CN115188594B - Three-dimensional carbon tube grid film with double-shell structure and preparation method and application thereof - Google Patents
Three-dimensional carbon tube grid film with double-shell structure and preparation method and application thereof Download PDFInfo
- Publication number
- CN115188594B CN115188594B CN202210856006.3A CN202210856006A CN115188594B CN 115188594 B CN115188594 B CN 115188594B CN 202210856006 A CN202210856006 A CN 202210856006A CN 115188594 B CN115188594 B CN 115188594B
- Authority
- CN
- China
- Prior art keywords
- carbon tube
- dimensional
- carbon
- grid film
- double
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 201
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003990 capacitor Substances 0.000 claims abstract description 42
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000005486 organic electrolyte Substances 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002799 BoPET Polymers 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 238000003486 chemical etching Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000002985 plastic film Substances 0.000 claims description 2
- 229920006255 plastic film Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- -1 tetraethylammonium tetrafluoroborate Chemical group 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical class Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 13
- 230000004044 response Effects 0.000 abstract description 13
- 230000037427 ion transport Effects 0.000 abstract description 8
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 238000012983 electrochemical energy storage Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 44
- 239000002041 carbon nanotube Substances 0.000 description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 description 12
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a three-dimensional carbon tube grid film with a double-shell structure, and a preparation method and application thereof. The invention takes porous anodic aluminum oxide with three-dimensional interconnection pore channels as a template, and sequentially carries out chemical vapor deposition to grow an outer carbon tube, atomic layer deposition to grow an aluminum oxide sacrificial layer and chemical vapor deposition to grow an inner carbon tube in the template holes, and the three-dimensional carbon tube network grid film formed by interconnecting carbon tube units of a carbon tube sleeve with separation gaps is obtained after the aluminum oxide template and the sacrificial layer are removed simultaneously. The preparation method is simple and convenient to operate, and the prepared sample has adjustable structure, good uniformity and high repeatability. The gaps among the vertical carbon tube sleeve and the carbon tube units with high orientation can be regulated and controlled by controlling the atomic layer deposition period, so that the specific surface area of the electrode material is increased, the energy density of an electric double layer electrochemical capacitor constructed by the electrode material is further increased, a straight rapid ion transport channel can be provided, and the electrode material can be widely used for electrochemical energy storage devices with high-frequency (< kHz) response.
Description
Technical Field
The invention relates to the technical field of nanostructure material preparation technology and electrochemical capacitor electrode material, in particular to a three-dimensional carbon tube grid film with a double-shell structure, and a preparation method and application thereof.
Background
With the rapid development of artificial intelligence and information technology, the wide application of wearable and portable electronic devices has led to an increasing demand for miniaturization and weight reduction of electronic components. In the application fields of high power output, alternating current filtering and the like, an aluminum electrolytic capacitor is used as an electric energy storage device and always occupies the primary position. However, since the energy density of the aluminum electrolytic capacitor is low, it is generally the largest element in the circuit, which hinders the miniaturization and portability of the device.
In 2015, yverick Rangom et al have found that the upright Carbon Nanotube array, due to its high orientation, can provide a straight and rapid ion transmission channel between nanotubes, thereby improving the response speed of ions to electric signals, and is expected to be used as an electrode of an electrochemical capacitor for rapid response (Carbon Nanotube-Based Supercapacitors with Excellent ac Line Filtering and Rate Capability via Improved Interfacial Impedance, ACS Nano 2015,9 (7): 7248-7255). However, as the length-diameter ratio of the carbon tubes increases in the vertical carbon tube array, the top ends of the carbon tubes are easy to agglomerate, so that ion transport is blocked, and the response performance of the vertical carbon tube array to frequency is reduced.
It is found that, by connecting adjacent parallel carbon tubes in a carbon tube array with carbon tubes supported transversely to form an integrated carbon tube film with a three-dimensional interconnection grid structure, a very stable structure can be formed, agglomeration between adjacent vertical carbon tubes can be effectively prevented, and the conductivity of the carbon tube film can be enhanced, so that the performance of the carbon tube film as an electrode of an electrochemical capacitor is hopefully improved, for example, a three-dimensional interconnection carbon tube grid film and a preparation method and application thereof in Chinese patent No. CN108217628A are disclosed, nickel sulfate particles are loaded on the hole wall of a three-dimensional through hole alumina template by using a dipping-drying method, and during chemical vapor deposition, the nickel sulfate particles can catalyze and grow finer carbon nanotubes, and simultaneously, vertical and transverse carbon nanotubes are grown under the limiting domain action of a template hole, so that the carbon nanotubes with finer structures are built in the vertical and transverse carbon nanotubes are prepared. However, the areal density of the carbon tubes cannot be adjusted therein, so that the specific surface area is not large enough, and thus the specific capacitance per unit area is relatively small. How to increase the specific surface area of the three-dimensional interconnected carbon tube grid film, and further increase the specific capacitance of the unit area of the three-dimensional interconnected carbon tube grid film becomes important.
Disclosure of Invention
The invention aims to provide a preparation method of a three-dimensional carbon tube grid film with a double-shell structure, and the prepared three-dimensional carbon tube grid film consists of carbon tube sleeve carbon tube units with separation gaps, so that the specific surface area of the three-dimensional interconnected carbon tube grid film can be effectively increased, and the specific area capacitance and the frequency response performance of the three-dimensional interconnected carbon tube grid film can be improved when the three-dimensional carbon tube grid film is used as an electrode material of an electrochemical capacitor, so that the three-dimensional carbon tube grid film is expected to be used in the fields of alternating current filtering, high power output and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme: the preparation method of the three-dimensional carbon tube grid film with the double-shell structure comprises the following steps:
s1, taking three-dimensional porous alumina with an interconnection pore canal inside as a template, and depositing a first layer of carbon on the inner wall of the interconnection pore canal as an outer layer of carbon tube by chemical vapor deposition to form the three-dimensional interconnection carbon tube with the alumina template;
s2, depositing a layer of alumina on the inner wall of a first layer of carbon in the three-dimensional interconnected carbon tube with the alumina template to serve as a sacrificial layer, so as to obtain an anodic alumina-carbon tube-sacrificial layer alumina three-dimensional structure composite material;
s3, growing a second layer of carbon serving as an inner layer carbon tube on the inner wall of the sacrificial layer alumina by chemical vapor deposition;
alternatively, repeating steps S2 and S3;
s4, removing the three-dimensional porous alumina template and the alumina sacrificial layer through chemical corrosion to obtain the three-dimensional carbon pipe network grid film formed by interconnecting carbon pipe sleeve and carbon pipe units with separation gaps, wherein the number of the carbon pipe layers is more than 2.
The preparation method of the three-dimensional carbon pipe network grid film with the double-shell structure is further improved:
preferably, the preparation method of the three-dimensional porous alumina in the step S1 is as follows: taking 0.25-0.35mol/L phosphoric acid solution as electrolyte, taking aluminum sheets containing trace impurities as anode and graphite as cathode, and carrying out anodic oxidation for 8-10h at the temperature of 0 ℃ and under the direct-current constant pressure of 185-195V; then placing the aluminum oxide into a saturated stannic chloride solution, and removing the residual aluminum which is not anodized to obtain anodized aluminum; then placing the anodized aluminum into a phosphoric acid solution with the weight percent of 3-7% at the temperature of 35-45 ℃ for soaking for 10-20min, and obtaining the three-dimensional porous aluminum oxide.
Preferably, the aluminum content in the aluminum sheet containing trace impurities is 99.5-99.8wt%, and the impurities are mainly iron, silicon and copper which are less than or equal to 0.5wt%.
Preferably, the specific steps of chemical vapor deposition in the steps S1 and S3 are: placing three-dimensional porous alumina in a high-temperature tube furnace at 900-1100 deg.C under vacuum degree of-0.1 Mpa, and reacting gas source acetylene C 2 H 4 At the flow rate of 55-65ml/min, chemical vapor deposition is carried out for 60-80min, cooling is carried out to room temperature after deposition is finished, and plasma cleaning is carried out on the surface of the sample.
Preferably, the specific steps of chemical vapor deposition in the steps S1 and S3 are: placing the three-dimensional porous alumina in a high-temperature tubular furnace, performing chemical vapor deposition for 70-110min by taking argon of 78-82ml/min as carrier gas under the conditions that the temperature of the high-temperature tubular furnace is 600-700 ℃ and the acetylene flow is 4-8ml/min, cooling to room temperature after the deposition is finished, and performing plasma cleaning on the surface of a sample.
Preferably, the specific steps of depositing a layer of alumina in step S2 are: the three-dimensional interconnected carbon tube with the alumina template is placed in an atomic layer deposition instrument, ozone and precursor trimethylaluminum TMA are used as reaction sources, or water and precursor trimethylaluminum TMA are used as reaction sources, the reaction temperature is 200-300 ℃, and the atomic layer deposition cycle number is 50-400.
Preferably, the etching solution used for the chemical etching in step S4 is a 10-30wt% hydrofluoric acid solution.
The second object of the present invention is to provide a three-dimensional carbon tube grid film manufactured by the above manufacturing method.
The invention also provides an application of the three-dimensional carbon tube grid film with the double-shell structure to an electrochemical capacitor, and the preparation method of the electrochemical capacitor comprises the following steps: and (3) evaporating a gold-plated film on one of the flat paved surfaces of the three-dimensional carbon pipe network grid film, then cutting into two symmetrical electrodes with the same area, taking the metal electrode plates as current collectors, and injecting aqueous electrolyte after the two symmetrical electrodes are isolated by an aqueous diaphragm for packaging, or injecting organic electrolyte after the two symmetrical electrodes are isolated by an organic electrolyte diaphragm for packaging.
Preferably, the aqueous electrolyte is a sulfuric acid solution of 0.8 to 1.2mol/L, and the organic electrolyte is a tetraethylammonium tetrafluoroborate TEABF of 0.8 to 1.2mol/L 4 The method comprises the steps of carrying out a first treatment on the surface of the And packaging by adopting a PET film or an aluminum plastic film.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a preparation method of a three-dimensional carbon tube grid film with a double-shell structure, wherein the double-shell structure is formed by mutually connecting double-shell carbon tube sleeve carbon tube units with separation gaps, and the gaps between the inner carbon tube and the outer carbon tube can be manually regulated and controlled. The invention takes porous anodic aluminum oxide with three-dimensional interconnected pore channels as a template, and deposits a carbon layer on the pore wall of the template by adopting a chemical vapor deposition method based on the space geometry finite field induction effect of the template pore to obtain a three-dimensional interconnected outer carbon tube; then adopting an atomic layer deposition method to deposit a layer of alumina serving as a sacrificial layer on the inner wall of the three-dimensional interconnected carbon tube; then growing an inner layer carbon tube on the inner wall of the sacrificial layer alumina nano tube by adopting a chemical vapor deposition method; finally, the alumina template and the alumina sacrificial layer are removed by a chemical corrosion method, and a self-supporting three-dimensional grid film which is formed by interconnecting carbon tube sleeve units with separation gaps is obtained.
The carbon tube unit in the three-dimensional carbon tube network grid film prepared by the invention is not a common carbon tube, but a carbon tube sleeve carbon tube double-shell structure (similar to a structure of Russian Luo Sitao baby) with uniform gaps, and the unique structure can improve the specific surface area of an electrode material, so that the energy density of an electric double-layer electrochemical capacitor constructed by the electrode material is improved. Meanwhile, the gaps among the upright carbon tube sleeve and the carbon tube units can provide straight and rapid ion transport channels, so that the method has important application value in the field of electrochemical capacitors with rapid response. The gap between the inner and outer carbon tubes can be regulated and controlled by controlling the atomic layer deposition period. The preparation method is simple and convenient to operate, and the prepared sample has adjustable structure, good uniformity and high repeatability.
(2) The application adopts higher anodic oxidation voltage when preparing the three-dimensional porous alumina template so as to improve the order of vertical holes in the porous alumina; the application adopts shorter anodic oxidation time to control the thickness of the porous alumina within the range of 10-12 microns, thereby regulating and controlling the performance of the sample.
(3) The three-dimensional carbon pipe network grid film formed by interconnecting the carbon pipe units with the separation gaps can be used as a high-frequency grid film<kHz) in response to the electrode material of the electrochemical capacitor, the thickness of the carbon tube film is 11 microns, and the area specific capacity of the carbon tube film is up to 2.015mF/cm when the gap between the inner carbon tube and the outer carbon tube is 24nm 2 The capacitor assembled by the capacitor is characterized in thatAt ultra-high scan rates of 500V/s, the cyclic voltammogram can still maintain a near rectangular shape with a phase angle of-82.1 ° at 120Hz frequency.
(4) The three-dimensional carbon pipe network grid membrane electrode formed by interconnecting the carbon pipe units with the separation gaps has a unique 'pipe sleeve' structure, can improve the arrangement density of the carbon pipes in unit area, provides a larger electrochemical activity specific surface area of an electrode material, improves the electronic conductivity of the electrode material, and further improves the energy density of the double-layer electrochemical capacitor constructed by the electrode material. Meanwhile, the gaps among the upright carbon tube sleeve and the carbon tube units can provide straight and rapid ion transport channels, and improve the frequency response performance of the capacitor assembled by the gaps, so that the capacitor can be used as an electrochemical capacitor electrode material with high energy density, ultrahigh power density and good frequency response performance.
(5) In the prior patent document CN108217628A, nickel sulfate particles are loaded on the pore wall of a three-dimensional through hole alumina template by utilizing a dipping-drying method, and the nickel sulfate particles can catalyze and grow thinner carbon nanotubes in chemical vapor deposition, and simultaneously grow vertical and transverse carbon nanotubes under the limiting effect of the template pore, so that thinner carbon nanotubes are built in the vertical and transverse carbon nanotubes to improve the specific surface area of the vertical and transverse carbon nanotubes; the carbon nanotubes grown catalytically by nickel sulfate particles are grown disordered. When the carbon nano tube is used as an electrode, unordered growth in a comparison file has an obstacle to ion transport;
according to the method, chemical vapor deposition, atomic layer deposition and chemical vapor deposition are sequentially carried out in an alumina template hole, and after the alumina template and an alumina sacrificial layer are removed, a three-dimensional carbon pipe network lattice film formed by carbon pipe sleeve carbon pipe units with separation gaps is prepared. The structure of the outer and inner three-dimensional interconnected carbon tubes grown in the holes of the alumina template by using a sacrificial layer auxiliary method is ordered. The three-dimensional carbon pipe network grid film has a unique 'pipe sleeve' structure, and can provide a smooth ion transport channel. By alternately performing chemical vapor deposition and atomic layer deposition in the porous alumina template holes a plurality of times in succession, the carbon tube sleeve carbon tube unit with separation gaps in the present application may be of a structure of two or more layers.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. Embodiments of the present invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a schematic illustration of a process for preparing a three-dimensional carbon pipe network grid film comprising interconnected carbon pipe units of the carbon pipe sleeve with separation gaps of the present invention.
Fig. 2 (a, b) is a Scanning Electron Microscope (SEM) image and a Transmission Electron Microscope (TEM) image of a three-dimensional carbon tube network grid film consisting of interconnected carbon tube units of the carbon tube sleeve prepared in example 1; FIG. 2 (c) is a TEM image of a three-dimensional carbon pipe network grid film made up of interconnected carbon pipe units of carbon pipe sleeve prepared in example 5; fig. 2 (d) is an SEM cross-sectional view of a three-dimensional carbon tube network grid film consisting of carbon tube sleeve carbon tube unit interconnections with separation gaps prepared in example 4.
FIG. 3 is a graph showing the electrochemical performance of an electrochemical capacitor assembled from three-dimensional carbon pipe grid films composed of interconnected carbon pipe units of carbon pipe sleeve of example 2, wherein (a, b) is a Cyclic Voltammetry (CV) curve at a sweep rate of 100mV/s to 500V/s; fig. (c, d) are constant current charge-discharge (GCD) curves.
FIG. 4 is a comparison of the performance of electrochemical capacitors assembled in examples 2, 3, and 4, respectively, wherein the bode plot (a), nyquist plot (b), and area specific capacitance versus frequency plot (c) were obtained from Electrochemical Impedance Spectroscopy (EIS); fig. 4 (d) is a graph showing the relationship between the frequency and the real and imaginary capacitances of the three-dimensional carbon pipe grid film composed of interconnected carbon pipe units of the carbon pipe sleeve of example 1.
Detailed Description
The present invention will be further described in detail with reference to the following examples, in order to make the objects, technical solutions and advantages of the present invention more apparent, and all other examples obtained by those skilled in the art without making any inventive effort are within the scope of the present invention based on the examples in the present invention.
Example 1
The embodiment provides a method for preparing a three-dimensional carbon tube grid film formed by interconnecting carbon tube units of a carbon tube sleeve, wherein the preparation flow is shown in fig. 1, and specifically comprises the following steps:
(1) Placing three-dimensional porous alumina with thickness of 11 μm and vertical and transverse channels in a high temperature tube furnace, and reacting at 1000deg.C under-0.1 Mpa vacuum degree to obtain acetylene (C) 2 H 4 ) The flow is 60ml/min, the reaction time is 60 minutes, a first layer of carbon is deposited on the inner walls of the vertical pore canal and the transverse pore canal to serve as an outer layer carbon tube, and the surface plasma cleaning is carried out after cooling to obtain the three-dimensional interconnected carbon tube with the alumina template;
(2) Placing the three-dimensional interconnected carbon tube with the alumina template obtained in the step (1) into an atomic layer deposition instrument, and obtaining the three-dimensional interconnected carbon tube with the alumina template and the sacrificial layer by taking Trimethylaluminum (TMA) and ozone as reaction sources, wherein the reaction temperature is 250 ℃ and the deposition cycle number is 200;
(3) Placing the three-dimensional interconnected carbon tube with the alumina template and the sacrificial layer obtained in the step (2) into a high-temperature tube furnace by taking the three-dimensional interconnected carbon tube with the alumina template and the sacrificial layer as a carrier, and depositing a second layer of carbon tube as an inner layer of carbon tube on the inner wall of the first layer of carbon tube according to the method and parameters of the step (1);
(4) And (3) carrying out plasma cleaning on the surface of the sample, then placing the sample in a 20wt% hydrofluoric acid solution to chemically corrode the alumina template and the sacrificial layer, and rinsing and drying the sample to obtain the three-dimensional carbon pipe network grid film formed by interconnecting carbon pipe units of the carbon pipe sleeve, wherein the gap between the inner and outer carbon pipes is about 24 nanometers.
A Scanning Electron Microscope (SEM) image of a three-dimensional carbon tube network grid film consisting of interconnected carbon tube units of the carbon tube sleeve prepared in example 1 is shown in fig. 2 (a, b); as can be seen from fig. 2a and b, a three-dimensional carbon tube mesh film composed of interconnected carbon tube units of a carbon tube sleeve was successfully produced, and the gap between the inner and outer carbon tubes was about 24nm, with a unique "carbon tube sleeve carbon tube" structure.
Example 2
The electrochemical capacitor is prepared by adopting the three-dimensional carbon tube grid film prepared in the embodiment 1, and the method specifically comprises the following steps:
(1) Evaporating a gold film on one surface of the three-dimensional carbon pipe network grid film prepared in the embodiment 1, which is not opened, and cutting the carbon pipe network grid film into two symmetrical electrodes with the same area;
(2) After the two symmetrical electrodes are isolated by a water-based diaphragm, 0.1mol/L sulfuric acid solution is injected to be used as a water-based electrolyte;
(3) The assembled capacitor is packaged using a PET film.
The electrochemical capacitor prepared in example 2 was subjected to electrochemical performance test, and the results are shown in FIG. 3, and FIG. 3 (a, b) is a Cyclic Voltammetry (CV) curve of the electrochemical capacitor in example 2 at a sweep rate of 100mV/s to 500V/s; fig. 3 (c, d) is a constant current charge-discharge (GCD) curve. As can be seen from fig. 3: at a sweeping speed of 100mV/s to 500V/s, the CV curve is approximately rectangular in shape, and the constant current charge and discharge test result shows an ideal isosceles triangle, and the prepared capacitor shows nearly ideal double-layer capacitor characteristics; and at a high sweeping speed of 500V/s, the shape of the three-dimensional carbon pipe network grid film can still maintain a nearly rectangular shape, which shows that the prepared three-dimensional carbon pipe network grid film formed by interconnecting carbon pipe units with separation gaps has better power performance when applied to an electrochemical capacitor electrode.
Example 3
The embodiment provides a preparation method of a single-layer three-dimensional carbon tube grid film, and the specific steps refer to embodiment 1, except that an alumina sacrificial layer and an inner layer carbon tube are not deposited, namely, steps (2) and (3) are not needed, and the preparation method is directly prepared by removing a three-dimensional porous alumina template through chemical corrosion.
And an electrochemical capacitor was prepared with reference to the procedure of example 2.
Example 4
The embodiment provides a three-dimensional carbon pipe network grid film formed by interconnecting carbon pipe units with separation gaps, wherein the carbon pipe units are of a 3-layer structure, and an electrochemical capacitor thereof, and the specific steps are as follows with reference to embodiment 1, wherein: and (3) after depositing the second layer of carbon tube, repeating the step (2) and the step (3), sequentially depositing the second layer of aluminum oxide sacrificial layer and the third layer of carbon tube according to the same method and parameters, and then preparing the three-dimensional carbon tube network grid film formed by interconnecting the carbon tube sleeve carbon tube units with the 3-layer structure and separation gaps according to the method in the step (4).
And an electrochemical capacitor was prepared with reference to the procedure of example 2.
As shown in fig. 2d, it can be seen from fig. 2d that the three-dimensional carbon pipe network lattice film formed by interconnecting the 3-layer carbon pipe sleeve units with the separation gaps can be successfully manufactured, and the gaps between the adjacent shell carbon pipes are about 24 nm.
Electrochemical capacitor assembled by three-dimensional carbon pipe network grid films formed by interconnecting carbon pipe sleeve units in example 2, electrochemical capacitor assembled by single-layer three-dimensional carbon pipe network grid films prepared in example 3 and electrochemical capacitor assembled by three-dimensional carbon pipe network grid films formed by interconnecting 3 layers of carbon pipe sleeve carbon pipe units prepared in example 4 are respectively subjected to electrochemical capacitance performance comparison, and the results are shown in fig. 4 (a-c), wherein a bode graph (a), a nyquist curve (b) and an area ratio capacitance and frequency relation curve (c) are obtained by Electrochemical Impedance Spectroscopy (EIS). The frequency versus real and imaginary capacitances of the electrochemical capacitors prepared in example 2 were tested as shown in fig. 4 (d).
As can be seen from fig. 4 (a-c): the electrochemical capacitor prepared in example 2 has an imaginary resistance approximately perpendicular to the real axis in the Nyquist diagram, shows ideal capacitance characteristics, and has a small equivalent series resistance (0.42 Ω); in the Bode graph reflecting the relation between the phase angle and the frequency, the phase angle of a low-frequency region is close to-90 degrees, the characteristics of an ideal capacitor are also described, the phase angle reaches-82.1 degrees at the frequency of 120Hz, and the good rapid frequency response capability is shown; the area specific capacitance at 120Hz can reach very high 2.015mF/cm 2 Far above 0.817mF/cm of example 3 2 . The capacitor of example 4 reached a phase angle of-81.5 ° at a frequency of 120Hz, exhibiting good frequency response performance; the area specific capacitance at 120Hz frequency can reach 1.837mF/cm 2 Has higher energy density.
As shown in the frequency versus real and imaginary capacitances plot of example 2 in fig. 4 (d), the characteristic frequency at which the imaginary capacitance reaches a maximum is 2318Hz, with a short relaxation time (0.431 ms), indicating efficient ion transport and electron conduction in the electrode. It can be seen that the three-dimensional carbon pipe network grid film consisting of carbon pipe sleeve and carbon pipe units with separation gaps prepared in example 2 has higher area specific capacitance and good high-frequency response performance. This is because the three-dimensional carbon pipe network grid film formed by interconnecting the carbon pipe units of the carbon pipe sleeve with the separation gaps has higher arrangement density of carbon pipes per unit area compared with the single-layer three-dimensional carbon pipe network grid film prepared in example 3, can provide larger electrochemical activity specific surface area of the electrode material, and further improves the energy density of the electric double layer electrochemical capacitor constructed by the same. At the same time, the gaps between the upstanding carbon tube sleeve carbon tube units provide a straight, rapid ion transport path, which improves the frequency response performance of the capacitor assembled therefrom.
Example 5
The embodiment provides a method for preparing a three-dimensional carbon tube grid film formed by interconnecting carbon tube units of a carbon tube sleeve, wherein the gap between an inner carbon tube and an outer carbon tube is about 36 nanometers, and the specific steps refer to embodiment 1, and the difference is that the atomic layer deposition cycle number in the step (2) is increased to 300.
A Scanning Electron Microscope (SEM) image of a three-dimensional carbon tube network grid film consisting of interconnected carbon tube units of the carbon tube sleeve prepared in example 5 is shown in fig. 2 (c); as can be seen from fig. 2 (c), the gap between the inner and outer carbon tubes in the three-dimensional carbon tube grid film prepared in example 5 is about 36 nm, compared with the three-dimensional carbon tube grid film (fig. 2 b) prepared in example 1, in which the gap between the inner and outer carbon tubes is about 24nm, which indicates that the gap between the two carbon tubes can be controlled by controlling the atomic layer deposition cycle.
Those skilled in the art will appreciate that the foregoing is merely a few, but not all, embodiments of the invention. It should be noted that many variations and modifications can be made by those skilled in the art, and all variations and modifications which do not depart from the scope of the invention as defined in the appended claims are intended to be protected.
Claims (10)
1. The preparation method of the three-dimensional carbon tube grid film with the double-shell structure is characterized by comprising the following steps of:
s1, taking three-dimensional porous alumina with an interconnection pore canal inside as a template, and depositing a first layer of carbon on the inner wall of the interconnection pore canal as an outer layer of carbon tube by chemical vapor deposition to form the three-dimensional interconnection carbon tube with the alumina template;
s2, depositing a layer of alumina on the inner wall of a first layer of carbon in the three-dimensional interconnected carbon tube with the alumina template to serve as a sacrificial layer, so as to obtain an anodic alumina-carbon tube-sacrificial layer alumina three-dimensional structure composite material;
s3, growing a second layer of carbon serving as an inner layer carbon tube on the inner wall of the sacrificial layer alumina by chemical vapor deposition;
alternatively, repeating steps S2 and S3;
s4, removing the three-dimensional porous alumina template and the alumina sacrificial layer through chemical corrosion to obtain the three-dimensional carbon pipe network grid film formed by interconnecting carbon pipe sleeve and carbon pipe units with separation gaps, wherein the number of the carbon pipe layers is more than 2.
2. The method for preparing a three-dimensional carbon tube grid film with a double-shell structure according to claim 1, wherein the method for preparing the three-dimensional porous alumina in the step S1 is as follows: taking 0.25-0.35mol/L phosphoric acid solution as electrolyte, taking aluminum sheets containing trace impurities as anode and graphite as cathode, and carrying out anodic oxidation for 8-10h at the temperature of 0 ℃ and under the direct-current constant pressure of 185-195V; then placing the aluminum oxide into a saturated stannic chloride solution, and removing the residual aluminum which is not anodized to obtain anodized aluminum; then placing the anodized aluminum into a phosphoric acid solution with the weight percent of 3-7% at the temperature of 35-45 ℃ for soaking for 10-20min, and obtaining the three-dimensional porous aluminum oxide.
3. The method for preparing a three-dimensional carbon tube grid film having a double-shell structure according to claim 2, wherein the aluminum content in the aluminum sheet containing a trace amount of impurities is 99.5 to 99.8wt%, the impurities include iron, silicon, copper and the total content of impurities is not more than 0.5wt%.
4. The method for preparing a three-dimensional carbon tube grid film with a double-shell structure according to claim 1, wherein the specific steps of chemical vapor deposition in the steps S1 and S3 are as follows: placing three-dimensional porous alumina in a high-temperature tube furnace at 900-1100 deg.C under vacuum degree of-0.1 Mpa, and reacting gas source acetylene C 2 H 4 The flow of the solution is 55-65ml/min, the chemical vapor deposition is carried out for 60-80min, the solution is cooled to room temperature after the deposition is finished, and the surface of the sample is subjected to plasma cleaning.
5. The method for preparing a three-dimensional carbon tube grid film with a double-shell structure according to claim 1, wherein the specific steps of chemical vapor deposition in the steps S1 and S3 are as follows: placing the three-dimensional porous alumina in a high-temperature tubular furnace, wherein the temperature of the high-temperature tubular furnace is 600-700 ℃, taking argon of 78-82ml/min as carrier gas under normal pressure and acetylene flow of 4-8ml/min, performing chemical vapor deposition for 70-110min, cooling to room temperature after deposition, and performing plasma cleaning on the surface of a sample.
6. The method for preparing a three-dimensional carbon tube grid film with a double-shell structure according to claim 1, wherein the specific steps of depositing a layer of aluminum oxide in step S2 are as follows: the three-dimensional interconnected carbon tube with the alumina template is placed in an atomic layer deposition instrument, ozone and precursor trimethylaluminum TMA are used as reaction sources, or water and precursor trimethylaluminum TMA are used as reaction sources, the reaction temperature is 200-300 ℃, and the atomic layer deposition cycle number is 50-400.
7. The method for preparing a three-dimensional carbon tube grid film having a double-shell structure according to claim 1, wherein the etching solution used for the chemical etching in step S4 is a 10-30wt% hydrofluoric acid solution.
8. A three-dimensional carbon network grid film of a double-shell structure produced by the production method of any one of claims 1 to 7.
9. Use of the three-dimensional carbon tube grid film with the double-shell structure as claimed in claim 8 in an electrochemical capacitor, characterized in that the electrochemical capacitor is prepared by the following method: and (3) evaporating a gold-plated film on one of the flat paved surfaces of the three-dimensional carbon pipe network grid film, then cutting into two symmetrical electrodes with the same area, taking the metal electrode plates as current collectors, and injecting aqueous electrolyte after the two symmetrical electrodes are isolated by an aqueous diaphragm for packaging, or injecting organic electrolyte after the two symmetrical electrodes are isolated by an organic electrolyte diaphragm for packaging.
10. The use of a three-dimensional carbon tube grid film with a double-shell structure according to claim 9 on an electrochemical capacitor, wherein the aqueous electrolyte is a sulfuric acid solution of 0.8-1.2mol/L, and the organic electrolyte is tetraethylammonium tetrafluoroborate TEABF of 0.8-1.2mol/L 4 The method comprises the steps of carrying out a first treatment on the surface of the And packaging by adopting a PET film or an aluminum plastic film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210856006.3A CN115188594B (en) | 2022-07-11 | 2022-07-11 | Three-dimensional carbon tube grid film with double-shell structure and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210856006.3A CN115188594B (en) | 2022-07-11 | 2022-07-11 | Three-dimensional carbon tube grid film with double-shell structure and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115188594A CN115188594A (en) | 2022-10-14 |
| CN115188594B true CN115188594B (en) | 2023-06-27 |
Family
ID=83519411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210856006.3A Active CN115188594B (en) | 2022-07-11 | 2022-07-11 | Three-dimensional carbon tube grid film with double-shell structure and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115188594B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324302A (en) * | 2011-06-13 | 2012-01-18 | 郑州大学 | Preparation method of super capacitor based on one-dimensional metal-carbon nano tube coaxial heterojunction |
| CN102543475A (en) * | 2012-02-15 | 2012-07-04 | 中国科学院合肥物质科学研究院 | Method for preparing photoanode thin film material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7758921B2 (en) * | 2005-05-26 | 2010-07-20 | Uchicago Argonne, Llc | Method of fabricating electrode catalyst layers with directionally oriented carbon support for proton exchange membrane fuel cell |
| US8614878B2 (en) * | 2008-01-17 | 2013-12-24 | Fraser W. SEYMOUR | Nanoscale intercalation materials on carbon powder, process for production, and use thereof |
-
2022
- 2022-07-11 CN CN202210856006.3A patent/CN115188594B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324302A (en) * | 2011-06-13 | 2012-01-18 | 郑州大学 | Preparation method of super capacitor based on one-dimensional metal-carbon nano tube coaxial heterojunction |
| CN102543475A (en) * | 2012-02-15 | 2012-07-04 | 中国科学院合肥物质科学研究院 | Method for preparing photoanode thin film material |
Non-Patent Citations (1)
| Title |
|---|
| 石墨烯的组装和织构调控:碳功能材料的液相制备方法;陶莹;杨全红;;科学通报(第33期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115188594A (en) | 2022-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gao et al. | Diamond-based supercapacitors: realization and properties | |
| Choudhary et al. | Directly deposited MoS 2 thin film electrodes for high performance supercapacitors | |
| Ding et al. | Crystalline NiCo2S4 nanotube array coated with amorphous NiCoxSy for supercapacitor electrodes | |
| Shah et al. | Electrochemical double layer capacitor electrodes using aligned carbon nanotubes grown directly on metals | |
| Sahoo et al. | A review on supercapacitors based on plasma enhanced chemical vapor deposited vertical graphene arrays | |
| Dai et al. | Ni (OH) 2/NiO/Ni composite nanotube arrays for high-performance supercapacitors | |
| US8213157B2 (en) | Single-wall carbon nanotube supercapacitor | |
| Ren et al. | Self-supported graphene nanosheet-based composites as binder-free electrodes for advanced electrochemical energy conversion and storage | |
| CN110574132B (en) | Deposited carbon film on etched silicon for on-chip supercapacitors | |
| TW201135769A (en) | High performance carbon nanotube energy storage device | |
| Hong et al. | Microstructuring of carbon/tin quantum dots via a novel photolithography and pyrolysis-reduction process | |
| WO2015008615A1 (en) | Metal hydroxide alignment electrode material, metal hydroxide-containing electrode, manufacturing method of these, and metal hydroxide-containing capacitor | |
| US20210134536A1 (en) | High frequency supercapacitors and methods of making same | |
| Dam et al. | Fabrication of a mesoporous Co (OH) 2/ITO nanowire composite electrode and its application in supercapacitors | |
| Wen et al. | Facile synthesis of a Bi 2 MoO 6/TiO 2 nanotube arrays composite by the solvothermal method and its application for high-performance supercapacitor | |
| Thulasi et al. | Facile synthesis of TNT-VO2 (M) nanocomposites for high performance supercapacitors | |
| Ghosh et al. | Performance dependence of electrochemical capacitor on surface morphology for vertically aligned graphene nanosheets | |
| Namsheer et al. | Molybdenum sulfo-selenides grown on surface engineered vertically aligned graphitic petal arrays for solid-state supercapacitors | |
| Zeng et al. | Hierarchically porous graphene/wood-derived carbon activated using ZnCl 2 and decorated with in situ grown NiCo 2 O 4 for high–performance asymmetric supercapacitors | |
| Dhaiveegan et al. | Pulse-reversal deposition of Ni3S2 thin films on carbon fiber cloths for supercapacitors | |
| Li et al. | MoS2 modified TiN nanotube arrays for advanced supercapacitors electrode | |
| CN115188594B (en) | Three-dimensional carbon tube grid film with double-shell structure and preparation method and application thereof | |
| Zhang et al. | Enlarged capacitance of TiO 2 nanotube array electrodes treated by water soaking | |
| EP4229664B1 (en) | Direct growth cross-linked carbon nanotubes on microstructured metal substrate for supercapacitor application | |
| He et al. | Preparation of Ni Nanoparticles-TiO 2 Nanotube Arrays Composite and Its Application for Electrochemical Capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |