CN106629813A - Foam copper-supported porous copper oxide nanowire composite material and preparation method and application thereof - Google Patents
Foam copper-supported porous copper oxide nanowire composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a foam copper-supported porous copper oxide nanowire composite material. The material comprises a foam copper substrate and a copper oxide nanowire supported on the surface, wherein the copper oxide nanowires are 8 to 12 mum in lengths, and are 150 to 250 nanometers in widths; the nanowires do not crack or fall easily; microscopically, the nanowires have porous structures, and pore diameters are 2 to 4 nanometers; macroscopically, the nanowires are distributed radially, and every 60 to 150 nanowires constitute a copper oxide micro-flower. The obtained composite material has a multi-grade and porous structure, and the whole three-dimensional structure is rich in apertures which are suitable for the permission of light rays and ion transport. When the composite material is taken as a photocatalytic degradation organic dye, the degradation efficiency can be increased by over 10 times; when the composite material is taken as a negative electrode material of a lithium ion battery, the capacity retention ratio can be increased by over 30 percent.
Description
Technical field
The present invention relates to copper oxide material technical field, specifically a kind of porous copper oxide loaded by foam copper 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, is lived with good electrochemistry
Property, in ceramics, glaze and enamel, petroleum sweetening agent, insecticide, the field such as hydrogen manufacturing, green glass has played great function, and
Photocatalytically degradating organic dye, show attracting application potential as aspects such as lithium ion battery negative materials.
In 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, the process complexity of later stage process is increased.CN104925846A discloses a kind of preparation of nano cupric oxide
Method and its application in lithium battery, the nano oxidized copper powders of the method gained can not be directly as lithium ion battery negative material
Material and use, need to add conductive agent, binding agent and after being well mixed, be applied on collector, reuse after drying, so as to increase
Production cycle and the cost for preparing.CN105514406A discloses a kind of nanowire array of copper oxide preparation side at room temperature
Method, the 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.Additionally, the patent is with copper sheet
Substrate is applied to lithium ion battery negative in copper sheet superficial growth nanowire array of copper oxide, due to copper sheet substrate sheet
Body reduces the adequacy of reaction without loose structure, increases the transmission range of lithium ion and internal nanowire, and repeatedly circulation
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 by foam copper anodic oxidation 30 minutes, then it is forged at 180 DEG C
Burn 1 hour, obtain the cupric oxide nano line composite based on foam copper, cupric oxide nano line synthesized by the method compared with
Slightly, diameter about 450nm, without more tiny nanoscale hole hole structure on nano wire, the material will be affected as photocatalytic degradation agent and
The performance and efficiency of lithium ion battery negative material, and made oxidation copper cash face checking Jing after calcining, have impact on its machinery complete
Whole property.
The content of the invention
The purpose of the present invention is for not enough 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.Based on foam copper, matrix surface is loaded with porous copper oxide to the material
Nano wire, nano wire radially distributes, and a cupric oxide micro-flowers is constituted per 60～150 nano wires, so as to define tool
There is the composite of multistage porous (nano-pore on micron openings-nano wire between the grand hole-nano wire of foam copper) structure.Its system
In Preparation Method, with three-dimensional porous foams copper metal as skeleton, potassium hydroxide solution is adopted for electrolyte, and utilize anodizing
It is obtained with subsequent calcine technology.Than ever material width is narrower for prepared nano wire of the 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 without cracking, completely
Property it is good, difficult for drop-off, nano wire has a loose structure on microcosmic, and bore dia is 2～4nm, macroscopically radial point of nano wire
Cloth, a cupric oxide micro-flowers are constituted per 60～150 nano wires, and load thickness of the cupric oxide on matrix is 8～12 μm；
Described matrix be foam copper, 0.9～1.0mm of thickness, 70～100 μm of tough 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, air-dry after take two identical foam Copper substrates respectively with the positive and negative electrode of dc source
It is connected, being dipped in 0.8～1.2M potassium hydroxide solutions 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 connection positive pole matrix cleaning after air-dry, obtain foam copper
The Kocide SD nanowire composite of load；
Second step, calcines porous oxidation copper nano-wire processed
By obtained in 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 vacuum dried, 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, one or more in methyl orange and methylene blue.
Supported porous cupric oxide nano line composite of above-mentioned 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 present invention preparation is with nanoporous knot
The nano wire of structure, and nano wire is radial, and per 60～150 nano wires a cupric oxide micro-flowers are constituted, and improves reaction
Activity and space, two is that than ever material width is narrower for prepared nano wire, and yardstick is thinner, and the chemical reaction of generation more fills
Point, three it is that prepared nano wire is more complete, does not ftracture, it is difficult from matrix to come off in the reaction, improve property retention rate.Prepare
In method, the substantive distinguishing features one of the present invention are selection sodium hydroxide solutions different from the past, and the present invention uses hydroxide
Potassium solution, brings therewith higher ion transportation, promotes the carrying out of anodic oxidation reactionses；Two is anodic oxidation reactionses
In each parameter setting from worked different in the past, solution concentration, reaction temperature, current density and reaction time all than ever work will
Low, so as to the autotelic appropriateness growth for controlling nano wire and its final form, three is the calcine technology matched with the reaction
It is lower than conventional treatment temperature, and process time extends, and so as to prevent the cracking of nanowire surface, contributes on nano wire
The formation of nano-pore.
The invention has the beneficial effects as follows：The present invention synthesizes with nanoporous on the good foam copper skeleton of electric conductivity
The cupric oxide nano line of structure, the hole of whole three-dimensional structure enriches, and is adapted to light and passes through, and also is adapted for ion transmission.Concrete body
Now：
(1) supported porous cupric oxide nano line composite of a kind of foam copper of the invention and its preparation method and application, with
Foam copper metal is skeleton, and in its surface construction three-dimensional porous cupric oxide nano structure is gone out, and its hole enriches, and is suitable to light saturating
Cross and photocatalytic degradation reaction carrying out, the abundant reaction that is suitable between lithium ion and cupric oxide, it is suppressed that battery capacity declines
Subtract；
(2) supported porous cupric oxide nano line composite of a kind of foam copper of the invention and its preparation method and application, material
Material preparation process is simple, reduces equipment complexity, reduces energy consumption, shortens process cycle, is suitable to large-scale production；
(3) supported porous cupric oxide nano line composite of a kind of foam copper of the invention and its preparation method and application, institute
Cupric oxide nano line is prepared in foam Copper substrate fabricated in situ, with reference to consolidating, surface is not ftractureed, and integrality is good, in photocatalysis drop
Will not fall off during solution organic dyestuff, be easy to after reaction to recycle, it is to avoid the secondary pollution that dusty material causes, and make
For lithium ion battery negative when need not be mixed into conductive agent and binding agent, eliminate film and drying operation, saved experimental cost,
Shorten technique duration；
(4) supported porous cupric oxide nano line composite of a kind of foam copper of the invention and its preparation method and application, institute
Also there is nano-porous structure on the cupric oxide nano line of synthesis, compared with the cupric oxide nano line for not possessing loose structure, should
Structure is used as the degradation efficiency of photocatalytically degradating organic dye can improve more than 10 times, as lithium ion battery negative material performance
Capability retention can improve more than 30%.
Description of the drawings
With reference to the accompanying drawings and examples the present invention is further described.
Fig. 1 is the low power SEM pattern that embodiment 1 is obtained the supported porous cupric oxide nano line composite material surface of foam copper
Figure.
Fig. 2 is the high power SEM pattern that embodiment 1 is obtained the supported porous cupric oxide nano line composite material surface of foam copper
Figure.
Fig. 3 is the TEM shape appearance figures that embodiment 1 is obtained porous oxidation copper nano-wire.
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 wire synthesized by substrate
Cyclic curve, Fig. 6 b copper sheets do the cyclic curve of CuO nano wires synthesized by substrate.
Specific embodiment
Embodiment 1
The first step, anodizing synthesis Kocide SD nano wire
Foam copper product (is purchased and contains Electronics Co., Ltd., material thickness 1.0mm, 80 μm of tough bandwidth, aperture in Kunshan good hundred million
200 μm, purity 99.95wt.%, porosity 80%) cutting growth 3cm, the sample of wide 1.5cm sizes, successively with acetone, anhydrous
Ethanol and ultra-pure water are cleaned, and are taken two samples after air-drying and are connected with the positive and negative electrode of dc source respectively, and 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-dry after successively the matrix of connection positive pole is cleaned into 2 times repeatedly with absolute ethyl alcohol and ultra-pure water, obtain
To the Kocide SD nanowire composite of foam copper load；
Second step, calcines porous oxidation copper nano-wire processed
By obtained in 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 the supported porous cupric oxide nano line composite of foam copper is obtained, process will vacuum drying after terminating
The temperature setting of case is 25 DEG C, and vacuum is set to -0.1MPa, by the supported porous cupric oxide nano line composite wood of made foam copper
Expect to retain standby in drying box.
Fig. 1～Fig. 3 show the pattern of the supported porous cupric oxide nano line composite of foam copper prepared by embodiment 1
Figure, cupric oxide nano line characteristic size is long 10 μm, wide 200nm in figure, and, without cracking, integrality is good, is difficult to take off for nanowire surface
Fall, nanometer bore dia 3nm on nano wire, nano wire radially distributes, constitute a cupric oxide per 60～150 nano wires micro-
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) of the synthesis of embodiment 1 has obvious CuO diffraction maximums, it was demonstrated that synthesized
Porous nano line is cupric oxide really.
It is organic photocatalytic degradation to be carried out with the supported porous cupric oxide nano line composite of foam copper obtained in the present embodiment
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 is constituted, and using the xenon lamp of 500W as light source, xenon lamp and the distance being degraded between solution are 10cm, light
It is 100mW cm according to intensity-2.During experiment, obtained sample is immersed in solution, investigate solution after 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, the degradation rate of (weekly 60 minutes) is still big after finding to degrade congruent, different batches dyestuff 5 weeks
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 itself, while also have benefited from the good mechanical integrity of material, in the reaction not
It is easy to fall off, it is ensured that performance is fully played.
Half-cell and progressive are assembled with the supported porous cupric oxide nano line composite of foam copper obtained in the present embodiment
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 used as to electrode, make barrier film, carry out cell package, the electricity after encapsulation by porous polypropylene (Celgard)
Pond to stand and carry out performance test in blue electricity battery test system after 6h.Fig. 6 a are cycle performance and the storehouse that the present embodiment is obtained battery
Human relations efficiency test result, as seen from the figure, battery illustrates good capacity and shows 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
Nor nano-porous structure, battery initial charge/discharge capacity is sufficiently close to nano wire with Fig. 6 a, but after the circle of circulation 10, capacity
Rapid decay, during to 100 circle, 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 shows as lithium ion battery negative and is more significantly circulated surely than general structure
Qualitative advantage.
Embodiment 2
The first step, anodizing synthesis Kocide SD nano wire
Foam copper product (is purchased and contains Electronics Co., Ltd., material thickness 0.9mm, 70 μm of tough bandwidth, aperture in Kunshan good hundred million
150 μm, purity 99.95wt.%, porosity 82%) cutting growth 3cm, the sample of wide 1.5cm sizes, successively with acetone, anhydrous
Ethanol and ultra-pure water are cleaned, and are taken two samples after air-drying and are connected with the positive and negative electrode of dc source respectively, and 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-dry after successively the matrix of connection positive pole is cleaned into 2 times repeatedly with absolute ethyl alcohol and ultra-pure water, steeped
The Kocide SD nanowire composite of foam copper load；
Second step, calcines porous oxidation copper nano-wire processed
By obtained in 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 the supported porous cupric oxide nano line composite of foam copper is obtained, process will vacuum drying after terminating
The temperature setting of case is 25 DEG C, and vacuum is set to -0.1MPa, by the supported porous cupric oxide nano line composite wood of made foam copper
Expect to retain standby in drying box.
The pattern of the supported porous cupric oxide nano line composite of foam copper prepared by the present embodiment is observed, is found
Cupric oxide nano line characteristic size is long 12 μm, wide 250nm, and, without cracking, integrality is good, difficult for drop-off, nanometer for nanowire surface
Nanometer bore dia 2nm on line, nano wire radially distributes, and per 60～150 nano wires a cupric oxide micro-flowers are constituted.
It is organic photocatalytic degradation to be carried out with the supported porous cupric oxide nano line composite of foam copper obtained in the present embodiment
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 is constituted, using the xenon lamp of 500W as light source, xenon
Lamp and the distance being degraded between solution are 10cm, and intensity of illumination is 100mW cm-2.During experiment, obtained sample is immersed into solution
In, the test case of solution after dyestuff degraded different time is investigated, the wherein relative absorbency of dyestuff passes through UV-vis spectroscopy
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 minutes, contrasted from the relative absorbency of solution, with the time 60 points are extended to
Clock, dyestuff is degradable.The material is circulated degradation experiment, after finding to degrade congruent, different batches dyestuff 5 weeks
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 itself, while also having benefited from material
Good mechanical integrity, it is difficult for drop-off in the reaction, it is ensured that performance is fully played.
Half-cell and progressive are assembled with the supported porous cupric oxide nano line composite of foam copper obtained in the present embodiment
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 used as to electrode, make barrier film, carry out cell package, the electricity after encapsulation by porous polypropylene (Celgard)
Pond to stand and carry out performance test in blue electricity battery test system after 6h.Battery illustrates good capacity and shows and stable circulation
Property, after circulating 100 weeks, reversible capacity is still maintained at 500mAh/g or so, and coulombic efficiency is remained 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 contains Electronics Co., Ltd., material thickness 0.95mm, 100 μm of tough bandwidth, hole in Kunshan good hundred million
250 μm of footpath, purity 99.95wt.%, porosity 78%) cutting growth 3cm, the sample of wide 1.5cm sizes, successively with acetone, nothing
Water-ethanol and ultra-pure water are cleaned, and are taken two samples after air-drying and are connected with the positive and negative electrode of dc source respectively, and 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-dry after successively the matrix of connection positive pole is cleaned into 2 times repeatedly with absolute ethyl alcohol and ultra-pure water, obtain
The Kocide SD nanowire composite of foam copper load；
Second step, calcines porous oxidation copper nano-wire processed
By obtained in 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 the supported porous cupric oxide nano line composite of foam copper is obtained, process will vacuum drying after terminating
The temperature setting of case is 25 DEG C, and vacuum is set to -0.1MPa, by the supported porous cupric oxide nano line composite wood of made foam copper
Expect to retain standby in drying box.
The pattern of the supported porous cupric oxide nano line composite of foam copper prepared by the present embodiment is observed, is found
Cupric oxide nano line characteristic size is long 8 μm, wide 150nm, and, without cracking, integrality is good, difficult for drop-off, nano wire for nanowire surface
Upper nanometer bore dia 4nm, nano wire radially distributes, and per 60～150 nano wires a cupric oxide micro-flowers are constituted.
It is organic photocatalytic degradation to be carried out with the supported porous cupric oxide nano line composite of foam copper obtained in the present embodiment
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 is constituted, and using the xenon lamp of 500W as light source, xenon lamp and the distance being degraded between solution are 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 minutes 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 is circulated degradation experiment,
It was found that the degradation rate of (weekly 60 minutes) is still more than 97% after degrading 5 weeks to congruent, different batches dyestuff, this reality is illustrated
The performance that the made three-dimensional composite material of example has good photocatalytically degradating organic dye is applied, the performance has benefited from material 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 is ensured that performance
Fully play.
Half-cell and progressive are assembled with the supported porous cupric oxide nano line composite of foam copper obtained in the present embodiment
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 used as to electrode, make barrier film, carry out cell package, the electricity after encapsulation by porous polypropylene (Celgard)
Pond to stand and carry out performance test in blue electricity battery test system after 6h.Battery illustrates good capacity and shows and stable circulation
Property, after circulating 100 weeks, reversible capacity is still maintained at 500mAh/g or so, and coulombic efficiency is remained 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 solution, other conditions are seen with embodiment 1
The surface microscopic topographic of sample is examined, the cupric oxide nano line of loose structure is not obtained, non-porous cupric oxide nano line is only obtained, and
The structure of cupric oxide micro-flowers is not macroscopically obtained.It is used as the efficiency of photocatalytically degradating organic dye less than the 1/ of embodiment 1
10, the capability retention shown as lithium ion battery negative material is less than the 3/4 of embodiment 1.
Comparative example 2：Anodic oxidation experiment is carried out at 30 DEG C, other conditions observe the surface microscopic shape of sample with embodiment 1
Looks, do not obtain the cupric oxide nano line of porous or non-porous structure, and macroscopically do not obtain the structure of cupric oxide micro-flowers.It is used as
The efficiency of photocatalytically degradating organic dye less than the 1/15 of embodiment 1, as the capacity that lithium ion battery negative material is shown
Conservation rate less than embodiment 1 1/2.
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, does not obtain the cupric oxide nano line of loose structure, only obtains non-porous cupric oxide nano line, and grand
The structure of cupric oxide micro-flowers is not obtained in sight.It is used as the efficiency of photocatalytically degradating organic dye less than the 1/10 of embodiment 1,
The capability retention shown as lithium ion battery negative material is less than the 3/4 of embodiment 1.
Comparative example 4：Anodizing time extends to 20min, and other conditions observe the surface microscopic of sample with embodiment 1
Pattern, does not obtain the cupric oxide nano line of loose structure, only obtains non-porous cupric oxide nano line, and is macroscopically aoxidized
The structure of copper micro-flowers.It is used as the efficiency of photocatalytically degradating organic dye less than the 1/10 of embodiment 1, as lithium ion battery
The capability retention that negative material is shown less than embodiment 1 3/4.
Comparative example 5：Anodised sample is calcined at 150 DEG C, other conditions observe sample with embodiment 1
Surface microscopic topographic, does not obtain the cupric oxide nano line of loose structure, only obtains non-porous cupric oxide nano line.It is used as light and urges
Change the efficiency of degradating organic dye less than the 1/10 of embodiment 1, keep as the capacity that lithium ion battery negative material is shown
Rate less than embodiment 1 3/4.
Comparative example 6：3h is calcined to anodised sample at 200 DEG C, other conditions observe the table of sample with embodiment 1
Face microscopic appearance, the cupric oxide nano line mechanical integrity of resulting loose structure is not enough, easy to fall off.It is used as photocatalysis drop
The efficiency of solution organic dyestuff less than the 1/2 of embodiment 1, the capability retention shown as lithium ion battery negative material 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 controlling each process procedure, many realities of Jing
Trample, finally develop it is a kind of with good Photocatalytic Degradation Property, can be used as the three-dimensional porous of lithium ion battery negative material
Oxidation carbon/carbon-copper composite material.
Unaccomplished matter of the present invention is known technology.
Claims (5)
1. a kind of supported porous cupric oxide nano line composite of foam copper, it is characterized by the material includes matrix, and loads
In the 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 nano wire has loose structure on microcosmic, and bore dia is 2 ~ 4nm, and macroscopically nano wire is radial
Distribution, a cupric oxide micro-flowers are constituted per 60 ~ 150 nano wires, 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 by described foam
Copper 0.9 ~ 1.0mm of thickness, 70 ~ 100 μm of tough 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 by
Comprise the following steps：
The first step, anodizing synthesis Kocide SD nano wire
By foam copper material clean, take two identical foam Copper substrates after air-drying and be connected with the positive and negative electrode of dc source respectively,
Being dipped in 0.8 ~ 1.2M potassium hydroxide solutions 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, then will connection positive pole matrix cleaning after air-dry, obtain foam copper load
Kocide SD nanowire composite；
Second step, calcines porous oxidation copper nano-wire processed
By the Kocide SD nanowire composite of foam copper load obtained in the first step, be placed in vacuum drying chamber in 170 ~
175 DEG C of 1.5 ~ 2.5h of calcining, after being then vacuum dried, obtain the supported porous cupric oxide nano line composite of foam copper.
4. the application of the supported porous cupric oxide nano line composite of a kind of foam copper as claimed in claim 1, it is characterized by
For photocatalytically degradating organic dye or the lithium ion battery negative material for self-supporting.
5. the application of the supported porous cupric oxide nano line composite of a kind of foam copper as claimed in claim 1, it is characterized by
Described organic dyestuff is preferably rhodamine B, one or more in methyl orange and methylene blue.
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