CN110085441A - A kind of Cu-Ag/ carbon nano-fiber composite material and its preparation method and application - Google Patents
A kind of Cu-Ag/ carbon nano-fiber composite material and its preparation method and application Download PDFInfo
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- CN110085441A CN110085441A CN201910349437.9A CN201910349437A CN110085441A CN 110085441 A CN110085441 A CN 110085441A CN 201910349437 A CN201910349437 A CN 201910349437A CN 110085441 A CN110085441 A CN 110085441A
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- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 82
- 229910017770 Cu—Ag Inorganic materials 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims description 54
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 26
- 229910052709 silver Inorganic materials 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 239000002121 nanofiber Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 238000009987 spinning Methods 0.000 claims description 10
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical group [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 5
- 229940071536 silver acetate Drugs 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 239000007772 electrode material Substances 0.000 abstract description 9
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 4
- 239000004917 carbon fiber Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229910052573 porcelain Inorganic materials 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000000835 fiber Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000011324 bead Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910017566 Cu-Mn Inorganic materials 0.000 description 1
- 229910017871 Cu—Mn Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001124569 Lycaenidae Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 241001481789 Rupicapra Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000014987 copper Nutrition 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention is prepared for Cu-Ag/ carbon nano-fiber composite material through charing again with method of electrostatic spinning, Cu-Ag/CNF composite material specific surface area with higher and conductivity obtained by the method for the present invention, higher specific surface area can generate more active site so that electronics or ion can be made to be easier to shift, it is big that specific capacitance can be efficiently generated when anode material applied to supercapacitor, good cycle, service life is long, pollute low electrode material, this is because the Ni metal and Ag that are supported on carbon fiber help somewhat to improve electrode conductivuty, improve coulombic efficiency, and finally improve the cycle performance of electrode；And technological reaction condition is optimized, synthesis technology has been significantly simplified and reduces cost.
Description
Technical field
The present invention relates to carbon fiber fields, and in particular to a kind of Cu-Ag/ carbon nano-fiber composite material and preparation method thereof
And application.
Background technique
Carbon-based material is widely used in various forms of electrode material for super capacitor, although carbon-based electrode is with excellent
Different cyclical stability, long-life and high power density, but compared with metal oxide, the specific capacitance of carbon-based electrode usually compared with
It is low；And although application of the metal oxide on electrode of super capacitor has certain advantage, especially its higher theory
Specific capacitance, but still come with some shortcomings, such as conductivity is low, generates volume change in charge and discharge process, these deficiencies are usually led
Rate capability and the long-time stability for sending a telegraph pole are poor, limit its practical application in supercapacitor；It then will be carbon-based
Material forms combination electrode in conjunction with metallic and is important research direction.
It is found for the prior art by retrieval: " the C MnO that Xu Jiren is delivered2The preparation of composite material and its electrochemical capacitance
Performance study " electrostatic spinning that uses and hydro-thermal process two-step method, CNF is prepared using electrostatic spinning, then passes through hydro-thermal method general
MnO2Be supported on CNF, but this method be readily incorporated during the preparation process impurity and also it is complicated for operation, be not easily accomplished work
Industry；" the Fabrication of Cu that Lihua Yang is delivered2O/Ag composite nanoframes as surface-
Enhanced Raman scattering substrates in a successive one-pot procedure " article,
Final product contains metal oxide, this is resulted in, and conductivity is lower and cyclical stability is poor.
Currently, the carrier of electrode material is mainly based on carbon black, and nano-carbon material is due to its preferable conductive and heat-conductive etc.
Performance is constantly studied, and carbon nano-fiber is as a kind of novel carbon material, due to a variety of superior physics and chemistry
Property is the preferable new material of application prospect.Research nano metal particles Cu, Ag is supported on conduct on carbon nano-fiber at present
The research of the electrode material this respect of supercapacitor is seldom.
Summary of the invention
The technical problem that specific capacitance is low when in order to solve carbon nano-fiber as carbon-based electrode, cycle performance is poor, and mention
For a kind of Cu-Ag/ carbon nano-fiber composite material and its preparation method and application.
The invention is realized by the following technical scheme:
A kind of Cu-Ag/ carbon nano-fiber composite material, metal simple-substance copper and silver are supported on carbon nano-fiber, the metal
The load capacity wt% of elemental copper and silver is respectively 17%~29% and 30%~58%.
The preparation method of above-mentioned Cu-Ag/ carbon nano-fiber composite material, includes the following steps:
(1) preparation of spinning solution: polyacrylonitrile is dissolved in good solvent, solution A is uniformly mixing to obtain；Mantoquita is poured into molten
In liquid A, mixed solution B is stirred to get at room temperature；Silver salt is poured into mixed solution B, stirs to get mixed solution C at room temperature；
(2) preparation of presoma: mixed solution C is subjected to electrostatic spinning, is dried at room temperature for, makes after the completion of electrostatic spinning
Obtain presoma Cu-Ag/PAN nanofiber；
(3) preparation of Cu-Ag/ carbon nano-fiber composite material: presoma obtained by step (2) is placed under inert gas and is forged
Fire to obtain Cu-Ag/ carbon nano-fiber composite material (Cu-Ag/CNF).
Further, good solvent described in step (1) is n,N-Dimethylformamide.
Further, mantoquita described in step (1) is copper acetate, copper chloride or copper nitrate.
Further, silver salt described in step (1) is silver acetate, silver chlorate or silver nitrate.
Further, mantoquita in step (1), silver salt, polyacrylonitrile mass ratio be 1:1:(0.1~5).
Preferably, mantoquita in step (1), silver salt, polyacrylonitrile mass ratio be 1:1:(0.5~5).
Further, electrostatic spinning described in step (2) is in 10~20kV of voltage, 0.8~2mL/h of flow velocity, height 10
It is carried out under~20cm.
Further, calcining described in step (3) is carried out at 450~700 DEG C of temperature, 2~5h of time.
Further, inert gas described in step (3) is N2Or Ar.
The present invention also provides a kind of Cu-Ag/ carbon nano-fiber composite material answering in supercapacitor positive electrode material
With.
It should be understood that in presoma Cu-Ag/PAN, Cu and Ag be not metal simple-substance copper in final product and
Silver, symbol Cu and Ag are only that there are coppers and silver element in expression presoma；And in final products Cu-Ag/CNF, Cu and Ag
It is to exist in the form of metal simple-substance, symbol Cu and Ag are the chemistry expression of metal simple-substance copper and silver.
By largely testing discovery: if the mass ratio of mantoquita, silver salt and polyacrylonitrile is 1:1:x, as x < 0.2,
Obtained sample cannot be completely at filiform, and can generate other impurities；As x > 3, the nanofiber of synthesis is easy to reunite
Together；If voltage is lower than 10kv in step (2), flow velocity is higher than 2mL/h, is highly higher than 20cm, the sample of ejection is by electric field
The effect of power becomes smaller, cannot be completely at filiform, along with solution drips；If the voltage in step (2) is higher than 20kv, flow velocity is low
In 1mL/h, highly it is lower than 15cm, electric spark can be generated, than relatively hazardous；If calcination temperature lower than 450 DEG C or is calcined in step (3)
Time is less than 2h, and sample charing not exclusively and with impurity such as CuO generates；If in step (3) calcination temperature be higher than 700 DEG C or
Calcination time is greater than 5h, then Cu, Ag particle distribution are uneven, reunite.
It is answered the beneficial effects of the present invention are: the present invention is prepared for Cu-Ag/ carbon nano-fiber through charing again with method of electrostatic spinning
Condensation material, Cu-Ag/CNF composite material specific surface area with higher and conductivity obtained by the method for the present invention, higher ratio
Surface area can generate sun of the more active site electronics or ion can be made to be easier to shift, applied to supercapacitor
Big specific capacitance can be efficiently generated when the material of pole, the electrode material that good cycle, the service life is long, pollution is low, this is because being supported on
Ni metal and Ag on carbon fiber help somewhat to improve electrode conductivuty, improve coulombic efficiency, and finally improve
The cycle performance of electrode；And technological reaction condition is optimized, synthesis technology has been significantly simplified and reduces cost.
Detailed description of the invention
Fig. 1 is Cu-Ag/PAN presoma XRD diagram made from embodiment 1.
Fig. 2 is the SEM shape appearance figure of Cu-Ag/PAN presoma made from embodiment 1.
Fig. 3 is the XRD diagram of Cu-Ag/CNF made from embodiment 1.
Fig. 4 is the SEM shape appearance figure of Cu-Ag/CNF made from embodiment 1.
Fig. 5 is Cu-CuO/CNF made from Ag/CNF made from Cu/CNF made from comparative example 1, comparative example 2, comparative example 3
Measured specific capacitance datagram when being applied to the positive electrode material of supercapacitor with Cu-Ag/CNF made from embodiment 1.
Fig. 6 is Cu-CuO/CNF made from Ag/CNF made from Cu/CNF made from comparative example 1, comparative example 2, comparative example 3
Measured cycle performance datagram when being applied to the positive electrode material of supercapacitor with Cu-Ag/CNF made from embodiment 1.
Specific embodiment
The present invention is further described below in conjunction with drawings and the specific embodiments, but does not limit the scope of the invention.
Embodiment 1
The preparation method of Cu-Ag/ carbon nano-fiber composite material, comprising the following steps:
(1) preparation of spinning solution: the polyacrylonitrile for weighing 1.102g is dissolved in the solvent of 12mL N,N-dimethylformamide
In, it is uniformly mixing to obtain solution A；It weighs 1.332g copper acetate to pour into solution A, stirs the 3h time at room temperature, obtain mixing molten
Liquid B；It weighs 1.331g silver acetate to pour into mixed solution B, stirs the 2h time at room temperature, obtain mixed solution C；
(2) preparation of presoma: mixed solution C is placed in syringe, and in 15kV voltage, flow velocity is 1mL/h and height
Electrostatic spinning effect is carried out under conditions of degree 15cm, is dried at room temperature for a night after the completion of electrostatic spinning, and presoma Cu- is made
Ag/PAN nanofiber；
(3) preparation of Cu-Ag/ carbon nano-fiber composite material: presoma obtained by step (2) is placed in porcelain boat, logical
N2Under conditions of, 450 DEG C are heated to from room temperature with the rate of 5 DEG C/min, 2.3h is calcined, sample Cu-Ag/CNF is made.
Calculate theoretical load capacity (the Theoretical Mass percentage of contained substance in product): the load capacity of Cu is 20.73%, Ag
Load capacity be 42.11%.
X-ray diffraction, gained are carried out to the presoma Cu-Ag/PAN nanofiber of step obtained by the present embodiment (2)
XRD spectra as shown in Figure 1, compares standard card, and the diffraction maximum of C and Ag occur in the structural phase diagrams of presoma Cu-Ag/PAN, respectively
23.3°、38.3°、44.5°、64.9°、77.8°、81.8°。
Electron microscope observation, gained are scanned to the presoma Cu-Ag/PAN of step obtained by the present embodiment (2)
SEM shape appearance figure is as shown in Fig. 2, from figure 2 it can be seen that presoma Cu-Ag/PAN Nanowire prepared by the embodiment of the present invention 1
It ties up as bead chain shape, Cu and Ag with pearlitic texture mutual load on PAN fiber.
X-ray diffraction is carried out to products C u-Ag/CNF obtained by the present embodiment, gained XRD spectra is as shown in figure 3, right
Than standard card, from the figure 3, it may be seen that after charing, at 38.7 °, 43.8 °, 45 °, 51 °, 64.9 °, 74.5 °, 77.8 °, 81.8 °
There is the corresponding diffraction maximum of Cu and Ag.
Electron microscope observation, gained SEM shape appearance figure such as Fig. 4 are scanned to Cu-Ag/CNF obtained by the present embodiment
Shown, figure 4, it is seen that Cu-Ag/CNF composite material is also at bead chain shape, and carbon mono-filaments diameter is about 1 micron,
Ni metal, Ag uniform particle are closely supported on the surface CNF.
The test of specific surface area and conductivity is carried out to the obtained Cu-Ag/CNF of this implementation, test result is shown in Table 1.
Embodiment 2
The preparation method of Cu-Ag/ carbon nano-fiber composite material, comprising the following steps:
(1) preparation of spinning solution: the polyacrylonitrile for weighing 0.302g is dissolved in the solvent of 12mL N,N-dimethylformamide
In, it is uniformly mixing to obtain solution A；It weighs 1.331g copper acetate to pour into solution A, stirs the 3h time at room temperature, obtain mixing molten
Liquid B；It weighs 1.332g silver acetate to pour into mixed solution B, stirs the 2h time at room temperature, obtain mixed solution C；
(2) preparation of presoma: mixed solution C is placed in syringe, and in 15kV voltage, flow velocity is 1mL/h and height
Electrostatic spinning effect is carried out under conditions of degree 20cm, is dried at room temperature for a night after the completion of electrostatic spinning, obtained Cu-Ag/PAN receives
Rice fiber；
(3) preparation of Cu-Ag/ carbon nano-fiber composite material: nanofiber obtained by step (2) is placed in porcelain boat,
Logical N2Under conditions of, 600 DEG C are heated to from room temperature with the rate of 5 DEG C/min, 2h is calcined, sample Cu-Ag/CNF is made.
Calculate theoretical load capacity (the Theoretical Mass percentage of contained substance in product): the load capacity of Cu is 28.46%, Ag
Load capacity be 57.85%.
The test of specific surface area and conductivity is carried out to composite material obtained by the present embodiment, measuring specific surface area is
640m2/ g, conductivity 19.1S/cm.
Embodiment 3
The preparation method of Cu-Ag/ carbon nano-fiber composite material, comprising the following steps:
(1) preparation of spinning solution: the polyacrylonitrile for weighing 0.801g is dissolved in the solvent of 12mL N,N-dimethylformamide
In, it is uniformly mixing to obtain solution A；It weighs 1.332g copper acetate to pour into solution A, stirs the 3h time at room temperature, obtain mixing molten
Liquid B；It weighs 1.335g silver acetate to pour into mixed solution B, stirs the 3.5h time at room temperature, obtain mixed solution C；
(2) preparation of presoma: mixed solution C is placed in syringe, in 20kV voltage, flow velocity be 0.8mL/h and
Electrostatic spinning effect is carried out under conditions of height 10cm, is dried at room temperature for a night after the completion of electrostatic spinning, obtained Cu/PAN receives
Rice fiber；
(3) preparation of Cu-Ag/ carbon nano-fiber composite material: nanofiber obtained by step (2) is placed in porcelain boat,
Under conditions of logical Ar, 550 DEG C are heated to from room temperature with the rate of 5 DEG C/min, 3h is calcined, sample Cu-Ag/CNF is made.
Calculate theoretical load capacity (the Theoretical Mass percentage of contained substance in product): the load capacity of Cu is 23.14%, Ag
Load capacity be 47.16%.
The test of specific surface area and conductivity is carried out to composite material obtained by the present embodiment, measuring specific surface area is
653m2/ g, conductivity 25.1S/cm.
Embodiment 4
The preparation method of Cu-Ag/ carbon nano-fiber composite material, comprising the following steps:
(1) preparation of spinning solution: the polyacrylonitrile for weighing 2.001g is dissolved in the solvent of 12mL N,N-dimethylformamide
In, it is uniformly mixing to obtain solution A；It weighs 1.333g copper nitrate to pour into solution A, stirs the 3h time at room temperature, obtain mixing molten
Liquid B；It weighs 1.334g silver nitrate to pour into mixed solution B, stirs the 3.5h time at room temperature, obtain mixed solution C；
(2) preparation of presoma: mixed solution C is placed in syringe, in 15kV voltage, flow velocity be 1.5mL/h and
Electrostatic spinning effect is carried out under conditions of height 15cm, is dried at room temperature for a night after the completion of electrostatic spinning, and Cu-Mn/PAN is made
Nanofiber；
(3) preparation of Cu-Ag/ carbon nano-fiber composite material: nanofiber obtained by step (2) is placed in porcelain boat,
Logical N2Under conditions of, 500 DEG C are heated to from room temperature with the rate of 5 DEG C/min, 5h is calcined, sample Cu-Ag/CNF is made.
Calculate theoretical load capacity (the Theoretical Mass percentage of contained substance in product): the load capacity of Cu is 17.00%, Ag
Load capacity be 31.89%.
The test of specific surface area and conductivity is carried out to composite material obtained by the present embodiment, measuring specific surface area is
645m2/ g, conductivity 20.8S/cm.
Embodiment 5
The preparation method of Cu-Ag/ carbon nano-fiber composite material, comprising the following steps:
(1) preparation of spinning solution: the polyacrylonitrile for weighing 2.504g is dissolved in the solvent of 12mL N,N-dimethylformamide
In, it is uniformly mixing to obtain solution A；It weighs 1.331g copper chloride to pour into solution A, stirs the 3h time at room temperature, obtain mixing molten
Liquid B；It weighs 1.330g silver chlorate to pour into mixed solution B, stirs the 3.5h time at room temperature, obtain mixed solution C；
(2) preparation of presoma: mixed solution C is placed in syringe, and in 10kV voltage, flow velocity is 2mL/h and height
Electrostatic spinning effect is carried out under conditions of degree 15cm, is dried at room temperature for a night after the completion of electrostatic spinning, obtained Cu-Ag/PAN receives
Rice fiber；
(3) preparation of Cu-Ag/ carbon nano-fiber composite material: nanofiber obtained by step (2) is placed in porcelain boat,
Logical N2Under conditions of, 700 DEG C are heated to from room temperature with the rate of 5 DEG C/min, 5h is calcined, sample Cu-Ag/CNF is made.
Calculate theoretical load capacity (the Theoretical Mass percentage of contained substance in product): the load capacity of Cu is 18.90%, Ag
Load capacity be 30.04%.
The test of specific surface area and conductivity is carried out to composite material obtained by the present embodiment, measuring specific surface area is
644m2/ g, conductivity 20.9S/cm.
Comparative example 1
The preparation method of Cu/ carbon nano-fiber composite material, comprising the following steps:
(1) preparation of spinning solution: the polyacrylonitrile for weighing 1.203g is dissolved in the solvent of 12mL N,N-dimethylformamide
In, it is uniformly mixing to obtain solution A；It weighs 1.021g copper chloride to pour into solution A, stirs the 5h time at room temperature, obtain mixing molten
Liquid B1；
(2) preparation of presoma: mixed solution B1 is placed in syringe, and in 20kV voltage, flow velocity is 1mL/h and height
Electrostatic spinning effect is carried out under conditions of degree 16cm, is dried at room temperature for a night after the completion of electrostatic spinning, is made Cu/PAN nanometers
Fiber；
(3) preparation of Cu/ carbon nano-fiber composite material: nanofiber obtained by step (2) is placed in porcelain boat, in logical N2
Under conditions of, 800 DEG C are heated to from room temperature with the rate of 5 DEG C/min, 11h is calcined, products C u/CNF is made.
The test of specific surface area and conductivity is carried out to this comparative example, test result is shown in Table 1.
Comparative example 2
The preparation method of Ag/ carbon nano-fiber composite material, comprising the following steps:
(1) preparation of spinning solution: the polyacrylonitrile for weighing 1.105g is dissolved in the solvent of 12mL N,N-dimethylformamide
In, it is uniformly mixing to obtain solution A；It weighs 1.331g silver nitrate to pour into solution A, stirs the 3h time at room temperature, obtain mixing molten
Liquid C1；
(2) preparation of presoma: mixed solution C 1 is placed in syringe, and in 15kV voltage, flow velocity is 1mL/h and height
Electrostatic spinning effect is carried out under conditions of degree 15cm, is dried at room temperature for a night after the completion of electrostatic spinning, is made Ag/PAN nanometers
Fiber；
(3) preparation of Ag/ carbon nano-fiber composite material: presoma obtained by step (2) is placed in porcelain boat, in logical N2's
Under the conditions of, 450 DEG C are heated to from room temperature with the rate of 5 DEG C/min, 2.3h is calcined, sample Ag/CNF is made.
The test of specific surface area and conductivity is carried out to this comparative example, test result is shown in Table 1.
Comparative example 3
The preparation method of Cu-CuO/ carbon nano-fiber composite material, comprising the following steps:
(1) preparation of spinning solution: the polyacrylonitrile for weighing 1.104g is dissolved in the solvent of 12mL N,N-dimethylformamide
In, it is uniformly mixing to obtain solution A；It weighs 1.331g copper acetate to pour into solution A, stirs the 3h time at room temperature, obtain mixing molten
Liquid B；
(2) preparation of presoma: mixed solution B is placed in syringe, and in 15kV voltage, flow velocity is 1mL/h and height
Electrostatic spinning effect is carried out under conditions of degree 15cm, is dried at room temperature for a night after the completion of electrostatic spinning, and Cu-CuO/PAN is made
Nanofiber；
(3) preparation of Cu-CuO/ carbon nano-fiber composite material: presoma obtained by step (2) is placed in porcelain boat, logical
N2Under conditions of, 700 DEG C are heated to from room temperature with the rate of 5 DEG C/min, 10.2h is calcined, sample Cu-CuO/CNF is made.
The test of specific surface area and conductivity is carried out to this comparative example, test result is shown in Table 1.
The specific surface area and Resistivity results of 1~3 product of embodiment 1 and comparative example are as shown in table 1.
The specific surface area and conductivity of table 1 embodiment 1 and 1~3 product of comparative example
As shown in Table 1, its specific surface area of the Cu-Ag/CNF of embodiment 1 is bigger than with the product of Conductivity Ratio comparative example 1~3,
Higher specific surface area can generate more active site so that electronics or ion can be made to be easier to shift；And higher conduction
Property is able to ascend cycle performance of the Cu-Ag/CNF as electrode material when, and then improves service life.This two o'clock is in application examples
Further embodied.
Application examples 1
Composite material prepared by embodiment 1 is applied to the positive electrode material of supercapacitor and carries out electrochemistry survey
Examination；Products application obtained by comparative example 1~3 in the positive electrode material of supercapacitor and is subjected to electro-chemical test.
Electrochemical property test is completed on Shanghai Chen Hua CHI660 electrochemical workstation.Using three-electrode system: glass
Carbon electrode (GC) is working electrodePlatinum electrode is to electrode, and saturated calomel electrode (SCE) is reference electrode.It is real
In testing, all current potentials carry out at room temperature both with respect to SCE, all experiments.GC electrode before the use, first uses Al2O3
PowderThen the sanding and polishing repeatedly on chamois leather is cleaned by ultrasonic, after drying according to this with dehydrated alcohol and distilled water
It is spare.
Electrode preparation: the sample of 5mg, the water of 1.25mL and 0.25mL Nafion solvent are mixed, and ultrasound makes sample in 5 minutes
Product sufficiently dissolve.6.4 microlitres of solution is taken to drip 80 DEG C of dryings of constant temperature in a vacuum drying oven on the working electrode (s with liquid-transfering gun afterwards
After 2h, the electrochemical property test of cyclic voltammetry, constant current charge-discharge is carried out in the electrolyte of 2M KOH.
The specific capacitance of embodiment 1 and comparative example 1~3 is measured as shown in figure 5, specific capacitance is to utilize formula C=I/v, Cs=
C/m=I/m/v is calculated, and wherein Cs is specific capacitance (F/g), and I is electric current (A), and m is electrode material quality (g), and v is scanning speed
(v/s), specific capacitance means the electricity that the battery of Unit Weight or active material can release.There is Fig. 5 it is found that Cu/CNF is electric
The specific capacitance of pole is 78F/g at 5mV/s；The specific capacitance of Ag/CNF electrode is 110F/g at 5mV/s；Cu-CuO/CNF electrode
Specific capacitance at 5mV/s be 88F/g；And the specific capacitance of Cu-Ag/CNF electrode material is greater than other three kinds of materials, specific capacitance value
Reduce with the increase of sweep speed, specific capacitance is up to 151F/g at 5mV/s.
The composite electrode of embodiment 2~5 its specific capacitance is measured in 147~153F/g or so.
Cyclic durability is one of most important chemical property of supercapacitor.Measure embodiment 1 and comparative example 1~3
Cycle performance as shown in fig. 6, Fig. 6 be 2000 circulation carry out constant current charge-discharges test, electrode current density be 10A/g
Under capacitor situation of change.It will be appreciated from fig. 6 that the cycle performance of Cu-Ag/CNF is clearly superior to other three kinds of materials, in high current
The holding capacity of long-term operation under density conditions, capacitor is still fine, after 2000 circulations, measures Cu-Ag/CNF
The capacity retention of electrode is 95.4%, this is because to provide enough redox anti-for fine and close Ag and Cu metallic
It answers, is unlikely to deform electrode structure made by Cu-Ag/CNF composite material, improves service life.
The composite electrode of embodiment 2~5 its cycle performance is measured to follow under the conditions of high current density by 2000
After ring, capacity retention is between 94%~97%.
Cu-Ag/CNF composite material specific surface area with higher and conductivity, higher obtained by the method for the present invention
Specific surface area can generate more active site electronics or ion can be made to be easier to shift, applied to supercapacitor
Big specific capacitance can be efficiently generated when anode material, the electrode material that good cycle, the service life is long, pollution is low, this is because load
Ni metal and Ag on carbon fiber help somewhat to improve electrode conductivuty, improve coulombic efficiency, and finally mention
The cycle performance of high electrode.
Claims (10)
1. a kind of Cu-Ag/ carbon nano-fiber composite material, which is characterized in that the structure of the composite material is in carbon Nanowire
The load capacity wt% of carried metal elemental copper and silver in dimension, the metal simple-substance copper and silver is respectively 17%~29% and 30%~
58%.
2. a kind of preparation method of Cu-Ag/ carbon nano-fiber composite material according to claim 1, which is characterized in that packet
Include following steps:
(1) preparation of spinning solution: polyacrylonitrile is dissolved in good solvent, solution A is uniformly mixing to obtain；Mantoquita is poured into solution A
In, mixed solution B is stirred to get at room temperature；Silver salt is poured into mixed solution B, stirs to get mixed solution C at room temperature；
(2) preparation of presoma: mixed solution C is subjected to electrostatic spinning, is dried at room temperature for after the completion of electrostatic spinning, before being made
Drive body Cu-Ag/PAN nanofiber；
(3) preparation of Cu-Ag/ carbon nano-fiber composite material: presoma obtained by step (2) is placed in calcine under inert gas and is made
Obtain Cu-Ag/ carbon nano-fiber composite material.
3. a kind of preparation method of Cu-Ag/ carbon nano-fiber composite material according to claim 2, which is characterized in that step
Suddenly good solvent described in (1) is N,N-dimethylformamide.
4. a kind of preparation method of Cu-Ag/ carbon nano-fiber composite material according to claim 2, which is characterized in that step
Suddenly mantoquita described in (1) is copper acetate, copper chloride or copper nitrate；The silver salt is silver acetate, silver chlorate or silver nitrate.
5. a kind of preparation method of Cu-Ag/ carbon nano-fiber composite material according to claim 2, which is characterized in that step
Suddenly mantoquita in (1), silver salt, polyacrylonitrile mass ratio be 1:1:(0.1~5).
6. a kind of preparation method of Cu-Ag/ carbon nano-fiber composite material according to claim 5, which is characterized in that step
Suddenly mantoquita in (1), silver salt, polyacrylonitrile mass ratio be 1:1:(0.5~5).
7. a kind of preparation method of Cu-Ag/ carbon nano-fiber composite material according to claim 2, which is characterized in that step
Suddenly electrostatic spinning described in (2) is carried out at 10~20kV of voltage, 0.8~2mL/h of flow velocity, 10~20cm of height.
8. a kind of preparation method of Cu-Ag/ carbon nano-fiber composite material according to claim 2, which is characterized in that step
Suddenly calcining described in (3) is carried out at 450~700 DEG C of temperature, 2~5h of time.
9. a kind of preparation method of Cu-Ag/ carbon nano-fiber composite material according to claim 2, which is characterized in that step
Suddenly inert gas described in (3) is N2Or Ar.
10. one kind is by Cu-Ag/ carbon nano-fiber composite material described in claim 1 in supercapacitor positive electrode material
Application.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102121193A (en) * | 2009-12-30 | 2011-07-13 | 第一毛织株式会社 | Carbon nanofiber-metal composite and method for preparing the same |
| CN103227334A (en) * | 2013-04-03 | 2013-07-31 | 上海交通大学 | Carbon-containing metal catalyst, preparation method and application thereof |
| CN109399691A (en) * | 2018-12-04 | 2019-03-01 | 江苏理工学院 | A kind of Cu-CuO/ carbon nano-fiber composite material and preparation method thereof |
-
2019
- 2019-04-28 CN CN201910349437.9A patent/CN110085441B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102121193A (en) * | 2009-12-30 | 2011-07-13 | 第一毛织株式会社 | Carbon nanofiber-metal composite and method for preparing the same |
| CN103227334A (en) * | 2013-04-03 | 2013-07-31 | 上海交通大学 | Carbon-containing metal catalyst, preparation method and application thereof |
| CN109399691A (en) * | 2018-12-04 | 2019-03-01 | 江苏理工学院 | A kind of Cu-CuO/ carbon nano-fiber composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 穆宏春 等: "碳纳米纤维载银-铜双金属催化剂的制备与应用", 《中国化学会第30届学术年会摘要集-第三十七分会：纳米催化》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111268673A (en) * | 2020-02-11 | 2020-06-12 | 西安理工大学 | Preparation method of supercapacitor electrode material taking foamed nickel as template |
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