
Burn 1 hour, obtain the cupric oxide nano line composite using foam copper as matrix, cupric oxide nano line synthesized by this method compared with
Slightly, diameter about 450nm, without more tiny nanoscale hole hole structure on nano wire, will influence the material as photocatalytic degradation agent with
The performance and efficiency of lithium ion battery negative material, and made oxidation copper cash face checking after calcining, it is complete to have impact on its machinery
Whole property.
The content of the invention
The purpose of the present invention is for insufficient present in current techniques, there is provided a kind of supported porous cupric oxide of foam copper is received
Rice noodles composite and its preparation method and application.For the material using foam copper as matrix, matrix surface is loaded with porous copper oxide
Nano wire, nano wire radially distribute, and every 60~150 nano wires form a cupric oxide micro-flowers, so as to form tool
There is the composite of multistage porous (nano-pore on micron openings-nano wire between grand hole-nano wire of foam copper) structure.It is made
In Preparation Method, using three-dimensional porous foams copper metal as skeleton, potassium hydroxide solution is used as electrolyte, and utilize anodizing
It is made with subsequent calcine technology.Material width is narrower than ever for nano wire prepared by the present invention, and yardstick is thinner, more completely, no
It is easy to crack, and nano wire also has loose structure, in photocatalytically degradating organic dye, as lithium ion battery negative material two
Field shows structure and performance advantage.
The technical scheme is that：
A kind of supported porous cupric oxide nano line composite of foam copper, the material includes matrix, and is supported on its table
The cupric oxide nano line in face；Wherein 8~12 μm of cupric oxide nano line length, wide 150~250nm, nanowire surface is without cracking, completely
Property is good, and difficult for drop-off, microcosmic upper nano wire has loose structure, and bore dia is 2~4nm, macroscopically radial point of nano wire
Cloth, every 60~150 nano wires form a cupric oxide micro-flowers, and load thickness of the cupric oxide on matrix is 8~12 μm；
Described matrix is foam copper, 0.9~1.0mm of thickness, tough 70~100 μm of bandwidth, 150~250 μm of aperture, purity
99.95wt.%, porosity 78~82%.
The preparation method of the supported porous cupric oxide nano line composite of described foam copper, comprises the following steps：
The first step, anodizing synthesis Kocide SD nano wire
By foam copper material clean, two identical foam Copper substrates positive and negative electrode with dc source respectively is taken after air-drying
It is connected, is dipped in 0.8~1.2M potassium hydroxide solutions and carries out anodic oxidation, wherein, solution temperature is set in 18~23 DEG C, 8
~9mA/cm2Current density 8~12min of anodic oxygenization, then will connect positive pole matrix cleaning after air-dry, obtain foam copper
The Kocide SD nanowire composite of load；
Second step, calcine porous oxidation copper nano-wire processed
By made from the first step foam copper load Kocide SD nanowire composite, be placed in vacuum drying chamber in
170~175 DEG C of 1.5~2.5h of calcining, after being then dried in vacuo, obtain the supported porous cupric oxide nano line composite wood of foam copper
Material.
A kind of application of the supported porous cupric oxide nano line composite of described foam copper, it is organic for photocatalytic degradation
Dyestuff or the lithium ion battery negative material for self-supporting.
Described organic dyestuff is preferably rhodamine B, the one or more in methyl orange and methylene blue.
Above-mentioned supported porous cupric oxide nano line composite of a kind of foam copper and its preparation method and application, original used
Material and facility is obtained by known approach, and operating procedure used is that those skilled in the art can grasp
's.
The present invention substantive distinguishing features be：
Obtained first in current techniques is non-porous nano-wire array, and prepared by the present invention is with nanoporous knot
The nano wire of structure, and nano wire is radial, every 60~150 nano wires form a cupric oxide micro-flowers, improve reaction
Activity and space, second, material width is narrower than ever for prepared nano wire, yardstick is thinner, and the chemical reaction of generation more fills
Point, third, prepared nano wire is more complete, does not ftracture, it is not easy to come off from matrix in the reaction, improves property retention rate.Prepare
In method, substantive distinguishing features one of the invention be it is different from the past select sodium hydroxide solution, the present invention is using hydroxide
Potassium solution, higher ion transportation is brought therewith, promote the progress of anodic oxidation reactionses；Second, anodic oxidation reactionses
In each parameter setting it is different from conventional work, solution concentration, reaction temperature, current density and reaction time all work than ever to be wanted
It is low, so as to the autotelic appropriateness growth for controlling nano wire and its final form, third, the calcine technology matched with the reaction
It is lower than conventional treatment temperature, and processing time extends, and so as to prevent the cracking of nanowire surface, contributes on nano wire
The formation of nano-pore.
The beneficial effects of the invention are as follows：The present invention synthesizes with nanoporous on foam copper skeleton with good conductivity
The cupric oxide nano line of structure, the hole of whole three-dimensional structure enrich, and are adapted to light to pass through, and also are adapted for ion transmission.Specific body
Now：
(1) a kind of supported porous cupric oxide nano line composite of foam copper of the present invention and its preparation method and application, with
Foam copper metal is skeleton, three-dimensional porous cupric oxide nano structure is gone out in its surface construction, its hole enriches, saturating suitable for light
The progress with photocatalytic degradation reaction is crossed, suitable for the abundant reaction between lithium ion and cupric oxide, it is suppressed that battery capacity declines
Subtract；
(2) a kind of supported porous cupric oxide nano line composite of foam copper of the present invention and its preparation method and application, material
Expect that preparation technology is simple, reduce equipment complexity, reduce energy consumption, shorten process cycle, suitable for large-scale production；
(3) a kind of supported porous cupric oxide nano line composite of foam copper of the present invention and its preparation method and application, institute
Cupric oxide nano line is prepared in foam Copper substrate fabricated in situ, with reference to firm, surface is not ftractureed, and integrality is good, is dropped in photocatalysis
It will not fall off during solution organic dyestuff, be easy to recycle after reaction, avoid the secondary pollution of dusty material initiation, and make
For conductive agent and binding agent need not be mixed into during negative electrode of lithium ion battery, film and drying operation are eliminated, has saved experimental cost,
Shorten technique duration；
(4) a kind of supported porous cupric oxide nano line composite of foam copper of the present invention and its preparation method and application, institute
Also there is nano-porous structure on the cupric oxide nano line of synthesis, should compared with the cupric oxide nano line for not possessing loose structure
The degradation efficiency that structure is used as photocatalytically degradating organic dye can improve more than 10 times, be showed as lithium ion battery negative material
Capability retention can improve more than 30%.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is the low power SEM patterns that the supported porous cupric oxide nano line composite material surface of foam copper is made in embodiment 1
Figure.
Fig. 2 is the high power SEM patterns that the supported porous cupric oxide nano line composite material surface of foam copper is made in embodiment 1
Figure.
Fig. 3 is the TEM shape appearance figures that porous oxidation copper nano-wire is made in embodiment 1.
Fig. 4 is the XRD for being related to material in embodiment 1：Wherein, Fig. 4 a original foams Copper substrate, the foam of Fig. 4 b embodiments 1
The supported porous cupric oxide nano line composite of copper.
Fig. 5 is phase of the supported porous cupric oxide nano line composite of the foam copper of embodiment 1 in photocatalytic degradation experiment
To absorption rate testing result.
Fig. 6 is the cycle performance of lithium ion battery figure of embodiment 1：Fig. 6 a foam coppers do porous C uO nano wires synthesized by substrate
Cyclic curve, Fig. 6 b copper sheets do the cyclic curve of CuO nano wires synthesized by substrate.
Embodiment
Embodiment 1
The first step, anodizing synthesis Kocide SD nano wire
Foam copper product (is purchased and praises hundred million Sheng Electronics Co., Ltd.s, material thickness 1.0mm, tough 80 μm of bandwidth, aperture in Kunshan
200 μm, purity 99.95wt.%, porosity 80%) cut growth 3cm, the sample of wide 1.5cm sizes, successively with acetone, anhydrous
Ethanol and ultra-pure water are cleaned, and take two samples to be connected respectively with the positive and negative electrode of dc source after air-drying, sample is dipped in
Anodic oxidation is carried out in 1.0M potassium hydroxide solutions, wherein, solution temperature is set in 20 DEG C, in 8.5mA/cm2Current density
Anodic oxygen 10min, then air-dried after the matrix for connecting positive pole is cleaned into 2 times repeatedly with absolute ethyl alcohol and ultra-pure water successively, obtain
To the Kocide SD nanowire composite of foam copper load；
Second step, calcine porous oxidation copper nano-wire processed
By made from the first step foam copper load Kocide SD nanowire composite, be placed in vacuum drying chamber in
175 DEG C of calcining 2.0h, so as to which the supported porous cupric oxide nano line composite of foam copper be made, processing will vacuum drying after terminating
The temperature setting of case is 25 DEG C, and vacuum is arranged to -0.1MPa, by the supported porous cupric oxide nano line composite wood of made foam copper
Expect to retain in drying box standby.
Fig. 1~Fig. 3 show the pattern of the supported porous cupric oxide nano line composite of foam copper prepared by embodiment 1
Scheme, cupric oxide nano line characteristic size is long 10 μm, wide 200nm in figure, and for nanowire surface without cracking, integrality is good, is not easy to take off
Fall, nanometer bore dia 3nm, nano wire radially distribute on nano wire, and it is micro- that every 60~150 nano wires form a cupric oxide
Popped rice.Fig. 4 show the XRD test curves of the material, and visible in the range of 35~40 ° of angles of diffraction in figure, original foam is copper-based
Body material (Fig. 4 a) is without obvious diffraction maximum, and the material (Fig. 4 b) that embodiment 1 synthesizes has obvious CuO diffraction maximums, it was demonstrated that synthesized
Porous nano line is cupric oxide really.
It is organic that the supported porous cupric oxide nano line composite of the foam copper made from the present embodiment carries out photocatalytic degradation
The experimentation of dyestuff is as follows：
Photocatalytic degradation experiment is carried out from organic dyestuff rhodamine B, solution is by 6ml 10mg L-1Rhodamine B and 2ml
30wt.%H2O2Oxidant forms, and using 500W xenon lamp as light source, the distance between xenon lamp and the solution that is degraded is 10cm, light
It is 100mW cm according to intensity-2.During experiment, obtained sample is immersed in solution, solution after investigation dyestuff degraded different time
The relative absorbency of test case, wherein dyestuff is entered by ultraviolet-visible spectrophotometer (Lambda-750PerkinElmer)
Row test.Fig. 5 show the made three-dimensional composite material of the present embodiment respectively to organic dyestuff rhodamine B degraded 0,5,10,20,
30th, after 60 minutes, the relative absorbency contrast of solution, it is seen that extend to 60 minutes with the time, dyestuff is degradable.The material enters
Row circulation degradation experiment, it is found that the degradation rate of (weekly 60 minutes) after being degraded 5 weeks to congruent, different batches dyestuff is still big
In 98%, illustrate that the made three-dimensional composite material of the present embodiment has the performance of good photocatalytically degradating organic dye, the performance
Have benefited from the advantage of the hierarchical porous structure of material in itself, while also have benefited from the good mechanical integrity of material, in the reaction not
It is easy to fall off, it ensure that performance fully plays.
The supported porous cupric oxide nano line composite assembling half-cell of the foam copper made from the present embodiment and progressive
It can test, method is：
Using the supported porous cupric oxide nano line composite of the foam copper of self-supporting as negative pole, made using lithium hexafluoro phosphate
For electrolyte, metal lithium sheet is used as to electrode, and porous polypropylene (Celgard) makees barrier film, carries out cell package, the electricity after encapsulation
After the standing 6h of pond performance test is carried out in blue electric battery test system.Fig. 6 a are cycle performance and the storehouse that battery is made in the present embodiment
Human relations efficiency test result, as seen from the figure, battery illustrate good capacity performance and cyclical stability, reversible after circulating 100 weeks
Capacity is still maintained at 500mAh/g or so, and coulombic efficiency remains at 100% or so after the circle of circulation 5.Fig. 6 b are copper sheet
Do the cyclic curve test result of CuO nano wires synthesized by substrate, contrast finds that the negative pole is not three dimensional skeletal structure, and CuO
Nano wire is nor nano-porous structure, battery initial charge/discharge capacity are sufficiently close to Fig. 6 a, but after the circle of circulation 10, capacity
Rapid decay, when being enclosed to 100, capacity attenuation to 100mAh/g or so.Three-dimensional foam copper manufactured in the present embodiment described above is born
The porous copper oxide nanowire composite of load is shown as negative electrode of lithium ion battery more significantly to be circulated surely than general structure
Qualitative advantage.
Embodiment 2
The first step, anodizing synthesis Kocide SD nano wire
Foam copper product (is purchased and praises hundred million Sheng Electronics Co., Ltd.s, material thickness 0.9mm, tough 70 μm of bandwidth, aperture in Kunshan
150 μm, purity 99.95wt.%, porosity 82%) cut growth 3cm, the sample of wide 1.5cm sizes, successively with acetone, anhydrous
Ethanol and ultra-pure water are cleaned, and take two samples to be connected respectively with the positive and negative electrode of dc source after air-drying, sample is dipped in
Anodic oxidation is carried out in 1.2M potassium hydroxide solutions, wherein, solution temperature is set in 18 DEG C, in 8mA/cm2Current density under
Anodic oxidation 8min, then air-dried after the matrix for connecting positive pole is cleaned into 2 times repeatedly with absolute ethyl alcohol and ultra-pure water successively, steeped
The Kocide SD nanowire composite of foam copper load；
Second step, calcine porous oxidation copper nano-wire processed
By made from the first step foam copper load Kocide SD nanowire composite, be placed in vacuum drying chamber in
180 DEG C of calcining 1.5h, so as to which the supported porous cupric oxide nano line composite of foam copper be made, processing will vacuum drying after terminating
The temperature setting of case is 25 DEG C, and vacuum is arranged to -0.1MPa, by the supported porous cupric oxide nano line composite wood of made foam copper
Expect to retain in drying box standby.
The pattern of the supported porous cupric oxide nano line composite of foam copper prepared by the present embodiment is observed, found
Cupric oxide nano line characteristic size is long 12 μm, wide 250nm, and nanowire surface is without cracking, and integrality is good, difficult for drop-off, nanometer
Nanometer bore dia 2nm, nano wire radially distribute on line, and every 60~150 nano wires form a cupric oxide micro-flowers.
It is organic that the supported porous cupric oxide nano line composite of the foam copper made from the present embodiment carries out photocatalytic degradation
The experimentation of dyestuff is as follows：
Degradation experiment is carried out from the mixed liquor of organic dyestuff rhodamine B, methyl orange, solution is by 3ml 10mg L-1Sieve
Red bright B, 3ml 10mg L-1Methyl orange, 2ml 30wt.%H2O2Oxidant forms, using 500W xenon lamp as light source, xenon
Distance between lamp and the solution that is degraded is 10cm, and intensity of illumination is 100mW cm-2.During experiment, obtained sample is immersed into solution
In, the test case of solution, the relative absorbency of wherein dyestuff pass through UV-vis spectroscopy after investigation dyestuff degraded different time
Photometer (Lambda-750PerkinElmer) is tested.Using the made three-dimensional composite material of the present embodiment respectively to organic
After mixed dye is degraded 0,5,10,20,30,60 minute, contrasted from the relative absorbency of solution, 60 points are extended to the time
Clock, dyestuff are degradable.The material carries out circulation degradation experiment, finds after being degraded 5 weeks to congruent, different batches dyestuff
The degradation rate of (weekly 60 minutes) is still more than 97.5%, illustrates that there is the made three-dimensional composite material of the present embodiment good light to urge
Change the performance of degradating organic dye, the performance has benefited from the advantage of the hierarchical porous structure of material in itself, while also has benefited from material
Good mechanical integrity, it is difficult for drop-off in the reaction, it ensure that performance fully plays.
The supported porous cupric oxide nano line composite assembling half-cell of the foam copper made from the present embodiment and progressive
It can test, method is：
Using the supported porous cupric oxide nano line composite of the foam copper of self-supporting as negative pole, made using lithium hexafluoro phosphate
For electrolyte, metal lithium sheet is used as to electrode, and porous polypropylene (Celgard) makees barrier film, carries out cell package, the electricity after encapsulation
After the standing 6h of pond performance test is carried out in blue electric battery test system.Battery illustrates good capacity performance and stable circulation
Property, after circulating 100 weeks, reversible capacity is still maintained at 500mAh/g or so, and coulombic efficiency remains at after the circle of circulation 5
100% or so.Embodiment 3
The first step, anodizing synthesis Kocide SD nano wire
Foam copper product (is purchased and praises hundred million Sheng Electronics Co., Ltd.s, material thickness 0.95mm, tough 100 μm of bandwidth, hole in Kunshan
250 μm, purity 99.95wt.% of footpath, porosity 78%) cut growth 3cm, the sample of wide 1.5cm sizes, successively with acetone, nothing
Water-ethanol and ultra-pure water are cleaned, and take two samples to be connected respectively with the positive and negative electrode of dc source after air-drying, sample is dipped in
Anodic oxidation is carried out in 0.8M potassium hydroxide solutions, wherein, solution temperature is set in 23 DEG C, in 9mA/cm2Current density under
Anodic oxidation 12min, then air-dried after the matrix for connecting positive pole is cleaned into 2 times repeatedly with absolute ethyl alcohol and ultra-pure water successively, obtain
The Kocide SD nanowire composite of foam copper load；
Second step, calcine porous oxidation copper nano-wire processed
By made from the first step foam copper load Kocide SD nanowire composite, be placed in vacuum drying chamber in
170 DEG C of calcining 2.5h, so as to which the supported porous cupric oxide nano line composite of foam copper be made, processing will vacuum drying after terminating
The temperature setting of case is 25 DEG C, and vacuum is arranged to -0.1MPa, by the supported porous cupric oxide nano line composite wood of made foam copper
Expect to retain in drying box standby.
The pattern of the supported porous cupric oxide nano line composite of foam copper prepared by the present embodiment is observed, found
Cupric oxide nano line characteristic size is long 8 μm, wide 150nm, and nanowire surface is without cracking, and integrality is good, difficult for drop-off, nano wire
Upper nanometer bore dia 4nm, nano wire radially distribute, and every 60~150 nano wires form a cupric oxide micro-flowers.
It is organic that the supported porous cupric oxide nano line composite of the foam copper made from the present embodiment carries out photocatalytic degradation
The experimentation of dyestuff is as follows：
Degradation experiment is carried out from the mixed liquor of organic dyestuff rhodamine B, methyl orange, methylene blue, solution is by 2ml
10mg L-1Rhodamine B, 2ml 10mg L-1Methyl orange, 2ml 10mg L-1Methylene blue, 2ml 30wt.%H2O2Oxygen
Agent forms, and using 500W xenon lamp as light source, the distance between xenon lamp and the solution that is degraded is 10cm, and intensity of illumination is
100mW cm-2.During experiment, obtained sample is immersed in solution, investigates the test case of solution after dyestuff degraded different time,
Wherein the relative absorbency of dyestuff is tested by ultraviolet-visible spectrophotometer (Lambda-750PerkinElmer).Make
After being degraded 0,5,10,20,30,60 minute to organic mixed dye respectively with the made three-dimensional composite material of the present embodiment, by solution
Relative absorbency contrast understand, extend to 60 minutes with the time, dyestuff is degradable.The material carries out circulation degradation experiment,
It was found that the degradation rate of (weekly 60 minutes) is still more than 97% after being degraded 5 weeks to congruent, different batches dyestuff, illustrate this reality
To apply the made three-dimensional composite material of example have a performance of good photocatalytically degradating organic dye, and the performance has benefited from material in itself
The advantage of hierarchical porous structure, while also have benefited from the good mechanical integrity of material, it is difficult for drop-off in the reaction, it ensure that performance
Fully play.
The supported porous cupric oxide nano line composite assembling half-cell of the foam copper made from the present embodiment and progressive
It can test, method is：
Using the supported porous cupric oxide nano line composite of the foam copper of self-supporting as negative pole, made using lithium hexafluoro phosphate
For electrolyte, metal lithium sheet is used as to electrode, and porous polypropylene (Celgard) makees barrier film, carries out cell package, the electricity after encapsulation
After the standing 6h of pond performance test is carried out in blue electric battery test system.Battery illustrates good capacity performance and stable circulation
Property, after circulating 100 weeks, reversible capacity is still maintained at 500mAh/g or so, and coulombic efficiency remains at after the circle of circulation 5
100% or so.
Comparative example 1：Anodic oxidation experiment is carried out from concentration 2.0M potassium hydroxide solutions, other conditions are seen with embodiment 1
The surface microscopic topographic of sample is examined, does not obtain the cupric oxide nano line of loose structure, only obtains non-porous cupric oxide nano line, and
The structure of cupric oxide micro-flowers is not obtained macroscopically.It is used as 1/ of efficiency less than embodiment 1 of photocatalytically degradating organic dye
10, as the capability retention that lithium ion battery negative material is shown less than embodiment 1 3/4.
Comparative example 2：Anodic oxidation experiments are carried out at 30 DEG C, other conditions observe the surface microscopic shape of sample with embodiment 1
Looks, porous or non-porous structure cupric oxide nano line is not obtained, and do not obtain the structure of cupric oxide micro-flowers macroscopically.It is used as
1/15 of the efficiency of photocatalytically degradating organic dye less than embodiment 1, the capacity shown as lithium ion battery negative material
1/2 of conservation rate less than embodiment 1.
Comparative example 3：In 20mA/cm2Current density under carry out anodic oxidation experiment, other conditions are with embodiment 1, observation
The surface microscopic topographic of sample, the cupric oxide nano line of loose structure is not obtained, only obtain non-porous cupric oxide nano line, and it is grand
The structure of cupric oxide micro-flowers is not obtained in sight.It is used as 1/10 of efficiency less than embodiment 1 of photocatalytically degradating organic dye,
As the capability retention that lithium ion battery negative material is shown less than embodiment 1 3/4.
Comparative example 4：Anodizing time extends to 20min, and other conditions observe the surface microscopic of sample with embodiment 1
Pattern, the cupric oxide nano line of loose structure is not obtained, only obtain non-porous cupric oxide nano line, and do not aoxidized macroscopically
The structure of copper micro-flowers.It is used as 1/10 of efficiency less than embodiment 1 of photocatalytically degradating organic dye, as lithium ion battery
3/4 of the capability retention that negative material is shown less than embodiment 1.
Comparative example 5：Calcined in 150 DEG C of samples to anodic oxidation, other conditions observe sample with embodiment 1
Surface microscopic topographic, the cupric oxide nano line of loose structure is not obtained, only obtain non-porous cupric oxide nano line.It is urged as light
Change 1/10 of efficiency less than embodiment 1 of degradating organic dye, kept as the capacity that lithium ion battery negative material is shown
3/4 of rate less than embodiment 1.
Comparative example 6：At 200 DEG C the samples of anodic oxidation are calcined with 3h, other conditions observe the table of sample with embodiment 1
Face microscopic appearance, the cupric oxide nano line mechanical integrity deficiency of resulting loose structure are easy to fall off.It drops as photocatalysis
Solve organic dyestuff 1/2 of efficiency less than embodiment 1, as the capability retention that lithium ion battery negative material is shown less than
The 3/4 of embodiment 1.
Above example and comparative example illustrate a kind of supported porous cupric oxide nano line composite of foam copper and its preparation
Methods and applications are by constantly attempting anode oxidation process and calcination condition, strictly control each process procedure, through repeatedly real
Trample, finally develop it is a kind of have good Photocatalytic Degradation Property, can be as the three-dimensional porous of lithium ion battery negative material
Aoxidize carbon/carbon-copper composite material.
Unaccomplished matter of the present invention is known technology.
Claims (3)
- A kind of 1. supported porous cupric oxide nano line composite of foam copper, it is characterized in that the material includes matrix, and load Cupric oxide nano line on its surface；Wherein 8 ~ 12 μm of cupric oxide nano line length, wide 150 ~ 250nm, nanowire surface without cracking, Integrality is good, difficult for drop-off, and microcosmic upper nano wire has loose structure, and bore dia is 2 ~ 4nm, and macroscopically nano wire is radial Distribution, every 60 ~ 150 nano wires form a cupric oxide micro-flowers, and load thickness of the cupric oxide on matrix is 8 ~ 12 μm；Institute The matrix stated is foam copper.
- 2. the supported porous cupric oxide nano line composite of foam copper as claimed in claim 1, it is characterized in that described foam 0.9 ~ 1.0mm of copper thickness, tough 70 ~ 100 μm of bandwidth, 150 ~ 250 μm of aperture, the wt.% of purity 99.95, porosity 78 ~ 82%.
- 3. the preparation method of the supported porous cupric oxide nano line composite of foam copper as claimed in claim 1, it is characterized in that Comprise the following steps：The first step, anodizing synthesis Kocide SD nano wireBy foam copper material clean, two identical foam Copper substrates are taken to be connected respectively with the positive and negative electrode of dc source after air-drying, It is dipped in 0.8 ~ 1.2M potassium hydroxide solutions and carries out anodic oxidation, wherein, solution temperature is set in 18 ~ 23 DEG C, in 8 ~ 9 mA/ cm2Current density 8 ~ 12min of anodic oxygenization, obtain foam copper load Kocide SD nanowire composite, will be made Air-dried after material clean；Second step, calcine porous oxidation copper nano-wire processedThe Kocide SD nanowire composite that foam copper made from the first step is loaded, be placed in vacuum drying chamber in 170 ~ 175 DEG C of 1.5 ~ 2.5h of calcining, after being then dried in vacuo, obtain the supported porous cupric oxide nano line composite of foam copper.
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| CN107366011B (en) * | 2017-07-18 | 2019-03-19 | 河北工业大学 | A kind of nano porous copper load ultrafine copper oxide nanowire composite and its preparation method and application |
| CN107986316A (en) * | 2017-11-20 | 2018-05-04 | 西安理工大学 | Nanoporous cupric oxide/cupric oxide nano line composite construction and preparation method thereof |
| CN107974691B (en) * | 2017-12-01 | 2020-04-21 | 宁波大学 | Phosphide/copper oxide electrode and preparation method thereof |
| CN108295854B (en) * | 2018-01-30 | 2019-06-14 | 河北工业大学 | A kind of multi-stage porous nano porous copper load nano cuprous oxide wire composite material and preparation method |
| CN108889264A (en) * | 2018-07-13 | 2018-11-27 | 北京京盛国泰科技有限公司 | A kind of preparation method of the foam copper of adsorption-decomposition function formaldehyde |
| CN110102301B (en) * | 2019-05-20 | 2021-04-20 | 上海海事大学 | Method for preparing nano metal oxide load based on anodic oxidation method |
| CN110342563A (en) * | 2019-07-17 | 2019-10-18 | 湖北大学 | A kind of cupric oxide nano line and its preparation method and application |
| CN110508280A (en) * | 2019-09-06 | 2019-11-29 | 厦门大学 | The cupric oxide nano line and the preparation method and application thereof of the micro- texture foam copper of laser |
| CN112093856B (en) * | 2020-07-31 | 2021-09-24 | 同济大学 | Single-metal integrated electrode with convertible oxidation state copper and preparation method and application method thereof |
| CN112897567A (en) * | 2021-03-31 | 2021-06-04 | 江南大学 | Preparation method of copper oxide with nanometer flower-like structure |
| CN114367671A (en) * | 2021-12-13 | 2022-04-19 | 山东黄海科技创新研究院有限责任公司 | Method for growing nano-wire on foam copper |
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