CN109659159A - A kind of metal oxide and the compound microtrabeculae energy storage electrode preparation method of carbon nanotube - Google Patents
A kind of metal oxide and the compound microtrabeculae energy storage electrode preparation method of carbon nanotube Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 108
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 108
- 150000001875 compounds Chemical class 0.000 title claims abstract description 56
- 238000004146 energy storage Methods 0.000 title claims abstract description 47
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 47
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 244000025254 Cannabis sativa Species 0.000 claims abstract description 50
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 43
- 230000008021 deposition Effects 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 106
- 238000000151 deposition Methods 0.000 claims description 33
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- 238000005530 etching Methods 0.000 claims description 16
- 238000004062 sedimentation Methods 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 239000007772 electrode material Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000004070 electrodeposition Methods 0.000 claims description 8
- 238000009616 inductively coupled plasma Methods 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 230000004087 circulation Effects 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical group [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 230000002708 enhancing effect Effects 0.000 claims description 5
- 238000002474 experimental method Methods 0.000 claims description 5
- 239000002048 multi walled nanotube Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 239000004821 Contact adhesive Substances 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000012876 topography Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 238000002484 cyclic voltammetry Methods 0.000 claims description 3
- 238000010849 ion bombardment Methods 0.000 claims description 3
- 239000002071 nanotube Substances 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 210000000498 stratum granulosum Anatomy 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229920002120 photoresistant polymer Polymers 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 229910019891 RuCl3 Inorganic materials 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000002238 carbon nanotube film Substances 0.000 claims 1
- 230000007423 decrease Effects 0.000 claims 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims 1
- 239000003643 water by type Substances 0.000 claims 1
- -1 carbon nanotube compound Chemical class 0.000 abstract description 5
- 238000010586 diagram Methods 0.000 description 5
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- 206010030113 Oedema Diseases 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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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
- H01G11/30—Electrodes characterised by their material
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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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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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
- H01G11/30—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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
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- 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
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Abstract
The invention discloses the compound micro-column structure energy storage electrode preparation methods of a kind of metal oxide and carbon nanotube that belong to micro- energy storage device field.The microtrabeculae energy storage electrode is successively to adhere to Si/SiO on a silicon substrate2, micro- careless and mini column array structure, then in three-dimensional micro- grass and the collector of mini column array structure surface deposition oxide and carbon nanotube compound active film and micro-column structure energy storage electrode, composition metal oxide and the compound microtrabeculae energy storage electrode of carbon nanotube.With ruthenium-oxide, manganese oxide etc. for metal oxide, microtrabeculae and " micro- grass " structure are processed first；It is deposition template with " micro- grass " structure, by being co-deposited technique, " fried dough twist " undulatory three-dimensional space network is formed in three-dimensional electrode surface, carbon nanotube and metal oxide are mutually wound, large specific surface area, the microtrabeculae energy storage electrode energy storage compound with carbon nanotube of the metal oxide of preparation is good, and specific capacity is up to 272mF/cm2, there is wide application potential.
Description
Technical field
The invention belongs to micro- energy device field, in particular to a kind of metal oxide is stored up with the compound microtrabeculae of carbon nanotube
It can electrode preparation method.
Background technique
Supercapacitor is the Typical Representative of micro- energy storage device, and electrode material can be divided mainly into carbon material system and metal
Oxide material system.Typical Representative in carbon material system is carbon nanotube, with loose porous stereoscopic three-dimensional space
Network structure, thus specific surface area with higher.Typical Representative in metal oxide materials system is ruthenium-oxide, is had
Good fake capacitance storage effect, is conducive to the enhancing of ultracapacitor energy storage performance.Therefore, metal oxide and carbon nanotube
Composite material the effective integration of carbon nanotube spacial framework Yu metal oxide micro-column structure may be implemented, will be electrode
The promotion of energy-storage property provides very big potentiality.However, metal oxide and carbon nano tube compound material are during the deposition process, it is special
It is not the phenomenon that chap, fall off, metal oxide and carbon nanotube easily occur in the deposition process of three-dimensional structure electrode surface
The also fusion relatively difficult to achieve of the microstructure form of material；Therefore, there is an urgent need to a kind of effective micro-nano technology techniques is based on to realize
Metal oxide and the compound micro-column structure energy storage electrode of carbon nanotube.
Summary of the invention
The object of the present invention is to provide a kind of metal oxide and the compound microtrabeculae energy storage electrode preparation method of carbon nanotube,
It is characterized in that, the microtrabeculae energy storage electrode is to adhere to one layer of Si/SiO on a silicon substrate2, in Si/SiO2Layer surface processes
Three-dimensional micro- grass and mini column array structure, then in three-dimensional micro- grass and mini column array structure surface deposition oxide and carbon nanotube
Compound active film prepares high thickness electrode film using the micro-nano effect of micro- grass, and then leads in active film surface deposition
Collector of the electrically good metal Au as energy storage electrode, the composition metal oxide microtrabeculae energy storage electricity compound with carbon nanotube
Pole.
The metal oxide is ruthenium-oxide, manganese oxide, nickel oxide or cobalt oxide.
There are micro- grass around the three-dimensional microtrabeculae microtrabeculae.
It is described to be in three-dimensional micro- careless and compound with carbon nanotube mini column array structure surface deposition oxide active film
Ruthenium-oxide and the compound active film of carbon nanotube, the compound active film show tubular structure.
The preparation method of the three-dimensional micro-pillar array active electrode based on tubular metal oxide, it is characterised in that described
The specific step of preparation process of the metal oxide microtrabeculae energy storage electrode preparation method compound with carbon nanotube is as follows:
(a) (ICP) technology is etched by inductively coupled plasma and etches three-dimensional micro-pillar array and micro- grass on a silicon substrate
Structure；
(b) golden collector is sputtered；
(c) etching groove between electrode；
(d) oxide and the compound active film of carbon nanotube are prepared using negative electrode electro-deposition；It is to be aoxidized by preparation
Ruthenium and the compound active film of carbon nanotube prepare high thickness electrode film, pass through carbon as a result, using the micro-nano effect of micro- grass
The porous spacial framework of nanotube improves the comprehensive performance of electrode, improves electrode specific capacity, power density and energy storage density.
The step (a) etches three-dimensional micro-pillar array and micro- grass structure, the key of ICP etching technics on a silicon substrate
It is that the integral forming of " micro- grass " structure and micro-pillar array first passes through ion bombardment effects that is, before etching, by the photoetching of carbonization
Glue splashes to the region that is entirely etched evenly dispersedly, forms " micro- mask " structure, in subsequent etching process, " micro- mask "
Silicon below structure is protected, it is difficult to be etched, and be formd " micro- grass " shape structure that a large amount of scale is hundreds of nanometers；Most
Eventually, mini column array structure has been formed simultaneously in the silicon base through over etching and " micro- grass " structure in entire substrate of gathering, it is " micro-
The contact area of grass " structure is big, while there is also a large amount of dislocations for Si lattice surface, this is heavy for the efficient electric of ruthenium oxide active film
Product provides good " template ", for promoting metal oxide active film efficient growth to have key effect.
Oxide and the compound active film of carbon nanotube are prepared using negative electrode electro-deposition in the step (d)；By
It deposits and is co-deposited metal oxide and carbon nanotube in liquid, prepare metal oxide in three-dimensional micro-pillar array and micro- grass structure surface
The compound active film with carbon nanotube, promotes the energy storage characteristic of electrode；It specifically prepares ruthenium-oxide and carbon nanotube is compound
Active film, specific thin film preparation process are as follows: using bipolar electrode cathodic deposition, the bipolar electrode cathodic deposition
For bipolar electrode DC cathode sedimentation, experimental facilities uses Shanghai Chen Hua CHI660B electrochemical workstation, wherein silicon substrate micro-structure
As cathode and working electrode, for platinum electrode as anode and auxiliary electrode, depositing liquid is using multi-walled carbon nanotube (MCNT), in fact
Carbon nanotube 1g, RuCl are taken in testing30.05g, NaNO30.85g and 50mL deionized water are configured to the mixed of ruthenic chloride and sodium nitrate
Heshui solution, ultrasonic vibration 30 minutes, so that Ru3+It is sufficiently adsorbed by carbon nanotube；Coprecipitated hydrops after being as ultrasonically treated；
Depositing current density is set as 500mA/cm2, it is compound with carbon nanotube to prepare ruthenium-oxide from 500 seconds to 2000 second sedimentation time
Active film, rinsed with deionized water after the completion of deposition, be then placed in 100 DEG C of air atmospheres dry 0.5 hour it is spare.
The active film pattern compound with carbon nanotube to oxide characterizes, in experiment, different sedimentation times
Under, prepared ruthenium-oxide is different from the surface topography of the compound active film of carbon nanotube, and the deposition at microtrabeculae position is not
It is identical to the greatest extent；As can be seen that depositing the complex function thin film prepared from electron microscope, there is not any crack or stripping
Phenomenon is fallen, laminated film forms special class fried dough twist class corrugated, fine and close, uniform spatial network frame structure；THIN COMPOSITE
In film, carbon nanotube mesh structures surface distributed uniform ruthenium-oxide particle, form specific surface area is higher, electrode activity more
The netted composite construction of strong porous three-dimensional；Moreover, the contact adhesive strength between function film and matrix is also than common oxidation
Ruthenium function film is higher；Laminated film surface is very smooth, and carbon nanotube mesh structures are also extremely compact and uniform；
When being 500s between when deposited, on microtrabeculae top, there is no apparent carbon nanotubes to occur, and in microtrabeculae bottom end,
Carbon nanotube abundant and ruthenium-oxide composite construction are then formd, silicon substrate " micro- grass " template is based on, with the increase of sedimentation time,
Ruthenium-oxide climbs upwards along " micro- grass ", formed cannulated structure, and the carbon nanotube of porous network structure then with tubulose oxygen
Change ruthenium structure to be interweaved winding；
When being stepped up 1000s between when deposited, it is observed that the ruthenium-oxide and carbon nanotube in microtrabeculae bottom end are multiple
Membrane structure growth is closed to be more and more obvious, deposition dramatically increases, meanwhile, on microtrabeculae top, also occur a certain amount of thick
The carbon nano tube structure of thick stratum granulosum package；
When reaching 2000s between when deposited, then there is more special appearance structure, all three-dimensional structures are whole all
It is wrapped up by thick carbon nano-tube coextruded film, around microtrabeculae, special corrugated is presented in compound structure film, in microtrabeculae
Top, the thickness of laminated film have been more than 5 μm；In microtrabeculae bottom end, these structures are mutually wound, perforation, fully wrapped around " micro-
Grass " structure, forms the higher special netted laminated film of thickness.
The cyclic voltammetry curve of the metal oxide and the compound microtrabeculae energy storage electrode of carbon nanotube, is surveyed by single electrode
Examination is analyzed, and under different scanning rates, changes discovery by the specific capacity of specific capacity and ruthenium-oxide electrode film to laminated film,
Under low sweep speed (5mV/s), the specific capacity of combination electrode material reaches 272mF/cm2, relative to ruthenium-oxide electrode, promoted
170%；With the increase of sweep speed, in 100mV/s, the specific capacity of combination electrode drops to 206mF/cm2, have dropped
24%, hereafter, fall off rate gradually slows down；It is multiple simultaneously due to being uniformly distributed for nano oxidized ruthenium material in combination electrode film
It is that bigger contact interface is provided between matrix and electrolyte that condensation material, which is formed by three-D nano-porous structure also, passes through carbon
Nanotube conductive channel, so that ion is diffused by nano pore, electron-transport Distance Shortened, material activity enhancing, electricity
The specific capacity of pole is increased dramatically；
In addition, the cycle life for having carried out under high sweep speed (80mV/s) to energy storage electrode is tested, preceding 2000 circulations
In, electrode specific capacity is gradually promoted to 220mF/cm2, this is because during this period of time, the electrode material in laminated film obtains
Sufficient activation is arrived, material activity is fully used, and embodies capacity and gos up steadily；It is circulated throughout at 2000~3000 times
Cheng Zhong, capacity is almost without decaying；Time circulation, capacity are basically stable at 217mF/cm from 3000 to 60002, relative to 220mF/
cm2, only decayed 1.4%, cyclical stability when showing combination electrode excellent long；This also has benefited from carbon nanotube mesh
Supporting role of the structure to electrode film avoids the cracking of film, falls off.
The beneficial effects of the invention are as follows
(1) complex function thin film prepared is deposited, any crack or peeling phenomenon, laminated film does not occur
Form special class fried dough twist class corrugated, fine and close, uniform spatial network frame structure；In laminated film, carbon nano-tube network
Shape body structure surface distributed uniform ruthenium-oxide particle, form that specific surface area is higher, the stronger porous three-dimensional net of electrode activity
Shape composite construction；Moreover, the contact adhesive strength between function film and matrix is also higher than common ruthenium-oxide function film；
Laminated film surface is very smooth, and carbon nanotube mesh structures are also extremely compact and uniform；It is excellent to show combination electrode
Cyclical stability when long；This also has benefited from supporting role of the carbon nanotube mesh structures to electrode film, avoids opening for film
It splits, fall off.
(2) discovery is changed by the specific capacity of specific capacity and ruthenium-oxide electrode film to laminated film, in low scanning speed
Under rate, the specific capacity of combination electrode material reaches 272mF/cm2, relative to ruthenium-oxide electrode, improve 170%；With scanning
The specific capacity of the increase of rate, combination electrode drops to 206mF/cm2, 24% is had dropped, hereafter, fall off rate gradually slows down；
In combination electrode film, due to being uniformly distributed for nano oxidized ruthenium material, while composite material be formed by it is three-D nano-porous
Structure is also that bigger contact interface is provided between matrix and electrolyte, by carbon nanotube conducting channel, so that ion is logical
It crosses nano pore to be diffused, electron-transport Distance Shortened, material activity enhancing, the specific capacity of electrode is increased dramatically；
(3) it using the ultracapacitor device of energy storage electrode production, is tested using direct current charge-discharge, in terms of test curve
Out, in 50mA/cm2High power discharge under the conditions of, curve still remains ideal isosceles triangle, can be calculated, device
Efficiency for charge-discharge is up to 98.6%.
Detailed description of the invention
Fig. 1 is the micro-pillar array supercapacitor structures schematic diagram of metal oxide/carbon nano-tube composite material, wherein a
Main view；B top view；
Fig. 2 is the mini column array structure processed and " micro- grass " structural schematic diagram.
Fig. 3 is the complex function thin film electron microscope of 500s sedimentation time, wherein (a) entirety pattern, the microtrabeculae top (b),
(c) microtrabeculae bottom end.
Fig. 4 is the complex function thin film electron microscope of 1000s sedimentation time, wherein (a) entirety pattern, the microtrabeculae top (b),
(c) microtrabeculae bottom end.
Fig. 5 is the complex function thin film electron microscope of 2000s sedimentation time, wherein (a) microtrabeculae top, the microtrabeculae bottom end (b),
(c) CNT electron microscope；
Fig. 6 is the field emission scanning electron microscope figure of complex function thin film.Wherein, the twisted shape corrugated knot of (a) laminated film
Structure；(b) carbon nano-tube coextruded film structure；
Fig. 7 is the electrode surface structures schematic diagram deposited after laminated film.
Fig. 8 is the specific capacity comparison of laminated film and oxidation ruthenium film under different scanning rates；
Fig. 9 is the cycle life test of three-dimensional composite film electrode.
The direct current charge-discharge test curve of Figure 10 micro super capacitor.
Specific embodiment
The present invention proposes a kind of metal oxide and the compound microtrabeculae energy storage electrode preparation method of carbon nanotube, the metal
It is to adhere to one layer of Si/ on a silicon substrate that oxide and the compound microtrabeculae energy storage electrode of carbon nanotube, which are in microtrabeculae energy storage electrode,
SiO2, in Si/SiO2Layer surface processes three-dimensional micro- grass and mini column array structure, then in three-dimensional micro- grass and micro-pillar array knot
Structure surface deposition oxide and the compound active film of carbon nanotube, the metal oxide are ruthenium-oxide, manganese oxide, nickel oxide
Or cobalt oxide；Using the micro-nano effect of micro- grass, high thickness electrode film is prepared, and then good in active film surface deposition electric conductivity
Collector of the good metal Au as energy storage electrode, composition metal oxide and the compound microtrabeculae energy storage electrode of carbon nanotube, can
As electrode of super capacitor, it is explained with reference to the accompanying drawing.
Fig. 1 show the micro-pillar array supercapacitor structures schematic diagram of metal oxide and carbon nano tube compound material,
Wherein, silicon based three-dimensional micro array structure is mainly processed using reaction and plasma lithographic technique on a silicon substrate, in turn
Collector of the metal with good conductivity as microelectrode is deposited using sputtering technology on its surface, passes through electrochemical deposition work
Skill, in metal oxide actives electrode films such as three-dimensional micro-pillar array electrode surface deposited oxide rutheniums, concrete technology mainly by
Four steps are completed below:
(a) (ICP) technology is etched by inductively coupled plasma and etches micro-pillar array and micro- grass structure on a silicon substrate；
(b) golden collector is sputtered；
(c) etching groove between electrode；Si/SiO shown in a, b as shown in figure 12Band, the Si/SiO2Band both sides are super
The positive and negative electrode of capacitor, groove plays buffer action between electrode；
(d) negative electrode electro-deposition oxide and the compound active film of carbon nanotube.
Wherein, the key of ICP etching technics is the integral forming of " micro- grass " structure and micro-pillar array.I.e. before etching,
Ion bombardment effects are first passed through, the photoresist of carbonization is splashed into the region that is entirely etched evenly dispersedly, is formed " micro- mask "
Structure.In subsequent etching process, the silicon below " micro- mask " structure is protected, it is difficult to be etched, and be formd big gage
" micro- grass " shape structure that degree is hundreds of nanometers.Finally, mini column array structure and close has been formed simultaneously in the silicon base through over etching
" micro- grass " structure of cloth in entire substrate, as shown in Figure 2.
The micro-pillar array electrode structure and " micro- grass " effect that Fig. 2 is processed, the contact area of above-mentioned " micro- grass " structure is big,
There is also a large amount of dislocations for Si lattice surface simultaneously, this provides good " mould for the efficient electro-deposition of ruthenium oxide electrode material
Plate ", for promoting metal oxide functional film efficient growth that there is key effect.The present invention utilizes the temperature in etching process
Effect and quadratic effect, the technological parameters such as adjustment projectile energy, beam current density, incident direction, can be in different electrode structures
On, obtain the micro- grass structure of silicon substrate abundant
By being co-deposited metal oxide and carbon nanotube in deposition liquid, metal oxygen is prepared in microtrabeculae three-dimensional electrode surface
Compound and carbon nanotube complex function thin film, promote the energy storage characteristic of electrode.Below with ruthenium-oxide and carbon nanotube (RuO2·
nH2O/CNT) for material, illustrate specific thin film preparation process.
Using multi-walled carbon nanotube (MCNT), carbon nanotube (1g), RuCl are taken in experiment3(0.05g), NaNO3(0.85g)
Solution is configured to 50mL deionized water, ultrasonic vibration 30 minutes, so that Ru3+It is sufficiently adsorbed by carbon nanotube.Based on ultrasound
Treated coprecipitated hydrops sets depositing current density as 500mA/cm using bipolar electrode cathodic deposition2, sedimentation time
From 500 seconds to 2000 second, ruthenium-oxide/carbon nanotube complex function thin film is prepared.
In experiment, under different sedimentation times, the surface topography of prepared ruthenium-oxide and carbon nanotube complex function thin film,
As shown in figure 3, when sedimentation time is 500s, it can be seen from the figure that the deposition at different microtrabeculaes position is not quite similar, micro-
Top end, there is no apparent carbon nanotubes to occur, and in microtrabeculae bottom end, then it is multiple to form carbon nanotube/ruthenium-oxide abundant
Structure is closed, silicon substrate " micro- grass " template is based on, with the increase of sedimentation time, ruthenium-oxide climbs upwards along " micro- grass ", forms pipe
Shape hollow structure, the winding and carbon nanotube of porous network structure is then interweaved with tubulose ruthenium-oxide structure.
As shown in figure 4, when being stepped up 1000s between when deposited, it is observed that microtrabeculae bottom end ruthenium-oxide/
Carbon nano-tube coextruded film structure growth is more and more obvious, and deposition dramatically increases, meanwhile, on microtrabeculae top, also occur one
The quantitative carbon nano tube structure wrapped up by thick stratum granulosum.
As shown in figure 5, then there is more special appearance structure when reaching 2000s between when deposited.All three-dimensionals
Structure is integrally all wrapped up by thick carbon nano-tube coextruded film, and around microtrabeculae, special wave is presented in compound structure film
Line shape, on microtrabeculae top, the thickness of laminated film has been more than 5 μm.In microtrabeculae bottom end, these structures are mutually wound, perforation, completely
" micro- grass " structure has been wrapped up, the higher special netted laminated film of thickness is formd.
As can be seen that deposit the complex function thin film prepared from electron microscope, do not occur any crack or
Peeling phenomenon, moreover, the contact adhesive strength between function film and matrix is also higher than common ruthenium-oxide function film.It is multiple
Conjunction film surface is very smooth, and carbon nanotube mesh structures are also extremely compact and uniform.It is swept using the Flied emission of higher resolution
It retouches Electronic Speculum to characterize the surface topography of laminated film, as shown in Figure 6.Can significantly more it find out, laminated film is formed
Class fried dough twist class corrugated is fine and close, uniform spatial network frame structure.In laminated film, carbon nanotube mesh structures surface point
The uniform ruthenium-oxide particle of cloth, forms that specific surface area is higher, the netted composite construction of the stronger porous three-dimensional of electrode activity.
The formation of this three-dimensional porous network structure has benefited from the special silicon substrate in microtrabeculae bottom end " micro- grass " structure, and Fig. 7 is indicated
The three-dimensional structure of laminated film forms schematic diagram.The preparation problem of carbon nano tube compound material is, carbon nanotube and matrix
Between adhesive force it is smaller, be easy to cause the cracking of laminated film and fall off.And microtrabeculae bottom end is formed by " micro- grass ", Ke Yiyou
Effect ground is provided a supporting role as carbon nanotube and the template of ruthinium oxide material deposition process for the deposition of laminated film, so that
Carbon nanotube can be bound more closely with matrix, to also promote ruthenium-oxide being uniformly distributed in carbon nano tube surface.
Ruthinium oxide material (the RuO that this method is prepared2·nH2O) not only have very high specific surface area, can be improved
The co-deposition efficiency of oxide and carbon nanotube, it may have relatively rich hole characteristic so that electrolyte can be entire
Distribution and transmission in three-dimensional space, further, since ruthenium-oxide be carbon nano tube surface is evenly distributed on thin layer form so that from
Sub- diffusion length shortens for nanoscale, moreover, because carbon nanotube being uniformly distributed in entire three-dimensional structure, improves whole
The electric conductivity of a electrode material.Electrolyte and charged particle therein can be infiltrated rapidly thin to function by three-dimensional netted channel
The inside of film makes reaction more thoroughly, sufficiently, quickly electrode capacity and response speed finally be made to get a promotion.
Single electrode test analysis mainly uses cyclic voltammetry.Under different scanning rates, the specific capacity of laminated film and
The specific capacity variation comparison of ruthenium-oxide electrode film is as shown in Figure 8.It can be found that (5mV/s), compound electric under low sweep speed
The specific capacity of pole material reaches 272mF/cm2, relative to ruthenium-oxide electrode, improves 170%.With the increase of sweep speed,
In 100mV/s, the specific capacity of combination electrode drops to 206mF/cm2, has dropped 24%, and hereafter, fall off rate gradually slows down.
In combination electrode film, due to being uniformly distributed for nano oxidized ruthenium material, while composite material is formed by three-dimensional
Nano-porous structure is also that bigger contact interface is provided between matrix and electrolyte, by carbon nanotube conducting channel, is made
It obtains ion to be diffused by nano pore, electron-transport Distance Shortened, material activity enhancing, the specific capacity of electrode obtains substantially
It is promoted.
In addition, the cycle life that the energy storage electrode processed to the present invention has carried out under high sweep speed (80mV/s) is surveyed
Examination.As shown in figure 9, electrode specific capacity is gradually promoted to 220mF/cm2, this is because at this section in first 2000 circulations
In, the electrode material in laminated film has obtained sufficient activation, and material activity is fully used, and it is steady to embody capacity
Step is gone up.In 2000~3000 cyclic processes, capacity is almost without decaying.Time circulation, capacity are basic from 3000 to 6000
Stablize in 217mF/cm2, relative to 220mF/cm2, has only decayed 1.4%, shown the excellent long Shi Xunhuan of combination electrode
Stability.This also has benefited from supporting role of the carbon nanotube mesh structures to electrode film, avoids the cracking of film, falls off.
Based on the energy storage electrode that the present invention is processed, ultracapacitor device is made, has been tested using direct current charge-discharge, surveyed
It is as shown in Figure 10 to try curve.As can be seen that curve still keeps ideal under the conditions of the high power discharge of 50mA/cm2
Isosceles triangle can be calculated, and device efficiency for charge-discharge is up to 98.6%.
1 ruthenium-oxide of table/carbon nanotube hybrid supercapacitor energy density and power density table
As shown in table 2, it can be seen that when current density is 10mA/cm2, the specific capacity of device reaches highest
56.75mF/cm2, power density 4.53mW/cm2.Under the conditions of high power discharge, when current density is 50mA/cm2, device
Specific capacity reach 37.26mF/cm2, power density has been also raised to 19.04mW/cm2.
Claims (9)
1. a kind of metal oxide and the compound microtrabeculae energy storage electrode of carbon nanotube, which is characterized in that the microtrabeculae energy storage electricity
Pole is to adhere to one layer of Si/SiO on a silicon substrate2, in Si/SiO2Layer surface processes three-dimensional micro- grass and mini column array structure, so
Afterwards in three-dimensional micro- grass and mini column array structure surface deposition oxide and the compound active film of carbon nanotube, the micro- of micro- grass is utilized
It receives effect, prepares high thickness electrode film, and then it is electric as energy storage on active film surface to deposit metal Au with good conductivity
The collector of pole, composition metal oxide and the compound microtrabeculae energy storage electrode of carbon nanotube.
2. metal oxide and the compound microtrabeculae energy storage electrode of carbon nanotube according to claim 1, which is characterized in that described
Metal oxide is ruthenium-oxide, manganese oxide, nickel oxide or cobalt oxide.
3. metal oxide and the compound microtrabeculae energy storage electrode of carbon nanotube according to claim 1, which is characterized in that described
There are micro- grass around three-dimensional microtrabeculae microtrabeculae.
4. metal oxide and the compound microtrabeculae energy storage electrode of carbon nanotube according to claim 1, which is characterized in that described
It is received for ruthenium-oxide with carbon in three-dimensional micro- grass and mini column array structure surface deposition oxide with the compound active film of carbon nanotube
The compound active film of mitron, the compound active film show tubular structure.
5. a kind of metal oxide and the compound microtrabeculae energy storage electrode preparation method of carbon nanotube, which is characterized in that specific preparation
Processing step is as follows:
(a) three-dimensional micro-pillar array and micro- grass structure are etched by inductively coupled plasma lithographic technique on a silicon substrate；
(b) golden collector is sputtered；
(c) etching groove between electrode；
(d) oxide and the compound active film of carbon nanotube are prepared using negative electrode electro-deposition；Be by prepare ruthenium-oxide with
The compound active film of carbon nanotube prepares high thickness electrode film using the micro-nano effect of micro- grass, passes through carbon nanometer as a result,
Porous spacial framework is managed, the comprehensive performance of electrode is improved, improves electrode specific capacity, power density and energy storage density.
6. metal oxide and the compound microtrabeculae energy storage electrode preparation method of carbon nanotube according to claim 5, feature
It is, the step (a) etches three-dimensional micro-pillar array and micro- grass structure, inductively coupled plasma etching on a silicon substrate
The key of technique is the integral forming of " micro- grass " structure and micro-pillar array, i.e., before etching, first passes through ion bombardment effects, will
The photoresist of carbonization splashes to the region that is entirely etched evenly dispersedly, " micro- mask " structure is formed, in subsequent etching process
In, the silicon below " micro- mask " structure is protected, it is difficult to be etched, and be formd " micro- grass " that a large amount of scale is hundreds of nanometers
Shape structure；Finally, it has been formed simultaneously mini column array structure in the silicon base through over etching and has gathered " micro- in entire substrate
Grass " structure, the contact area of " micro- grass " structure is big, while there is also a large amount of dislocations for Si lattice surface, this is thin for ruthenium oxide active
The efficient electro-deposition of film provides good " template ", for promoting metal oxide active film efficient growth to have crucial make
With.
7. metal oxide and the compound microtrabeculae energy storage electrode preparation method of carbon nanotube according to claim 5, feature
It is, oxide and the compound active film of carbon nanotube is prepared using negative electrode electro-deposition in the step (d)；By depositing
It is co-deposited metal oxide and carbon nanotube in liquid, prepares metal oxide and carbon in three-dimensional micro-pillar array and micro- grass structure surface
The compound active film of nanotube, promotes the energy storage characteristic of electrode；Specifically prepare ruthenium-oxide and the compound activity of carbon nanotube
Film, specific thin film preparation process are as follows: using bipolar electrode cathodic deposition, the bipolar electrode cathodic deposition is double
Electrode DC cathodic deposition, experimental facilities use Shanghai Chen Hua CHI660B electrochemical workstation, wherein silicon substrate micro-structure conduct
Cathode and working electrode, for platinum electrode as anode and auxiliary electrode, depositing liquid is to take using in multi-walled carbon nanotube MCNT) experiment
Carbon nanotube 1 g, RuCl3 0.05 g, NaNO30.85 g and 50 mL deionized waters are configured to ruthenic chloride and sodium nitrate
Mixed aqueous solution, ultrasonic vibration 30 minutes, so that Ru3+It is sufficiently adsorbed by carbon nanotube；Co-deposition after being as ultrasonically treated
Liquid；Depositing current density is set as 500 mA/cm2, sedimentation time prepares ruthenium-oxide and carbon nanotube from 500 seconds to 2000 second
Compound active film is rinsed after the completion of deposition with deionized water, is then placed in 100 DEG C of air atmospheres and dries 0.5 hour
It is spare.
8. metal oxide and the compound microtrabeculae energy storage electrode preparation method of carbon nanotube according to claim 5, feature
It is, to oxide, the active film pattern compound with carbon nanotube is characterized, made under different sedimentation times in experiment
Standby ruthenium-oxide is different from the surface topography of the compound active film of carbon nanotube, and the deposition at microtrabeculae position is not quite similar；
As can be seen that depositing the complex function thin film prepared from electron microscope, there is not any crack or peeling phenomenon,
Laminated film forms special class fried dough twist class corrugated, fine and close, uniform spatial network frame structure；In laminated film, carbon
The netted body structure surface of nanotube distributed uniform ruthenium-oxide particle, form that specific surface area is higher, electrode activity is stronger more
The three-dimensional netted composite construction in hole；Moreover, the contact adhesive strength between function film and matrix is also than common ruthenium-oxide function
Film is higher；Laminated film surface is very smooth, and carbon nanotube mesh structures are also extremely compact and uniform；
When being 500 s between when deposited, on microtrabeculae top, there is no apparent carbon nanotubes to occur, and in microtrabeculae bottom end, then shape
At carbon nanotube abundant and ruthenium-oxide composite construction, it is based on silicon substrate " micro- grass " template, with the increase of sedimentation time, oxidation
Ruthenium climbs upwards along " micro- grass ", formed cannulated structure, and the carbon nanotube of porous network structure then with tubulose ruthenium-oxide
Structure is interweaved winding；
When be stepped up between when deposited to 1000 s, it is observed that the ruthenium-oxide and carbon nanotube in microtrabeculae bottom end are compound
Membrane structure growth is more and more obvious, and deposition dramatically increases, meanwhile, on microtrabeculae top, also occur a certain amount of thick
Stratum granulosum package carbon nano tube structure；
When reaching 2000 s between when deposited, then there is more special appearance structure, all three-dimensional structures it is whole all by
Thick carbon nano-tube coextruded film is wrapped up, and around microtrabeculae, special corrugated is presented in compound structure film, on microtrabeculae top
End, the thickness of laminated film has been more than 5 μm；In microtrabeculae bottom end, these structures are mutually wound, perforation, fully wrapped around " micro- grass "
Structure forms the higher special netted laminated film of thickness.
9. metal oxide and the compound microtrabeculae energy storage electrode preparation method of carbon nanotube according to claim 5, feature
It is, the cyclic voltammetry curve of the metal oxide and the compound microtrabeculae energy storage electrode of carbon nanotube is tested by single electrode
It analyzes, under different scanning rates, discovery is changed by the specific capacity of specific capacity and ruthenium-oxide electrode film to laminated film,
Under the low sweep speed of 5 mV/s, the specific capacity of combination electrode material reaches 272 mF/cm2, relative to ruthenium-oxide electrode, promoted
170%；With the increase of sweep speed, in 100 mV/s, the specific capacity of combination electrode drops to 206 mF/cm2, decline
24%, hereafter, fall off rate gradually slows down；In combination electrode film, due to being uniformly distributed for nano oxidized ruthenium material, simultaneously
It is that bigger contact interface is provided between matrix and electrolyte that composite material, which is formed by three-D nano-porous structure also, is passed through
Carbon nanotube conducting channel, so that ion is diffused by nano pore, electron-transport Distance Shortened, material activity enhancing,
The specific capacity of electrode is increased dramatically；
In addition, the cycle life under the high sweep speed of 80 mV/s of energy storage electrode progress is tested, in preceding 2000 circulations, electricity
Ultimate ratio capacity is gradually promoted to 220 mF/cm2, this is because during this period of time, the electrode material in laminated film obtains
Adequately activation, material activity are fully used, embody capacity and go up steadily；In 2000 ~ 3000 cyclic processes,
Capacity is almost without decaying；Time circulation, capacity are basically stable at 217 mF/cm from 3000 to 60002, relative to 220 mF/cm2,
Only decay 1.4%, cyclical stability when showing combination electrode excellent long；This also has benefited from carbon nanotube mesh structures
Supporting role to electrode film avoids the cracking of film, falls off.
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| CN114366092A (en) * | 2021-12-20 | 2022-04-19 | 中山大学 | Micro-needle sensor based on electro-codeposition electron mediator and preparation method thereof |
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| CN114366092A (en) * | 2021-12-20 | 2022-04-19 | 中山大学 | Micro-needle sensor based on electro-codeposition electron mediator and preparation method thereof |
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