CN117776102A - Preparation method of fullerene hydrogen storage material and fullerene hydrogen storage film - Google Patents
Preparation method of fullerene hydrogen storage material and fullerene hydrogen storage film Download PDFInfo
- Publication number
- CN117776102A CN117776102A CN202410212729.9A CN202410212729A CN117776102A CN 117776102 A CN117776102 A CN 117776102A CN 202410212729 A CN202410212729 A CN 202410212729A CN 117776102 A CN117776102 A CN 117776102A
- Authority
- CN
- China
- Prior art keywords
- fullerene
- hydrogen storage
- material layer
- metal
- sputtering
- 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.)
- Granted
Links
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims abstract description 255
- 229910003472 fullerene Inorganic materials 0.000 title claims abstract description 255
- 239000001257 hydrogen Substances 0.000 title claims abstract description 113
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 113
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000003860 storage Methods 0.000 title claims abstract description 55
- 239000011232 storage material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 163
- 238000004544 sputter deposition Methods 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 230000007547 defect Effects 0.000 claims abstract description 30
- 238000000151 deposition Methods 0.000 claims abstract description 30
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 17
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 10
- 230000001678 irradiating effect Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 150000001721 carbon Chemical group 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 141
- 239000007769 metal material Substances 0.000 description 25
- 125000004432 carbon atom Chemical group C* 0.000 description 22
- -1 polyethylene Polymers 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 239000013077 target material Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000000168 high power impulse magnetron sputter deposition Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
The application provides a preparation method of a fullerene hydrogen storage material and a fullerene hydrogen storage film. The preparation method of the fullerene hydrogen storage material comprises the following steps: depositing a layer of fullerene material on a substrate; placing the substrate deposited with the fullerene material layer in a sputtering chamber with a metal target, sputtering the metal target to form metal ions, and enabling the metal ions to bombard the fullerene material layer; and depositing lithium metal on the surface of the fullerene material layer to dope lithium atoms in the fullerene material layer. The preparation method mainly forms carbon atom vacancy defects on the surface of the fullerene without affecting the internal volume of the fullerene, and can effectively improve the hydrogen storage amount of the fullerene hydrogen storage material.
Description
Technical Field
The invention relates to the technical field of hydrogen storage, in particular to a preparation method of a fullerene hydrogen storage material and a fullerene hydrogen storage membrane.
Background
Hydrogen has a wide source of raw materials, has extremely high heat value, and compared with the fossil energy commonly used at present, the combustion product of hydrogen is only water and can be prepared by electrolysis of water, so that the hydrogen is considered to be an ideal clean energy carrier. However, a big bottleneck that restricts the further utilization of hydrogen is how to store hydrogen efficiently. Currently available hydrogen storage modes include gaseous hydrogen storage, liquid hydrogen storage and solid hydrogen storage, and the requirements of the gaseous hydrogen storage and the liquid hydrogen storage modes on a container and the environment are extremely high, compared with the solid hydrogen storage mode, which is a mode easy to realize.
Fullerene is a hollow molecule completely composed of carbon elements, and has a spherical, ellipsoidal, columnar or tubular shape. Fullerenes have a structure similar to graphite, in which a large number of six-membered rings made up of carbon atoms are contained, in addition to five-membered rings and seven-membered rings. The carbon atoms of the fullerene surface are in an unsaturated state, which is capable of reacting through hydrogenation to form the corresponding hydride. Because the fullerene is in a closed hollow structure, only the outer side surface of the fullerene can be utilized in the hydrogenation process, and the space inside the fullerene is difficult to fully utilize, so that the hydrogen storage capacity of the fullerene is low. Some conventional techniques etch the fullerene to expose the interior space of the fullerene and further deposit the hydrogen storage metal material. The etching method can expose the space inside the fullerene, but the etching method also brings about the problem of overlarge gaps of the fullerene, so that the surface area and the volume of the fullerene are excessively reduced, and the problem of low hydrogen storage amount still exists.
Disclosure of Invention
In view of the above, it is desirable to provide a method for producing a fullerene hydrogen storage material capable of further increasing the hydrogen storage amount of a fullerene.
According to some embodiments of the present invention, there is provided a method for preparing a fullerene hydrogen storage material, comprising the steps of:
depositing a layer of fullerene material on a substrate;
placing the substrate deposited with the fullerene material layer in a sputtering chamber with a metal target, sputtering the metal target to form metal ions, and enabling the metal ions to bombard the fullerene material layer; the method comprises the steps of,
and depositing lithium metal on the surface of the fullerene material layer so as to dope lithium atoms in the fullerene material layer.
In some embodiments of the invention, before depositing lithium metal on the surface of the fullerene material layer, the method further comprises: and reaming the fullerene material layer based on the defects formed on the surface of the fullerene material layer.
In some embodiments of the invention, the reaming process is performed by irradiating the layer of fullerenic material with a laser.
In some embodiments of the present invention, in the step of irradiating the fullerene material layer with laser light, a pulse width of the laser light is controlled to be less than 1ns, and an average power of the laser light is controlled to be 10w to 50w.
In some embodiments of the present invention, in the step of sputtering the metal target, a high-energy pulse magnetron sputtering method is used to ionize a working gas, and sputtering treatment is performed on the metal target by the ionized working gas.
In some embodiments of the invention, the peak power is controlled to be 10 during ionization of the working gas by high energy pulse magnetron sputtering 5 W~10 7 W。
In some embodiments of the invention, the pulse width is controlled to be 10-100 mu s in the process of ionizing the working gas by adopting a high-energy pulse magnetron sputtering method.
In some embodiments of the present invention, the substrate is disposed on a cooling roller during the sputtering process of the metal target by the ionized working gas, and a negative voltage with a voltage value of-100V to-500V is applied to the cooling roller.
In some embodiments of the present invention, in the step of depositing lithium metal on the surface of the fullerene material layer, the mass ratio of the deposited lithium metal to the fullerene material layer is 1 (3-10).
In some embodiments of the invention, the metal target is a germanium target.
Further, the invention also provides a fullerene hydrogen storage membrane, which comprises a base membrane and the fullerene hydrogen storage material prepared by the preparation method in the embodiment, wherein the fullerene hydrogen storage material is arranged on the base membrane.
The preparation method of the fullerene hydrogen storage material provided by the invention comprises the steps of depositing a fullerene material layer on a substrate, bombarding the fullerene material layer by adopting metal ions, and depositing lithium metal on the surface of the fullerene material layer to dope lithium atoms. The metal ions bombard the fullerene material layer, so that partial carbon atoms on the surface of the fullerene can be removed, defects can be formed on the surface of the fullerene, and further lithium metal can be doped on the surface of the fullerene and the inside of the fullerene, and lithium doped fullerene can be formed. The doping of lithium atoms can effectively enhance the binding capacity of the surface of the fullerene to hydrogen molecules, so that both the outer surface and the inner surface of the fullerene can be used for binding and storing hydrogen. In addition, the preparation method mainly forms carbon atom vacancy defects on the surface of the fullerene without affecting the internal volume of the fullerene, so that the resistance of hydrogen atom inclusion into a fullerene cage can be reduced, the hydrogen storage space of the fullerene cage is more fully utilized, and the hydrogen storage amount of the prepared fullerene hydrogen storage material is obviously improved.
Drawings
Fig. 1 is a schematic step diagram of a method for preparing a fullerene-based hydrogen storage material according to the present invention.
Detailed Description
To facilitate an understanding of this document, a more complete description of this document will follow. Preferred embodiments herein are presented. This may, however, be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description presented herein is for the purpose of describing particular embodiments only and is not intended to be limiting.
It will be understood that when an element or layer is referred to as being "on," "adjacent," "connected to," or "coupled to" another element or layer, it can be directly on, adjacent, connected, or coupled to the other element or layer, or intervening elements or layers may also be present. In contrast, when an element is referred to as being "directly on," "directly adjacent to," "directly connected to," or "directly coupled to" another element or layer, there are no intervening elements or layers present. It will be understood that, although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section.
Spatially relative terms, such as "under", "below", "beneath", "under", "above", "over" and the like, may be used herein for ease of description to describe one element or feature's relationship to another element or feature. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use and operation. For example, if the device in the figures is turned over, elements or features described as "under" or "beneath" other elements would then be oriented "on" the other elements or features. Thus, the exemplary terms "below" and "under" may include both an upper and a lower orientation. The device may be otherwise oriented (e.g., rotated 90 degrees or other orientations) and the spatial descriptors used herein interpreted accordingly.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. As used herein, the term "and/or" includes any and all combinations of the associated listed items.
Conventional techniques etch the fullerene to expose the interior space of the fullerene and further deposit the hydrogen storage metal material. The etching method can expose the space inside the fullerene, but the structure of the fullerene can be seriously damaged by the etching method. For example, plasma etching can result in at most half of the carbon atoms in the fullerene being removed, such that the fullerene is transformed from a cage structure to a hemispherical or bowl structure. This can expose the internal space of the fullerene, but also results in a significant reduction in the internal space of the fullerene. And the subsequently deposited hydrogen storage metal material completely covers the surface of the fullerene, and the hydrogen storage metal material rather than the fullerene mainly plays a role in hydrogen storage at the moment, so that the structure of the fullerene is difficult to fully utilize.
The invention provides a preparation method of a fullerene hydrogen storage material, which comprises the following steps: a layer of fullerene material is deposited on a substrate. The substrate with the layer of fullerene material deposited is placed in a sputtering chamber with a metal target, and the metal target is sputtered to form metal ions, which bombard the layer of fullerene material. And depositing lithium metal on the surface of the fullerene material layer to dope lithium atoms in the fullerene material layer.
The preparation method of the fullerene hydrogen storage material provided by the invention comprises the steps of depositing a fullerene material layer on a substrate, bombarding the fullerene material layer by adopting metal ions, and depositing lithium metal on the surface of the fullerene material layer to dope lithium atoms. The metal ions bombard the fullerene material layer, so that partial carbon atoms on the surface of the fullerene can be removed, defects can be formed on the surface of the fullerene, and further lithium metal can be doped on the surface of the fullerene and the inside of the fullerene, and lithium doped fullerene can be formed. The doping of lithium atoms can effectively enhance the binding capacity of the surface of the fullerene to hydrogen molecules, so that both the outer surface and the inner surface of the fullerene can be used for binding and storing hydrogen. In addition, the preparation method mainly forms carbon atom vacancy defects on the surface of the fullerene without affecting the internal volume of the fullerene, so that the resistance of hydrogen atom inclusion into a fullerene cage can be reduced, the hydrogen storage space of the fullerene cage is more fully utilized, and the hydrogen storage amount of the prepared fullerene hydrogen storage material is obviously improved.
Fig. 1 is a schematic diagram of a preparation method of a fullerene hydrogen storage material according to the present invention, and referring to fig. 1, the preparation method includes steps S1 to S3.
Step S1, depositing a layer of fullerene material on a substrate.
It will be appreciated that during deposition of the layer of fullerenic material, the substrate acts as a growth base for the layer of fullerenic material, and the bonding force between the layer of fullerenic material and the substrate is dependent on the type of substrate. In some examples of this embodiment, the material of the substrate may include a metal material on which the layer of fullerene material is deposited and in contact with the metal material to ensure a greater bonding force between the layer of fullerene material and the substrate.
In some examples of this embodiment, the substrate may include a base film and a metal material layer disposed in a stacked arrangement, the metal material layer being disposed on the base film.
In some examples of this embodiment, the material of the base film may be a flexible material, for example, the material of the base film may be selected from a polymeric material. Further, the material of the base film is selected from one or more of polyethylene, polypropylene, polyethylene terephthalate and polyimide. In this example, polyethylene terephthalate was used as the base film.
In some examples of this embodiment, the thickness of the base film may be 1 μm to 10 μm. For example, the thickness of the base film may be 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 8 μm, 10 μm, or the thickness of the base film may be in a range between any two of the above thicknesses. Wherein, the thickness of the base film can be set to be lower so as to reduce the mass ratio of the base film as much as possible, but when the thickness of the base film is lower than 1 mu m, the base film is easy to break in the preparation process, thereby influencing the preparation yield of the fullerene hydrogen storage material.
In some examples of this embodiment, the desired metal material layer may be deposited on the base film prior to depositing the fullerene material layer on the substrate to form a substrate for carrying the fullerene material layer. The metal material layer is prepared in a deposition mode, so that a flat and thin metal material layer can be obtained, oxidation of the metal material layer can be avoided, and a subsequently prepared fullerene material layer can be stably attached to a substrate. Further, the manner of depositing the metal material layer may be sputtering.
In some examples of this embodiment, the sputtered metal material layer may have a thickness of 20nm to 500nm. For example, the thickness of the metal material layer may be 20nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, or the thickness of the metal material layer may be in a range between any two of the above thicknesses. Wherein the thickness of the sputtered metal material layer may be suitably thin.
In this embodiment, the material of the metal material layer may be copper.
In some examples of this embodiment, a layer of fullerene material may be deposited on the substrate by means of sputtering. Specifically, a substrate may be disposed in a sputtering chamber, and a target containing a fullerene material may be used as the target, and the fullerene material in the target may be sputtered and deposited on the substrate.
In some examples of this embodiment, the fullerene material layer deposited on the substrate has a thickness of 5nm to 20nm. For example, the thickness of the deposited layer of fullerenic material may be 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 15nm, 18nm, 20nm, or the thickness of the deposited layer of fullerenic material may range between any two of the above thicknesses. It will be appreciated that the thickness of the layer of fullerenic material may be controlled by controlling the deposition time and other conditions. When the thickness of the fullerene material layer is 5-20 nm, more defects can be generated on the surface of the fullerene material while the uniformity and the structural stability of the whole fullerene material layer are ensured. Because metal ions can only act on partial carbon atoms positioned on the surface layer in the bombardment process, if the thickness of the fullerene material layer is higher than 20nm, a large amount of fullerene materials positioned on the bottom layer are difficult to generate defects, so that the hydrogen storage capacity of the fullerene hydrogen storage material is obviously lower.
In some examples of this embodiment, the layer of fullerenic material may be deposited by sputtering. In the step of sputtering the fullerene material layer, the sputtering power can be controlled to be 100-300W. For example, the sputtering power may be controlled to be 100W, 120W, 150W, 180W, 200W, 220W, 250W, 280W, 300W, or the sputtering power may be controlled to be within a range between any two of the above sputtering powers. The sputtering power is controlled to be 100W-300W, so that the fullerene material layer can be sputtered uniformly.
In some examples of this embodiment, the sputtering time may be controlled to be 10min to 30min in the step of depositing the fullerene material layer. For example, the sputtering time may be controlled to be 10min, 12min, 15min, 18min, 20min, 22min, 25min, 28min, 30min, or the sputtering time may be controlled to be within a range between any two of the above.
It will be appreciated that a layer of fullerene material can be deposited on the substrate by step S1.
And S2, placing the substrate deposited with the fullerene material layer in a sputtering chamber with a metal target, sputtering the metal target to form metal ions, and enabling the metal ions to bombard the fullerene material layer.
In this embodiment, the sputtering chamber typically contains a working gas, such as argon. In the sputtering process, argon is ionized and bombards the metal target for sputtering, and after the metal target is sputtered to form metal ions, the metal target collides carbon atoms in the fullerene at a high speed, so that the carbon atoms are separated from the fullerene, and accordingly, vacancy defects are formed in situ.
Conventional dc sputtering processes or pulsed sputtering processes can generally only reach 10 3 The maximum sputtering power of W magnitude is relatively low in probability that metal ions generated under the sputtering power bombard carbon atoms on the surface of the fullerene material and generate lattice defects, but more metal ions are deposited on the surface of the fullerene material. In some examples of this embodiment, in the step of sputtering the metal target, high-energy pulse magnetron sputtering (High Power Impulse Magnetron Sputtering, hiPIMS for short) is used to ionize the working gas, and the metal target is subjected to sputtering treatment by the ionized working gas. The high-energy pulse magnetron sputtering is a sputtering mode capable of outputting extremely high power instantaneously, and the peak power can reach 10 5 W is more than or equal to W. The high-energy pulse magnetron sputtering mode is adopted to remarkably improve the kinetic energy of sputtered metal ions, and carbon atoms are easier to separate from fullerene when the metal ions bombard the fullerene material, so that the vacancy defect on the surface of the fullerene material is remarkably increased while the deposition of the metal ions is reduced, and lithium atoms are convenient to further dope in the subsequent steps.
In some examples of this embodiment, the peak power of a single pulse may be controlled to be 5×10 during ionization of the working gas by high energy pulse magnetron sputtering 5 W~1×10 7 W. For example, the peak power of a single pulse can be controlled to be 5×10 5 W、6×10 5 W、7×10 5 W、8×10 5 W、9×10 5 W、1×10 6 W、2×10 6 W、3×10 6 W、5×10 6 W、7×10 6 W、1×10 7 W, or alternatively, the peak power of a single pulse may be controlled to be between any two of the peak powers.
In some examples of this embodiment, in the step of ionizing the working gas using the high-energy pulse magnetron sputtering method, an inert gas may be selected as the working gas. For example, the inert gas may be at least one of helium, neon, and argon.
In some examples of this embodiment, the pulse width may be controlled to be 10 μs to 100 μs in the step of ionizing the working gas using the high-energy pulse magnetron sputtering method. Where pulse width refers to the duration of the peak power in a single pulse. For example, the pulse width may be controlled to be 10 μs, 20 μs, 30 μs, 40 μs, 50 μs, 60 μs, 70 μs, 80 μs, 100 μs, or the range between any two of the above times may be controlled.
In some examples of this embodiment, in the step of bombarding the fullerene material layer with metal ions, the pulse frequency may be controlled to be 100hz to 1000hz, and the total time of bombarding the fullerene material layer may be controlled to be 1s to 10s. For example, the total time of bombardment of the fullerene material layer may be controlled to be 1s, 2s, 3s, 4s, 5s, 6s, 7s, 8s, 9s, or the total time of bombardment of the fullerene material layer may be controlled to be in a range between any two of the above. It will be appreciated that by controlling the pulse frequency and controlling the total time of bombardment, the amount of metal ions deposited can be reduced while creating sufficient defects on the surface of the layer of fullerenic material.
In some examples of this embodiment, in the step of bombarding the layer of fullerenic material with metal ions, the substrate may be disposed on a chill roll and a negative voltage applied to the chill roll. It will be appreciated that the metal ions lose electrons and carry a positive charge after ionization and that applying a negative voltage to the chill roll can direct the metal ions toward the substrate on the chill roll and bombard the layer of fullerenic material. And, applying a negative voltage to the cooling roller can further increase the kinetic energy of the metal ions.
In some examples of this embodiment, in the step of ionizing the working gas, the voltage value applied across the cooling roller may be-100V-500V. For example, the voltage value applied to the cooling roller may be-100V, -150V, -200V, -250V, -300V, -350V, -400V, -450V, -500V, or the voltage value applied may be between any two of the above voltage values.
It is understood that after the carbon atoms on the surface of the fullerene material layer are bombarded and create vacancy defects, the carbon atoms around the vacancy defects may have unstable dangling bonds, and may easily re-bond with other carbon atoms or hetero atoms during subsequent processing, thereby causing the defects to disappear. In some examples of this embodiment, after bombarding the layer of fullerene material with metal ions, further comprising: and reaming the fullerene material layer based on defects formed on the surface of the fullerene material layer. The purpose of the reaming process is to further remove carbon atoms around the vacancy defects, which not only enables the original defects to further form holes with larger sizes, but also enables the carbon atoms around the defects to be more stable, thereby avoiding the problem of defect repair.
It will be appreciated that the reaming process may be performed by etching with an oxidizing agent. Wherein the oxidizing agent may include one or more of potassium permanganate, concentrated sulfuric acid and nitric acid, and carbon atoms around the defect can be removed by using the oxidizing agent because atoms at the defect have high reactivity. Although the oxidant can play a good role in reaming, the method not only can enable oxygen-containing groups to be generated on the surface of the fullerene, but also needs to transfer the fullerene material layer from the sputtering chamber to the oxidant, so that the production efficiency is affected.
In some examples of this embodiment, the reaming process may be performed by irradiating the layer of fullerenic material with a laser. The laser can provide extremely high energy instantly, and when the fullerene material layer is irradiated by the laser, carbon atoms in an unstable state around the defect are easily further excited to form plasma, so that the carbon atoms are separated from the surface of the fullerene material, and the aim of reaming is fulfilled. In this embodiment, the step of laser irradiation may be performed directly in the sputtering chamber.
In some examples of this embodiment, in the step of irradiating the fullerene material layer with the laser light, a pulse width of the laser light may be controlled to be 1ns or less. The pulse duration of the laser with a pulse width below 1ns is close to the thermal diffusion time, and when the laser acts on unstable carbon atoms, the energy is insufficient to diffuse in the form of thermal energy, resulting in ionization and removal of the irradiated carbon atoms in the form of plasma. It will be appreciated that picosecond lasers may be employed to provide lasers having pulse widths below 1 ns.
In some examples of this embodiment, in the step of irradiating the fullerene material layer with the laser, a pulse width of the laser may be 1ps to 100ps. For example, the pulse width of the laser may be 1ps, 5ps, 10ps, 20ps, 30ps, 40ps, 50ps, 60ps, 80ps, 100ps, or the pulse width of the laser may be in a range between any two of the above.
In some examples of this embodiment, in the step of irradiating the fullerene material layer with the laser light, the average power of the laser light may be 10w to 50w. For example, the average power of the laser may be 10W, 15W, 20W, 25W, 30W, 35W, 40W, 45W, or 50W, or the average power of the laser may be controlled to be between any two of the above powers.
And S3, depositing lithium metal on the surface of the fullerene material to dope lithium atoms in the fullerene material.
In the prior art, a hydrogen storage metal material with a hydrogen storage function is deposited on the fullerene, but the fullerene is mainly used as a matrix material for bearing the hydrogen storage metal material, and finally the hydrogen storage metal material is still actually used as a main hydrogen storage function instead of the fullerene.
In this embodiment, the effect of doping lithium atoms in the fullerene material is to increase the hydrogen storage capacity of the fullerene material layer. The lithium metal is not a hydrogen storage metal material and does not have a hydrogen storage function, but when lithium atoms are doped in the fullerene material to form a lithium-carbon composite material, the hydrogen storage amount can be remarkably improved compared with an undoped fullerene material. By forming defects on the surface of the fullerene material and doping lithium atoms on the surface and inside of the fullerene, the adsorption capacity of the surface and inside of the fullerene on hydrogen molecules can be effectively increased, and the hydrogen storage capacity of the fullerene is obviously improved. In addition, the lithium atoms can also eliminate the dangling bonds on the surface of the fullerene material, so that the gaps on the surface of the fullerene material can be further ensured to exist stably.
In some examples of this embodiment, the manner in which lithium metal is deposited on the surface of the fullerene material may be physical vapor deposition. Further, lithium metal may be deposited on the surface of the fullerene material by sputtering.
In some examples of this embodiment, in the step of depositing lithium metal on the surface of the fullerene material layer, the mass ratio of the deposited lithium metal to the fullerene material layer is set to 1 (3-10). For example, the mass ratio of lithium metal to the fullerene material layer may be 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, or the mass ratio of lithium metal to the fullerene material layer may be between any two of the above mass ratios. If the mass ratio of lithium metal to the fullerene material layer is higher than 1:3, excessive lithium atoms are deposited in the form of lithium metal, which not only does not contribute to the hydrogen storage capacity, but also causes a decrease in the hydrogen storage capacity due to shielding of the fullerene material layer. If the mass ratio of the lithium metal to the fullerene material layer is lower than 1:10, the doping amount of the lithium metal is lower, and the improvement range of the hydrogen storage amount of the fullerene material layer is smaller.
In some examples of this embodiment, after depositing a layer of the fullerene-containing hydrogen material and performing lithium doping as in step S1 to step S3, the deposition of the fullerene material layer, the bombardment of the fullerene material layer and the doping of lithium atoms may be repeated a plurality of times to increase the number of layers of the lithium-doped fullerene material layer, thereby increasing the overall hydrogen storage capacity of the fullerene-containing hydrogen material.
In some examples of this embodiment, after repeating depositing the fullerene material layer, bombarding the fullerene material layer, and doping the lithium atoms a number of times, the total thickness of all the fullerene material layers may be 1 μm to 10 μm. If the total thickness of the whole fullerene material layer is less than 1 mu m, the whole hydrogen storage amount is relatively small, and the actual hydrogen storage amount is relatively limited. If the total thickness of the whole fullerene material layer is higher than 10 μm, the fullerene material layer at the bottom is not easy to absorb hydrogen, so that the utilization rate of the fullerene material layer is low.
It will be appreciated that the total thickness of the layer of fullerenic material is related to the thickness of the single layer of fullerenic material and the number of times the layer of fullerenic material is deposited. In some examples of this embodiment, the number of times the layer of fullerene material is deposited may be 100 times to 1000 times.
In some examples of this embodiment, in the step of depositing the layer of fullerene material, the layer of fullerene material may be deposited on both opposite side surfaces of the substrate. In the step of causing metal ions to bombard the layer of fullerenic material, two metal targets may be employed to bombard the layer of fullerenic material on both sides of the substrate simultaneously. In the depositing lithium metal step, lithium metal may be deposited on both opposite side surfaces of the substrate.
Through the steps S1-S3, the corresponding fullerene hydrogen storage material can be prepared. The fullerene hydrogen storage material comprises a fullerene material layer, wherein the fullerene material in the fullerene material layer has carbon atom vacancy defects, and the fullerene material layer is doped with lithium atoms.
Further, the application also provides a fullerene hydrogen storage membrane, which comprises a base membrane and the fullerene hydrogen storage material prepared in the embodiment, wherein the fullerene hydrogen storage material is arranged on the base membrane.
In some examples of this embodiment, the material of the base film may be a flexible material, for example, the material of the base film may be selected from a polymeric material. Further, the material of the base film is selected from one or more of polyethylene, polypropylene, polyethylene terephthalate and polyimide. In this example, polyethylene terephthalate was used as the base film.
Further, the fullerene hydrogen storage film may further include a metal material layer disposed on the base film. The material of the metal material layer may be copper.
It is understood that the base film and the metallic material layer constitute a substrate to which the fullerene hydrogen storage material can be attached.
The following examples are also provided to illustrate specific implementations of the methods of preparing the fullerene-containing hydrogen material. The advantages of the present invention will also become more apparent from the description of the examples and comparative examples.
Example 1
Polyethylene terephthalate with a thickness of 2 μm was provided as a base film, which was put on a transfer roller, transferred into a sputtering chamber containing a copper target, and a copper metal layer with a thickness of 200nm was sputtered as a substrate.
Transferring the substrate into a sputtering chamber containing a fullerene target material, sputtering a fullerene material layer with the thickness of 10nm, transferring into a high-energy pulse magnetron sputtering chamber, and setting the peak power to be 10 6 And sputtering the germanium target material with the pulse width of 20 mu s, and stopping after continuously bombarding the fullerene material layer for 5 s. Then picosecond laser with pulse width of 2.1ps is adopted to scan the fullerene material layer for reaming treatment, and then the fullerene material layer is transferred into a sputtering chamber containing a lithium metal target material to sputter lithium metal, and controlThe sputtering time was set such that the ratio of the mass of lithium metal to the mass of the fullerene target was about 1:5.
The above steps are repeated 100 times to form the fullerene-like hydrogen storage material. Through tests, the maximum hydrogen storage capacity of the fullerene hydrogen storage material is 5.26 weight percent, and the hydrogen storage effect is good.
Comparative example 1
Polyethylene terephthalate with a thickness of 2 μm was provided as a base film, which was put on a transfer roller, transferred into a sputtering chamber containing a copper target, and a copper metal layer with a thickness of 200nm was sputtered as a substrate.
The substrate was transferred to a sputtering chamber containing a fullerene target, and a fullerene material layer with a thickness of 1000nm was sputtered as a fullerene hydrogen storage material. The maximum hydrogen storage capacity of the fullerene hydrogen storage material was tested to be 1.32wt%.
Comparative example 2
Polyethylene terephthalate with a thickness of 2 μm was provided as a base film, which was put on a transfer roller, transferred into a sputtering chamber containing a copper target, and a copper metal layer with a thickness of 200nm was sputtered as a substrate.
Transferring the substrate into a sputtering chamber containing a fullerene target material, sputtering a fullerene material layer with the thickness of 10nm, transferring into a high-energy pulse magnetron sputtering chamber, and setting the peak power to be 10 6 And sputtering the germanium target material with the pulse width of 20 mu s, and stopping after continuously bombarding the fullerene material layer for 5 s. The fullerene material layer was then scanned with a picosecond laser having a pulse width of 2.1ps to perform a reaming process.
The above steps are repeated 100 times to form the fullerene-like hydrogen storage material. The maximum hydrogen storage capacity of the fullerene hydrogen storage material was tested to be 2.12wt%.
Comparative example 3
Polyethylene terephthalate with a thickness of 2 μm was provided as a base film, which was put on a transfer roller, transferred into a sputtering chamber containing a copper target, and a copper metal layer with a thickness of 200nm was sputtered as a substrate.
And conveying the substrate into a sputtering chamber containing a fullerene target, sputtering a fullerene material layer with the thickness of 10nm, transferring the substrate into the sputtering chamber containing a lithium metal target, sputtering the lithium metal, and controlling the sputtering time so that the ratio of the mass of the lithium metal to the mass of the fullerene target is about 1:5.
The above steps are repeated 100 times to form the fullerene-like hydrogen storage material. The maximum hydrogen storage capacity of the fullerene hydrogen storage material was tested to be 1.53wt%.
In comparison with comparative example 1, comparative example 2 bombarded the fullerene material layer only by sputtering a metal target to generate defects, which removed part of carbon atoms on the fullerene surface but did not undergo lithium atom doping, so that the improvement effect on the hydrogen storage capacity was limited. Comparative example 3 lithium metal was directly deposited on the surface of the fullerene material layer, and lithium atoms were only doped in a small amount of fullerene at the surface layer, and the improvement effect on the hydrogen storage capacity was more limited.
In contrast to comparative examples 1-3, example 1 bombards the fullerene material layer with a sputtered metal target to create defects, and then sputters lithium metal to dope lithium atoms in the fullerene material layer. The metal ions bombard the fullerene material layer, so that partial carbon atoms on the surface of the fullerene can be removed, defects can be formed on the surface of the fullerene, lithium atoms can be fully doped on the surface of the fullerene and the inside of the fullerene, and the doping effect is remarkably improved. The doping of lithium atoms can effectively enhance the binding capacity of the surface of the fullerene to hydrogen molecules, so that both the outer surface and the inner surface of the fullerene can be used for binding and storing hydrogen. In addition, the preparation method mainly forms carbon atom vacancy defects on the surface of the fullerene without affecting the surface area and volume of the fullerene, and can fully utilize the hydrogen storage space in the cage of the fullerene. In combination, the hydrogen storage capacity of the fullerene hydrogen storage material can be significantly improved.
Note that the above embodiments are for illustrative purposes only and are not meant to be limiting herein.
It should be understood that the steps are not strictly limited to the order of execution unless explicitly recited herein, and the steps may be executed in other orders. Moreover, at least a portion of the steps in the preparation process may include a plurality of sub-steps or stages, which are not necessarily performed at the same time, may be performed at different times, may not necessarily be performed sequentially, and may be performed alternately or alternately with at least a portion of the sub-steps or stages of other steps or other steps.
In this specification, each embodiment is described in a progressive manner, and each embodiment is mainly described by differences from other embodiments, and identical and similar parts between the embodiments are all enough to be referred to each other.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
Claims (10)
1. The preparation method of the fullerene hydrogen storage material is characterized by comprising the following steps of:
depositing a layer of fullerene material on a substrate;
placing the substrate deposited with the fullerene material layer in a sputtering chamber with a metal target, sputtering the metal target to form metal ions, and enabling the metal ions to bombard the fullerene material layer; the method comprises the steps of,
and depositing lithium metal on the surface of the fullerene material layer so as to dope lithium atoms in the fullerene material layer.
2. The method for preparing a fullerene hydrogen storage material according to claim 1, further comprising, before depositing lithium metal on the surface of the fullerene material layer: and reaming the fullerene material layer based on the defects formed on the surface of the fullerene material layer.
3. The method for producing a fullerene hydrogen storage material according to claim 2, wherein the pore expansion treatment is performed by irradiating the fullerene material layer with laser light.
4. The method of producing a hydrogen storage material of fullerene according to claim 3, wherein in the step of irradiating the fullerene material layer with laser light, a pulse width of the laser light is controlled to be 1ns or less and an average power of the laser light is controlled to be 10w to 50w.
5. The method for producing a hydrogen storage material for fullerenes according to any one of claims 1 to 4, wherein in the step of sputtering the metal target, a high-energy pulse magnetron sputtering method is used to ionize a working gas, and the metal target is subjected to sputtering treatment by the ionized working gas.
6. The method according to claim 5, wherein the peak power is controlled to be 10 during ionization of the working gas by high-energy pulse magnetron sputtering 5 W~10 7 W is a metal; and/or the number of the groups of groups,
the pulse width is controlled to be 10 mu s-100 mu s.
7. The method according to claim 5, wherein the substrate is placed on a cooling roller and a negative voltage having a voltage value of-100V to-500V is applied to the cooling roller during the sputtering treatment of the metal target by the ionized working gas.
8. The method for producing a hydrogen storage material for fullerenes according to any one of claims 1 to 4 and 6 to 7, wherein in the step of depositing lithium metal on the surface of the fullerene material layer, the mass ratio of the deposited lithium metal to the fullerene material layer is 1 (3 to 10).
9. The method for preparing a fullerene hydrogen storage material according to any one of claims 1 to 4 and 6 to 7, wherein the metal target is a germanium target.
10. The fullerene hydrogen storage membrane is characterized by comprising a base membrane and the fullerene hydrogen storage material prepared by the preparation method according to any one of claims 1-9, wherein the fullerene hydrogen storage material is arranged on the base membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410212729.9A CN117776102B (en) | 2024-02-27 | 2024-02-27 | Preparation method of fullerene hydrogen storage material and fullerene hydrogen storage film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410212729.9A CN117776102B (en) | 2024-02-27 | 2024-02-27 | Preparation method of fullerene hydrogen storage material and fullerene hydrogen storage film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117776102A true CN117776102A (en) | 2024-03-29 |
| CN117776102B CN117776102B (en) | 2024-05-07 |
Family
ID=90380136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410212729.9A Active CN117776102B (en) | 2024-02-27 | 2024-02-27 | Preparation method of fullerene hydrogen storage material and fullerene hydrogen storage film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117776102B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557702A (en) * | 2004-02-05 | 2004-12-29 | 武汉理工大学 | Fullerene hydrogen storage material etched by microwave plasma and method for preparing the same |
| JP2005336118A (en) * | 2004-05-28 | 2005-12-08 | Ideal Star Inc | Method for producing hydrogenated fullerene and apparatus therefor |
| JP2006016285A (en) * | 2004-07-05 | 2006-01-19 | Ideal Star Inc | Method of manufacturing fullerene with openings and method of manufacturing inclusion fullerene |
| CN101469402A (en) * | 2007-12-25 | 2009-07-01 | 中国科学院兰州化学物理研究所 | Preparation of fullerene-like carbon film |
| TW201412638A (en) * | 2012-09-24 | 2014-04-01 | Nat Univ Chung Hsing | Hydrogen storage material and its manufacturing method |
| CN113233442A (en) * | 2021-06-18 | 2021-08-10 | 中国人民解放军国防科技大学 | Single-atom embedded fullerene and in-situ synthesis method thereof |
-
2024
- 2024-02-27 CN CN202410212729.9A patent/CN117776102B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557702A (en) * | 2004-02-05 | 2004-12-29 | 武汉理工大学 | Fullerene hydrogen storage material etched by microwave plasma and method for preparing the same |
| JP2005336118A (en) * | 2004-05-28 | 2005-12-08 | Ideal Star Inc | Method for producing hydrogenated fullerene and apparatus therefor |
| JP2006016285A (en) * | 2004-07-05 | 2006-01-19 | Ideal Star Inc | Method of manufacturing fullerene with openings and method of manufacturing inclusion fullerene |
| CN101469402A (en) * | 2007-12-25 | 2009-07-01 | 中国科学院兰州化学物理研究所 | Preparation of fullerene-like carbon film |
| TW201412638A (en) * | 2012-09-24 | 2014-04-01 | Nat Univ Chung Hsing | Hydrogen storage material and its manufacturing method |
| CN113233442A (en) * | 2021-06-18 | 2021-08-10 | 中国人民解放军国防科技大学 | Single-atom embedded fullerene and in-situ synthesis method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117776102B (en) | 2024-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5690714B2 (en) | Thin film production method | |
| KR100878718B1 (en) | Silicon thin film anode for lithium secondary battery, preparatuon mehode thereof and lithium secondary battery therewith | |
| JP4705091B2 (en) | Method for growing carbon nanotube arrays | |
| JP2001515965A (en) | Thin film deposition method | |
| JP2009283275A (en) | Current collecting foil for secondary battery, and method for manufacturing thereof | |
| Morintale et al. | Thin films development by pulsed laser-assisted deposition | |
| WO2011007412A1 (en) | Method for producing positive electrode active material layer | |
| Li et al. | Pulsed laser 3D-micro/nanostructuring of materials for electrochemical energy storage and conversion | |
| CN117776102B (en) | Preparation method of fullerene hydrogen storage material and fullerene hydrogen storage film | |
| Huang et al. | Crystallization control of sputtered Ta 2 O 5 thin films by substrate bias | |
| JP2005293899A (en) | Manufacturing method of electrode for lithium secondary battery | |
| CN110783547A (en) | Preparation method of lithium-gold-carbon nanotube composite foil | |
| JPH08287901A (en) | Manufacture of positive electrode for lithium secondary battery | |
| JP2007123096A (en) | Method of manufacturing electrode for lithium secondary battery | |
| JP2003159700A (en) | Method of processing carbon nanotubes | |
| CN109267016A (en) | Pulse laser deposits MoS2The method of film | |
| JP2011142034A (en) | Solid electrolyte membrane and method of manufacturing the same, and solid electrolyte battery | |
| US9748569B2 (en) | Porous, thin film electrodes for lithium-ion batteries | |
| JP2007184205A (en) | Method of manufacturing electrode for lithium secondary battery | |
| CN117712389B (en) | Method for producing porous current collector, apparatus for producing porous current collector, electrode, and secondary battery | |
| KR100838167B1 (en) | Manufacturing Method of Back Contacts for CIGS Solar Cell | |
| KR101836386B1 (en) | Method for preparing large-area graphene sheet by using fullerene as precursor | |
| JPH0931629A (en) | Production of aluminum porous body | |
| Bhattacharyya et al. | Morphological evolution of films composed of energetic and size-selected silver nanocluster ions | |
| JP7477898B2 (en) | Cathode foil for electrolytic capacitor, and electrolytic 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 |