CN109659142A - A kind of graphitic carbon/metal nitride composite nano tube array and its preparation method and application - Google Patents
A kind of graphitic carbon/metal nitride composite nano tube array and its preparation method and application Download PDFInfo
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- CN109659142A CN109659142A CN201811287039.0A CN201811287039A CN109659142A CN 109659142 A CN109659142 A CN 109659142A CN 201811287039 A CN201811287039 A CN 201811287039A CN 109659142 A CN109659142 A CN 109659142A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 154
- 239000002184 metal Substances 0.000 title claims abstract description 154
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 150
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 133
- 239000002131 composite material Substances 0.000 title claims abstract description 114
- 239000002071 nanotube Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002073 nanorod Substances 0.000 claims abstract description 74
- 238000004070 electrodeposition Methods 0.000 claims abstract description 31
- 239000002079 double walled nanotube Substances 0.000 claims abstract description 27
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 24
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 24
- 239000003990 capacitor Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 157
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 25
- -1 cobalt nitride Chemical class 0.000 claims description 24
- 229910017052 cobalt Inorganic materials 0.000 claims description 20
- 239000010941 cobalt Substances 0.000 claims description 20
- 229910021529 ammonia Inorganic materials 0.000 claims description 18
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 14
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 10
- 235000019257 ammonium acetate Nutrition 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000005695 Ammonium acetate Substances 0.000 claims description 7
- 229940043376 ammonium acetate Drugs 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 235000011389 fruit/vegetable juice Nutrition 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002402 hexoses Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002972 pentoses Chemical class 0.000 claims description 2
- 150000004965 peroxy acids Chemical class 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims 3
- 239000003738 black carbon Substances 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 238000005554 pickling Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000011787 zinc oxide Substances 0.000 description 74
- 239000011701 zinc Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000008103 glucose Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 238000003491 array Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution 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
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention relates to electrode material for super capacitor fields, more particularly, to a kind of graphitic carbon/metal nitride double-walled nanotubes array and preparation method thereof.The present invention realizes surface and graphitic carbon and metal nitride that metal oxide is attached to graphite carbon-coating to the double-coating of ZnO nanorod by ZnO template electrodeposition process, by nitrogen treatment to metal oxide and pickling, to prepare graphitic carbon/metal nitride composite nano tube array.Preparation method of the present invention is able to achieve the controlledly synthesis of graphitic carbon/metal nitride composite nano tube array, and regulate and control graphite carbon-coating and each thickness degree of metal nitride layer, it is remarkably improved the electric conductivity of metal nitride, improves the transmission speed of electro-active species, improves the performance of electrode material.Simple process, is suitble to scale or industrialized production, and graphitic carbon/metal nitride composite nano tube array of preparation has superior electrochemical capacitance performance.
Description
Technical field
The present invention relates to electrode material for super capacitor fields, multiple more particularly, to a kind of graphitic carbon/metal nitride
Close nano-tube array and its preparation method and application.
Background technique
The critical component of supercapacitor is electrode material, its performance decides the performance of supercapacitor.Nanotube
Array electrode is widely used in high-performance super capacitor electrode material because of the unique pattern advantage such as high-sequential and bigger serface
The research of material.Transition metal oxide MnO2、NiO、Co3O4, hydroxide Co (OH)2、Ni(OH)2, li-ion electrode materials
Li4Ti5O12、H2Ti6O13Deng due to the advantages that cheap, capacitive property is high, science has been caused as electrode material for super capacitor
Family extensive concern.However, a fatal defects of above-mentioned material are poorly conductives, the charge and discharge speed of electrode is drastically influenced
Rate, energy density and power density, it has also become an important bottleneck of capacitor electrode material development.Metal nitride is due to height
Electric conductivity and receive significant attention, can be used for improving the electric conductivity of capacitor material.But currently, how by metal nitride with
Nano-tube array combines, and forms composite nano tube array, the electric conductivity that collaboration improves material is always metal nitride nanometer
The Research Challenges of pipe arrays of conductive material.At present with graphitic carbon/metal nitride composite nano tube of superior chemical property
Array has become the research hotspot and difficult point in the field, and graphitic carbon is received with metal nitride formation in electrode material for super capacitor
Mitron is still a big difficulty.
The present invention is by being compounded to form the ordered composite nanotube with high-conductivity for transition metal nitride and graphitic carbon
Array can significantly improve electronics, the ion transmission performance of transition metal nitride, give full play to boundary abundant in nanostructure
Face advantage and synergistic effect provide so that low cost and high performance combination electrode material can be obtained for supercapacitor production
A kind of electrode material of high conduction performance.
Summary of the invention
The technical problem to be solved by the present invention is in order to overcome graphite in electrode material for super capacitor in the prior art
Carbon and metal nitride form the difficult point of nanotube, provide a kind of graphitic carbon/metal nitride composite nano tube array.
Another object of the present invention is to provide a kind of graphitic carbon/metal nitride composite nano tube array preparation sides
Method.
Another object of the present invention is to provide graphitic carbon/metal nitride composite nano tube arrays in super capacitor electrode
Application in the material of pole.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of graphitic carbon/metal nitride composite nano tube array, is compounded to form graphite by graphitic carbon and metal nitride
Nanocarbon/metal nitride double-walled nanotubes array.
Relative to the nano-array electrode material of other shapes, such as the accumulation of flaky material, graphitic carbon/metal nitride
The tubular structure of double-walled nanotubes array is capable of increasing the specific surface area of material, improves the capacitance of electrode material, is conducive to mention
Its high charge/discharge speed, and then improve the electric conductivity of material entirety.
It is compound by graphitic carbon and metal nitride, it is remarkably improved the electric conductivity of metal nitride, improves electric active matter
The transmission speed of kind, while the reunion of electrode material can be inhibited well, improve the performance of electrode material.
Preferably, the metal nitride is violent nitridation, cobalt nitride, nitrided iron, nickel oxide or nitrogenized manganese cobalt.Nitride metal
The electric conductivity of object is generally greater than metal oxide, so being advantageously implemented the swift electron transmission performance of capacitance material needs.No
Electric conductivity with metal nitride has different, by nitride with graphitic carbon is compound can further promote integral capacitor material
Electric conductivity.
Preferably, the graphitic carbon/metal nitride double-walled nanotubes array caliber is 300~1000nm, length 1
~20 μm, graphitic carbon wall thickness is 20~200nm, and metal nitride wall thickness is 20~400nm.
Composite nano tube is made of graphitic carbon and metal nitride, and overall conductivity is mainly by the thickness of materials at two layers
It influences, each wall layer thickness directly affects the electron-transport path of electrode material, to influence its electric conductivity.
Preferably, the graphitic carbon/metal nitride double-walled nanotubes array caliber is 600~1000nm, and length is
10~20 μm, graphitic carbon wall thickness is 50~150nm, and metal nitride wall thickness is 200~400nm.
A kind of preparation method of graphitic carbon/metal nitride composite nano tube array, includes the following steps:
S1. ZnO nano-rod array is immersed in pentose or hexose solution, heat treatment obtains ZnO/ under vacuum conditions
Graphitic carbon composite nanorod array, sugar juice concentration are 1~10mol/L, and the immersion time is 0.5~6h, heat treatment temperature 900
~1100 DEG C, heat treatment time is 1~6h；
S2: using the ZnO/ graphitic carbon composite nanorod array prepared in S1 as cathode, pass through electricity in metal salt solution
Deposition method is prepared ZnO/ graphitic carbon/metal oxide composite nanorod array, and the concentration of metal salt solution is 0.5~
2mol/L, current density are 1~20mA/cm2, electrodeposition time is 20~30min；
S3: the S2 ZnO/ graphitic carbon/metal oxide composite nanorod array prepared is heat-treated under ammonia and is obtained
ZnO/ graphitic carbon/metal nitride composite nanorod array, heat treatment temperature be 500~1000 DEG C, heat treatment time be 0.5~
2h, ammonia flow are 20~200sccm；
S4: by S3 preparation ZnO/ graphitic carbon/metal nitride composite nanorod array lead to peracid treatment obtain graphitic carbon/
Metal nitride composite nano tube array, acid concentration are 0.2~1.0mol/L, and the acid processing time is 0.2~2h.
General nitride is directly Nitration synthesis, heat treatment under the conditions of ammonia by the metal oxide particle of dense distribution
Condition be easy to cause the nitride particles of generation to melt aggregation, and this patent is synthesized first in zinc oxide nano rod area load
Graphitic carbon/metal oxide reduces the particle size and dispersion degree of oxide precursor, while array-support structure can mention
The thermal stability of integral composite, occurs during height nitridation so as to avoid reuniting.
In order to overcome graphitic carbon in the prior art and metal nitride to form the difficulty of composite nano tube array, inventor
Grope by constantly testing, graphite nanocarbon/metal can be well realized by the electro-deposition method that ZnO template instructs in discovery
The preparation of nitride composite nano tube array.It can realize that metal oxide is attached to graphite carbon-coating well by electrochemical deposition
Surface, realize that graphitic carbon and metal nitride to the double-coating of ZnO nanorod, pass through the nitrogen treatment to metal oxide
And pickling, to prepare graphitic carbon/metal nitride composite nano tube array, electro-deposition can control graphite simultaneously well
The pipe thickness of carbon and metal nitride.During heat treatment, vacuum condition can guarantee graphene/carbon nanotube not by by oxygen
Change, better ensures that its electric conductivity.
Preferably, 2~6mol/L of sugar juice concentration described in S1, immersion time are 0.5~1h, heat treatment temperature 1000
DEG C, 1~3h of heat treatment time.
Preferably, heat treatment time is 3h in above-mentioned S1.Heat treatment time will have a direct impact on graphite linings thickness and graphitization
Degree.
Preferably, metal salt solution described in S2 is Mn (NO3)2、Fe(NO3)2、Co(NO3)2Or Ni (NO3)2。
It is highly preferred that metal salt solution is Co (NO in above-mentioned S23)2.The oxide of Co and the composite array of graphitic carbon have
Excellent chemical property and stability.
Preferably, the processing time of acid described in S4 is 20min.Acid treatment step, acid is dense excessively high to will lead to nano-tube array
Collapse, be unable to get tubular material, acid it is dense it is too low not can be removed ZnO nanorod, cannot get nano-tube array, control acid processing
Acid concentration can be with controlledly synthesis graphitic carbon/metal nitride composite nano tube array.
Preferably, the acid of acid processing is hydrochloric acid or sulfuric acid or acetic acid in above-mentioned S4.
It is highly preferred that the acid is acetic acid.It is acid smaller, the corrosion process of zinc oxide can be controlled better.
Above-mentioned ZnO nano-rod array can be existing ZnO nano-rod array, can also preferably following method be prepared into
It arrives: in Zn (NO3)2Aqueous solution in be added ammonium acetate, constant temperature, stirring, ZnO nano-rod array, constant temperature temperature is prepared in electro-deposition
Degree is 60~100 DEG C, 0.5~6h of constant temperature time, 2~30min of mixing time.
Preferably, the Zn (NO3)2The concentration of aqueous solution is 0.01~4.00mol/L, the concentration of ammonium acetate is 0.01~
0.1mol/L。
Preferably, the cathode of the electro-deposition be metal titanium sheet, electrodeposition time be 1~3h, current density be 1~
10mA/cm2。
Preferably, electrodeposition time 2h.By electrochemical deposition, the synthesis of ZnO nano-rod array can be realized well,
Control battery time can be very good the thickness of control ZnO nano-rod array, receive to control graphitic carbon/metal nitride double-walled
The caliber of mitron array.
The graphitic carbon/metal nitride composite nano tube array can be used as electrode material applied in supercapacitor.
Graphitic carbon/metal nitride composite nano tube array of this hair invention has excellent charge/discharge speed and energy density, sufficiently
The excellent electric property for combining graphitic carbon and metal nitride, transition metal nitride and graphitic carbon, which are compounded to form, has height
The ordered composite nano-tube array for the property led can significantly improve electronics, the ion transmission performance of transition metal nitride, sufficiently send out
Interface advantage and synergistic effect abundant, which are waved in nanostructure, so that low cost and high performance combination electrode material can be obtained is
Supercapacitor production provides a kind of electrode material of high conduction performance.
Compared with prior art, the beneficial effects of the present invention are:
The present invention provides a kind of graphitic carbon/metal nitride composite nano tube arrays, pass through metal nitride and graphite
Carbon is compounded to form the ordered composite double-walled nanotubes array of high-conductivity, and the tubular structure of double-walled nanotubes array is capable of increasing material
Specific surface area, improve the capacitance of electrode material, be conducive to improve its charge/discharge speed, with excellent charge/discharge speed and
Energy density, preparation method are simple and efficient, and metal oxide can be well realized by ZnO template electric-sedimentation method and is attached to
Graphitic carbon/metal nitride composite nano tube array, Simultaneous Electrodeposition are prepared in the surface of graphite carbon-coating, nitrogen treatment and pickling
The pipe thickness of graphitic carbon and metal nitride can also be controlled well, and controlledly synthesis, the electrode yield being prepared can be wide
In the general production applied to supercapacitor.
Detailed description of the invention
Fig. 1 is graphitic carbon/metal nitride composite nano tube array preparation method flow chart.
Fig. 2 is graphitic carbon/metal nitride composite nano tube array scanning electron microscope (SEM) photograph (amplification prepared by embodiment 1
2000 times).
Fig. 3 is that graphitic carbon/metal nitride composite nano tube array difference prepared by embodiment 1 sweeps the cyclic voltammetric under speed
Figure.
Fig. 4 is to fill (a) under graphitic carbon/metal nitride composite nano tube array difference constant current prepared by embodiment 1
Put (b) electric curve graph.
Specific embodiment
The present invention is further illustrated With reference to embodiment, but embodiment the present invention is not done it is any
The restriction of form.Unless otherwise indicated, source chemicals used in the embodiment of the present invention are the source chemicals routinely bought.
Embodiment 1
A kind of graphitic carbon/metal nitride composite nano tube array, by graphitic carbon and metal nitride cobalt nitride complex
At graphitic carbon/metal nitride double-walled nanotubes array, graphitic carbon/metal nitride double-walled nanotubes array caliber is
600nm, length are 10 μm, and graphitic carbon wall thickness is 50nm, and cobalt nitride wall thickness is 250nm.
The electro-deposition method that above-mentioned graphitic carbon/metal nitride composite nano tube array is instructed by ZnO template, according to
Following steps preparation:
S1: ZnO nano-rod array is immersed in 3mol/L glucose solution 60 minutes, then under vacuum conditions 1000 DEG C
Heat treatment 3 hours, obtains ZnO/ graphitic carbon composite nanorod array；
S2: ZnO/ graphitic carbon composite nanorod array is made into cathode, in 1.0mol/L Co (NO3)2It is close in electric current in solution
Degree is 3.0mA/cm2Lower progress electro-deposition 30 minutes obtains ZnO/ graphitic carbon/metal oxide composite nanorod array；
S3: ZnO/ graphitic carbon/metal oxide composite nanorod array is heat-treated by ammonia, in 800 DEG C of heat of temperature
Processing 2 hours, ammonia flow 100sccm, obtains ZnO/ graphitic carbon/metal nitride composite nanorod array；
S4: by ZnO/ graphitic carbon/metal nitride composite nanorod array in acetate concentration in 0.5mol/L solution
Reason obtains preparing graphitic carbon/metal nitride composite nano tube array for 1 hour.
Wherein ZnO nano-rod array the preparation method comprises the following steps: taking 148.75 grams of Zn (NO3)2Salt is dissolved in forming 500 in water
Milliliter solution (1.0mol/L), and be added 0.35 gram of ammonium acetate (0.01mol/L), 60 DEG C constant temperature 1 hour, stir 10 minutes, benefit
Use 1cm2Titanium metal plate does cathode, in the above solution electro-deposition 30 minutes, current density 5mA/cm2, prepare ZnO nano
Stick array.
Fig. 1 is graphitic carbon/metal nitride composite nano tube array preparation flow figure.
The graphitic carbon being prepared/metal nitride composite nano tube array scanning electron microscope (SEM) photograph is as shown in Fig. 2, from Fig. 2
It can clearly be seen that orderly aligned nano-tube array.
Graphitic carbon/metal nitride composite nano tube array cyclic voltammogram is as shown in figure 3, illustrate that the material has very
Good electrochemical capacitance performance.Fig. 3 is the cyclic voltammetry curve of scanning speed 100mV/s, and potential window -0.8-0V, curve is symmetrical
Property it is preferably approximate rectangular, illustrate the material have good electric double layer capacitance feature, be calculated specific capacitance be 72mF/cm2。
Graphitic carbon/metal nitride composite nano tube array charging and discharging curve figure is as shown in figure 4, illustrate that the material has very
Good charge-discharge performance.Fig. 4 is current density 6mA/cm2Charging and discharging curve, the curve symmetry is good, also shows that good
Electric double layer capacitance characteristic.It is 70mF/cm that specific capacitance, which is calculated,2。
Embodiment 2
A kind of graphitic carbon/metal nitride composite nano tube array, by graphitic carbon and metal nitride cobalt nitride complex
At graphitic carbon/metal nitride double-walled nanotubes array, graphitic carbon/metal nitride double-walled nanotubes array caliber is
600nm, length are 10 μm, and graphitic carbon wall thickness is 60nm, and cobalt nitride wall thickness is 120nm.
Embodiment 3
A kind of graphitic carbon/metal nitride composite nano tube array, by graphitic carbon and metal nitride cobalt nitride complex
At graphitic carbon/metal nitride double-walled nanotubes array, graphitic carbon/metal nitride double-walled nanotubes array caliber is
1000nm, length are 10 μm, and graphitic carbon wall thickness is 150nm, and cobalt nitride wall thickness is 200nm.
Embodiment 4
A kind of graphitic carbon/metal nitride composite nano tube array, by graphitic carbon and metal nitride cobalt nitride complex
At graphitic carbon/metal nitride double-walled nanotubes array, graphitic carbon/metal nitride double-walled nanotubes array caliber is
600nm, length are 1 μm, and graphitic carbon wall thickness is 150nm, and cobalt nitride wall thickness is 200nm.
Embodiment 5
A kind of graphitic carbon/metal nitride composite nano tube array, by graphitic carbon and metal nitride cobalt nitride complex
At graphitic carbon/metal nitride double-walled nanotubes array, graphitic carbon/metal nitride double-walled nanotubes array caliber is
600nm, length are 20 μm, and graphitic carbon wall thickness is 150nm, and cobalt nitride wall thickness is 200nm.
Embodiment 6
A kind of graphitic carbon/metal nitride composite nano tube array, by graphitic carbon and metal nitride cobalt nitride complex
At graphitic carbon/metal nitride double-walled nanotubes array, graphitic carbon/metal nitride double-walled nanotubes array caliber is
600nm, length are 10 μm, and graphitic carbon wall thickness is 20nm, and cobalt nitride wall thickness is 200nm.
Embodiment 7
A kind of graphitic carbon/metal nitride composite nano tube array, by graphitic carbon and metal nitride cobalt nitride complex
At graphitic carbon/metal nitride double-walled nanotubes array, graphitic carbon/metal nitride double-walled nanotubes array caliber is
600nm, length are 10 μm, and graphitic carbon wall thickness is 200nm, and cobalt nitride wall thickness is 200nm.
Embodiment 8
A kind of graphitic carbon/metal nitride composite nano tube array, by graphitic carbon and metal nitride cobalt nitride complex
At graphitic carbon/metal nitride double-walled nanotubes array, graphitic carbon/metal nitride double-walled nanotubes array caliber is
600nm, length are 10 μm, and graphitic carbon wall thickness is 150nm, and cobalt nitride wall thickness is 400nm.
Embodiment 9
A kind of graphitic carbon/metal nitride composite nano tube array, by graphitic carbon and metal nitride cobalt nitride complex
At graphitic carbon/metal nitride double-walled nanotubes array, graphitic carbon/metal nitride double-walled nanotubes array caliber is
600nm, length are 10 μm, and graphitic carbon wall thickness is 100nm, and cobalt nitride wall thickness is 20nm.
Embodiment 10
A kind of preparation method of graphitic carbon/metal nitride composite nano tube array, includes the following steps:
S1: ZnO nano-rod array is immersed in 3mol/L glucose solution 30 minutes, then under vacuum conditions 1000 DEG C
Heat treatment 1 hour, obtains ZnO/ graphitic carbon composite nanorod array；
S2: ZnO/ graphitic carbon composite nanorod array is made into cathode, in 2mol/L Co (NO3)2In solution, in current density
For 20.0mA/cm2Lower progress electro-deposition 20 minutes obtains ZnO/ graphitic carbon/metal oxide composite nanorod array, ammonia flow
Amount is 200sccm；
S3: ZnO/ graphitic carbon/metal oxide composite nanorod array is heat-treated by ammonia, in 800 DEG C of heat of temperature
Processing 30 minutes, ammonia flow 200sccm, prepares ZnO/ graphitic carbon/metal nitride composite nanorod array；
S4: by ZnO/ graphitic carbon/metal nitride composite nanorod array in acetate concentration in 0.2mol/L solution
Reason 2 hours, obtains graphitic carbon/metal nitride composite nano tube array.
Wherein ZnO nano-rod array the preparation method comprises the following steps: taking 29.74 grams of Zn (NO3)2Salt is dissolved in forming 500 in water
Milliliter solution (0.2mol/L), and be added 0.14 gram of ammonium acetate (0.02mol/L), 60 DEG C constant temperature 30 minutes, stir 5 minutes, benefit
Use 1cm2Titanium metal plate does cathode, in the above solution electro-deposition 12 minutes, current density 10mA/cm2, obtain out ZnO nano
Stick array.
The electro-deposition method instructed by ZnO template, is prepared according to the following steps that graphitic carbon/metal nitride is compound to be received
Mitron array.
Embodiment 11
A kind of preparation method of graphitic carbon/metal nitride composite nano tube array, includes the following steps:
S1: ZnO nano-rod array is immersed in 2mol/L glucose solution 40 minutes, then under vacuum conditions 1000 DEG C
Heat treatment 2 hours, obtains ZnO/ graphitic carbon composite nanorod array；
S2: ZnO/ graphitic carbon composite nanorod array is made into cathode, in 0.5mol/L Co (NO3)2It is close in electric current in solution
Degree is 10.0mA/cm2Lower carry out electro-deposition, electrodeposition time 30min obtain ZnO/ graphitic carbon/metal oxide is compound and receive
Rice stick array；
S3: ZnO/ graphitic carbon/metal oxide composite nanorod array is heat-treated by ammonia, at 800 DEG C of temperature
Heat treatment 1 hour, ammonia flow 100sccm, obtains ZnO/ graphitic carbon/metal nitride composite nanorod array；
S4: by ZnO/ graphitic carbon/metal nitride composite nanorod array in acetate concentration in 0.3mol/L solution
Reason 50 minutes, obtains graphitic carbon/metal nitride composite nano tube array.
Wherein ZnO nano-rod array the preparation method comprises the following steps: taking 72.37 grams of Zn (NO3)2Salt is dissolved in forming 500 in water
Milliliter solution (0.5mol/L), and 0.7 gram of ammonium acetate (0.1mol/L) is added, 60 DEG C of constant temperature 40min are stirred 7 minutes, are utilized
1cm2Titanium metal plate does cathode, in the above solution electro-deposition 15 minutes, current density 8mA/cm2, obtain ZnO nanorod battle array
Column.
Embodiment 12
A kind of preparation method of graphitic carbon/metal nitride composite nano tube array, includes the following steps:
S1: ZnO nano-rod array is immersed in 4mol/L glucose solution 30 minutes, then under vacuum conditions 1000 DEG C
Heat treatment 2.5 hours, obtains ZnO/ graphitic carbon composite nanorod array；
S2: ZnO/ graphitic carbon composite nanorod array is made into cathode, in 0.75mol/L Co (NO3)2In solution, in electric current
Density is 4.0mA/cm2Lower carry out electro-deposition deposits 20min, obtains ZnO/ graphitic carbon/metal oxide composite nanorod battle array
Column；
S3. ZnO/ graphitic carbon/metal oxide composite nanorod array is heat-treated by ammonia, at 800 DEG C of temperature
Heat treatment 90 minutes, ammonia flow 50sccm, obtains ZnO/ graphitic carbon/metal nitride composite nanorod array；
It S4. is the processing of 0.75mol/L solution in acetate concentration by ZnO/ graphitic carbon/metal nitride composite nanorod array
20 minutes, obtain graphitic carbon/metal nitride composite nano tube array.
Wherein ZnO nano-rod array the preparation method comprises the following steps: taking 111.56 grams of Zn (NO3)2Salt is dissolved in forming 500 in water
Milliliter solution (0.75mol/L), is added 2.1 grams of ammonium acetates (0.3mol/L), 60 DEG C constant temperature 1 hour, stir 10 minutes, utilize
1cm2Titanium metal plate does cathode, in the above solution electro-deposition 20 minutes, current density 6mA/cm2, prepare ZnO nanorod
Array.
Embodiment 13
A kind of preparation method of graphitic carbon/metal nitride composite nano tube array, includes the following steps:
S1: immersing 30min in 5mol/L glucose solution for ZnO nano-rod array, and then under vacuum conditions 1000 DEG C
Heat treatment 2 hours, obtains ZnO/ graphitic carbon composite nanorod array；
S2. ZnO/ graphitic carbon composite nanorod array is made into cathode, in 1.0mol/LNi (NO3)2It is close in electric current in solution
Degree is 2.0mA/cm2Lower carry out electro-deposition deposits 30min, obtains ZnO/ graphitic carbon/metal oxide composite nanorod array；
S3: ZnO/ graphitic carbon/metal oxide composite nanorod array is heat-treated by ammonia, at 900 DEG C of temperature
Heat treatment 1.5 hours, ammonia flow 20sccm, obtains ZnO/ graphitic carbon/metal nitride composite nanorod array；
S4: by ZnO/ graphitic carbon/metal nitride composite nanorod array acetate concentration be 1.0mol/L solution handle
20 minutes, obtain graphitic carbon/metal nitride composite nano tube array.
Wherein ZnO nano-rod array the preparation method comprises the following steps: taking 297.5 grams of Zn (NO3)2Salt is dissolved in forming 500 in water
Milliliter solution (2mol/L), and be added 15.4 grams of ammonium acetates (0.4mol/L), 70 DEG C constant temperature 30 minutes, stir 15 minutes, utilize
1cm2Titanium metal plate does cathode, in the above solution electro-deposition 30 minutes, current density 4mA/cm2, prepare ZnO nanorod
Array.
Embodiment 14
A kind of preparation method of graphitic carbon/metal nitride composite nano tube array, includes the following steps:
S1: immersing 30min in 6mol/L glucose solution for ZnO nano-rod array, and then under vacuum conditions 1000 DEG C
Heat treatment 6 hours, obtains ZnO/ graphitic carbon composite nanorod array；
S2: ZnO/ graphitic carbon composite nanorod array is made into cathode, in 1.0mol/LMn (NO3)2It is close in electric current in solution
Degree is 3.0mA/cm2Lower carry out electro-deposition, sedimentation time 20min obtain ZnO/ graphitic carbon/metal oxide composite nanorod battle array
Column；
S3: ZnO/ graphitic carbon/metal oxide composite nanorod array is heat-treated by ammonia, in 1000 DEG C of heat of temperature
Processing 1 hour, ammonia flow 20sccm, obtains ZnO/ graphitic carbon/metal nitride composite nanorod array；
S4: by ZnO/ graphitic carbon/metal nitride composite nanorod array in acetate concentration in 0.25mol/L solution
Reason 2 hours, can prepare graphitic carbon/metal nitride composite nano tube array.
Wherein ZnO nano-rod array the preparation method comprises the following steps: taking 595 grams of Zn (NO3)2Salt is dissolved in forming 500 millis in water
Rise solution (4mol/L), and be added 30.8 grams of ammonium acetates (0.8mol/L), 80 DEG C constant temperature 30 minutes, stir 2 minutes, utilize
1.5cm2Titanium metal plate does cathode, in the above solution electro-deposition 60 minutes, current density 2mA/cm2, prepare ZnO nano
Stick array.
As a result it detects
Graphitic carbon/metal nitride composite nano tube array size such as following table table 1 prepared by embodiment 10~14.
Table 1
| Serial number | Caliber/nm | Length/μm | Graphitic carbon wall thickness/nm | Metal nitride wall thickness/nm |
| Embodiment 10 | 800 | 10 | 25 | 400 |
| Embodiment 11 | 600 | 10 | 25 | 330 |
| Embodiment 12 | 600 | 10 | 40 | 180 |
| Embodiment 13 | 400 | 10 | 45 | 180 |
| Embodiment 14 | 400 | 10 | 40 | 200 |
Detection can be carried out to graphitic carbon prepared by the present invention/metal nitride composite nano tube array electrochemistry, examine
Survey index are as follows: capacitance, charge/discharge speed and energy density, testing result are shown in Table 2.
The wherein detection method of specific capacitance are as follows: 100mV/s sweeps the cyclic voltammetry curve that device is obtained under speed, and ratio is calculated
Capacitor.
Detection (or calculating) method of energy density are as follows:
Wherein E represents energy density, W.h/Kg or mWh/cm3；
CspFor the specific capacitance value that two electrode systems are tested, F/g；
U is the potential window difference in electro-chemical test；
P is power density, W/Kg or mW/cm3；
T represents discharge time, s.
Table 2
Claims (10)
1. a kind of graphitic carbon/metal nitride composite nano tube array, which is characterized in that compound by graphitic carbon and metal nitride
Form graphitic carbon/metal nitride double-walled nanotubes array.
2. graphitic carbon as described in claim 1/metal nitride composite nano tube array, which is characterized in that the nitride metal
Object is violent nitridation, cobalt nitride, nitrided iron, nickel oxide or nitrogenized manganese cobalt.
3. such as above-mentioned graphitic carbon described in claim 1/metal nitride composite nano tube array, which is characterized in that the stone
The caliber of black nanocarbon/metal nitride double-walled nanotubes array is 300 ~ 1000nm, and length is 1 ~ 20 μm, and graphitic carbon wall thickness is 20
~ 200nm, metal nitride wall thickness are 20 ~ 400nm.
4. a kind of preparation method of the described in any item graphitic carbons of claim 1 ~ 3/metal nitride composite nano tube array,
It is characterized in that, includes the following steps:
S1. ZnO nano-rod array is immersed in pentose or hexose solution, heat treatment obtains ZnO/ stone under vacuum conditions
Black carbon composite nano stick array, sugar juice concentration are 1 ~ 10 mol/L, and the immersions time is 0.5 ~ 6h, heat treatment temperature for 900 ~
1100 DEG C, heat treatment time is 1 ~ 6h；
S2: using the ZnO/ graphitic carbon composite nanorod array prepared in S1 as cathode, pass through electro-deposition in metal salt solution
ZnO/ graphitic carbon/metal oxide composite nanorod array is prepared in method, and the concentration of metal salt solution is 0.5 ~ 2 mol/
L, current density are 1 ~ 20mA/cm2, electrodeposition time is 20 ~ 30min；
S3: the S2 ZnO/ graphitic carbon/metal oxide composite nanorod array prepared is heat-treated under ammonia and obtains ZnO/ stone
Black nanocarbon/metal nitride composite nanorod array, heat treatment temperature are 500 ~ 1000 DEG C, and heat treatment time is 0.5 ~ 2h, ammonia
Flow is 20 ~ 200sccm；
S4: ZnO/ graphitic carbon/metal nitride composite nanorod array of S3 preparation is led into peracid treatment and obtains graphite nanocarbon/metal
Nitride composite nano tube array, acid concentration are 0.2 ~ 1.0 mol/L, and the acid processing time is 0.2 ~ 2h.
5. graphitic carbon as claimed in claim 4/metal nitride composite nano tube array preparation method, which is characterized in that
Metal salt solution described in S2 is Mn (NO3)2、Fe(NO3)2、Co(NO3)2Or Ni (NO3)2。
6. graphitic carbon as claimed in claim 4/metal nitride composite nano tube array preparation method, which is characterized in that
Acid described in S4 handles the time as 20min.
7. graphitic carbon as claimed in claim 3/metal nitride composite nano tube array preparation method, which is characterized in that
ZnO nano-rod array described in S1 is prepared by following steps: in Zn (NO3)2Aqueous solution in ammonium acetate is added, constant temperature stirs
It mixes, ZnO nano-rod array is prepared in electro-deposition, and thermostat temperature is 60 ~ 100 DEG C, 0.5 ~ 6h of constant temperature time, mixing time 2 ~
30min。
8. preparation method as claimed in claim 7, which is characterized in that the Zn (NO3)2The concentration of aqueous solution is 0.2 ~ 4.00
Mol/L, the concentration of ammonium acetate are 0.01 ~ 0.8 mol/L.
9. preparation method as claimed in claim 7, which is characterized in that the cathode of the electro-deposition is metal titanium sheet, when electro-deposition
Between be 12 ~ 60min, current density be 1 ~ 10 mA/cm2。
10. if the described in any item graphitic carbons of claim 1 ~ 3/metal nitride composite nano tube array is in super capacitor electrode
Application in the material of pole.
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