Electrode of energy storage component and manufacturing method thereof

Abstract

The manufacturing method of the electrode of the energy storage assembly comprises the following steps: providing a substrate in microwave plasma equipment; introducing a carrier gas and a carbon precursor gas into the microwave plasma equipment; forming a plurality of layers of graphene walls on the substrate by a microwave plasma chemical vapor deposition method; immersing the substrate containing the multiple layers of graphene walls into an electrolyte solution to perform electrochemical activation treatment, so that ions in the electrolyte solution are embedded between the adjacent graphene walls; the volume ratio of the carrier gas to the carbon precursor gas is (1: 10)-(10: 1). The invention further provides an electrode of the energy storage assembly.

Description

Technical Field

[0001] The present disclosure relates to an energy storage assembly and a method for manufacturing the same. Background Art

[0002] Electric double-layer capacitors (also called supercapacitors; Electrostatic double-layer capacitor; EDLC) have the characteristics of short charging time, long cycle life, good temperature resistance and green environmental protection. Therefore, they are widely used in electronics, industry, national defense and other related fields; however, the two major factors of low energy density and high energy storage cost of electric double-layer capacitors limit the scope of their application.

[0003] In response to this, a hybrid supercapacitor has recently been developed that combines the characteristics of a double-layer capacitor and a lithium-ion battery. Specifically, the hybrid supercapacitor includes a positive electrode of a double-layer capacitor and a negative electrode of a lithium-ion battery, and can have the characteristics of both the high power density of a double-layer capacitor and the high energy density of a lithium-ion battery.

[0004] In existing double-layer capacitors or hybrid supercapacitors, carbon composite materials such as graphene are used as positive electrodes. In order to increase the energy density of energy storage components, multiple processes are performed to improve the physical and chemical properties of graphene; however, the above-mentioned processes are complicated and require a lot of process time and process costs. Summary of the invention

[0005] The electrode manufacturing method of the energy storage component according to one embodiment of the present disclosure includes the following steps: providing a substrate in a microwave plasma device; introducing a carrier gas and a carbon precursor gas into the microwave plasma device; forming a multilayer graphene wall on the substrate by microwave plasma chemical vapor deposition; immersing the substrate containing the multilayer graphene wall in an electrolyte solution for electrochemical activation treatment so that ions in the electrolyte solution are embedded between adjacent graphene walls; the volume ratio of the carrier gas to the carbon precursor gas is 1:10-10:1.

[0006] Another embodiment of the present disclosure provides an electrode of an energy storage assembly.

[0007] The electrode of the energy storage assembly of one embodiment of the present disclosure is formed by using the above-mentioned method for manufacturing the electrode of the energy storage assembly, and includes a substrate and graphene. The graphene is disposed on the substrate and includes multiple layers of graphene walls. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1A The present invention is a flow chart of a method for manufacturing an electrode of an energy storage assembly according to an embodiment of the present disclosure.

[0009] Figure 1B as well as Figure 1Cfor Figure 1A Scanning electron microscope (SEM) image of graphene formed by microwave plasma chemical vapor deposition.

[0010] Figure 2 Raman spectra of graphene of Examples 1 to 3 of the present disclosure are shown.

[0011] Figure 3A Raman spectra of graphene of Examples 12 to 14 of the present disclosure are shown.

[0012] Figure 3B as well as Figure 3C X-ray photoelectron spectroscopy (XPS) spectra of graphene of Examples 12 to 14 of the present disclosure are shown.

[0013] Figure 4A A charge and discharge curve diagram of electrochemical activation of a titanium sheet with graphene grown thereon according to Example 3 of the present disclosure using a constant current method is shown.

[0014] Figure 4B The charge and discharge curves of the titanium sheet with grown (grown) graphene according to Example 3 of the present disclosure (1) before electrochemical activation and (2) after electrochemical activation using a constant current method are shown respectively.

[0015] Figure 5 The titanium sheet with graphene grown thereon according to Example 3 of the present disclosure is shown Figure 4A After the constant current method, the charge and discharge curve of the electrochemical activation was obtained by cyclic voltammetry.

[0016] Figure 6 The graph shows the charge and discharge curves of electrochemically activating the titanium sheet with grown graphene according to Example 4 of the present disclosure using cyclic voltammetry.

[0017] Fig. 7A The charge and discharge curves of electrochemically activating the titanium sheets with grown graphene in Examples 8, 9 and 11 of the present disclosure using cyclic voltammetry are shown, wherein the operating potential (voltage) range is -2.4V to 0V.

[0018] Figure 7B The charge-discharge curves of electrochemically activating the titanium sheets with grown graphene in Examples 8, 9 and 11 of the present disclosure using cyclic voltammetry are shown, wherein the operating potential range is 0V to 1.5V.

[0019] Fig. 8AThe graphs show the charge and discharge curves of the titanium sheets grown with graphene according to Examples 8 to 11 of the present disclosure without electrochemical activation.

[0020] Figure 8B The graph shows the charge and discharge curves of electrochemically activating the titanium sheets with grown graphene according to Examples 8 to 11 of the present disclosure using cyclic voltammetry. DETAILED DESCRIPTION

[0021] The present disclosure can be understood by referring to the following detailed description in conjunction with the accompanying drawings. It should be noted that in order to facilitate the understanding of the readers and the simplicity of the drawings, the multiple drawings in the present disclosure only depict a portion of the electronic device, and the specific components in the drawings are not drawn according to the actual scale. In addition, the number and size of each component in the drawings are only for illustration and are not intended to limit the scope of the present disclosure.

[0022] Directional terms mentioned in the present disclosure, such as "up", "down", "front", "back", "left", "right", etc., are only referenced to the directions of the accompanying drawings. Therefore, the directional terms used are for illustration and not for limiting the present disclosure. In the accompanying drawings, each figure shows the general characteristics of the methods, structures and / or materials used in a particular embodiment. However, these drawings should not be interpreted as defining or limiting the scope or nature covered by these embodiments. For example, for clarity, the relative size, thickness and position of each film layer, region and / or structure may be reduced or enlarged.

[0023] The terms "approximately," "equal," "equal," or "same," "substantially," or "approximately" are generally interpreted as within 20% of a given value or range, or within 10%, 5%, 3%, 2%, 1% or 0.5% of a given value or range.

[0024] It should be noted that the following embodiments can replace, reorganize, or mix features in several different embodiments to complete other embodiments without departing from the spirit of the present disclosure. The features between the embodiments can be mixed and matched as long as they do not violate the spirit of the invention or conflict with each other.

[0025] Exemplary embodiments of the present disclosure are illustrated below, and the same component symbols are used in the drawings and the description to indicate the same or similar parts.

[0026] Figure 1A is a flow chart of a method for manufacturing an electrode of an energy storage assembly according to an embodiment of the present disclosure, and Figure 1B as well as Figure 1C for Figure 1AScanning electron microscope (SEM) image of graphene formed by microwave plasma chemical vapor deposition.

[0027] Please refer to Figure 1A , the manufacturing method of the electrode 10 of the energy storage component of the present embodiment may include the following steps, but the present disclosure is not limited thereto. It is worth noting that the electrode 10 of the energy storage component of the present embodiment can be applied to, for example, an electric double-layer capacitor (EDLC), a hybrid supercapacitor or other suitable energy storage components. Taking a hybrid supercapacitor as an example, the positive electrode thereof is the electrode 10 of the energy storage component of the present embodiment, and the negative electrode is the negative electrode in a lithium-ion battery (for example, a carbon material that can embed lithium ions), but the present disclosure is not limited thereto.

[0028] First, a substrate SB is provided to a microwave plasma device (not shown). The material of the substrate SB may include, for example, a metal material, a conductive polymer material, or other conductive materials. For example, the material of the substrate SB may include copper, gold, silver, titanium, nickel, tin, platinum, palladium, aluminum, or a combination thereof; or the material of the substrate SB may include polyaniline, polyacetylene, polyphenylvinylene, poly-p-phenylene, polypyrrole, polythiophene, or a combination thereof, and the present disclosure is not limited thereto.

[0029] In some embodiments, the microwave plasma device may include a processing chamber, a loading platform, a microwave generating component, a microwave introduction component (waveguide), and a gas supply component. The loading platform may be, for example, disposed in the processing chamber to carry the substrate SB. The microwave generating component may, for example, be used to generate microwaves, and the generated microwaves may be provided to the processing chamber, for example, through the microwave introduction component. The gas supply component may, for example, be connected to the processing chamber to provide the carrier gas and the carbon precursor gas to be described below to the processing chamber.

[0030] In some embodiments, the microwave plasma device may further include a microwave isolator, a microwave power meter, a dual directional coupler, and a 3-stub tuner, but the present disclosure is not limited thereto.

[0031] Next, a carrier gas and a carbon precursor gas are introduced into the microwave plasma device. In the present embodiment, the carrier gas includes an inert gas. For example, the inert gas may include argon or nitrogen. In the present embodiment, the carbon precursor gas includes a hydrocarbon gas (hydrocarbon gas). For example, the hydrocarbon gas may include methane (CH4), ethylene (C2H4), acetylene (C2H2) or a combination thereof.

[0032] Afterwards, a multi-layer graphene wall is formed on the substrate by microwave plasma chemical vapor deposition.

[0033] In detail, the microwave plasma chemical vapor deposition method is performed by using the plasma of the carrier gas generated by the microwave in the microwave plasma device to dissociate the carbon precursor gas to form the graphene G on the substrate SB. Figure 1B as well as Figure 1C As shown, the graphene G formed on the substrate SB is in the form of a multi-layer graphene wall. In detail, in this embodiment, the graphene G formed by the microwave plasma chemical vapor deposition method may include a multi-layer graphene wall having a nanometer scale.

[0034] It is worth noting that when the inert gas includes nitrogen, the generated graphene can be doped with nitrogen to form nitrogen-doped nanographene, such as the following Examples 12 to 14 and Figure 3B and Figure 3C As described.

[0035] In some embodiments, in addition to providing the carbon precursor gas, other Group IV precursors or Group VI precursors may also be provided. For example, during the microwave plasma chemical vapor deposition method, the carrier gas may additionally include silicon or sulfur, so that the generated graphene may be doped with silicon or sulfur, wherein when the carrier gas includes silicon, silicon-doped nanographene is formed, and when the carrier gas includes sulfur, sulfur-doped nanographene is formed, but the present disclosure is not limited thereto.

[0036] In the present embodiment, (1) the frequency of the microwaves used in the microwave plasma chemical vapor deposition method is greater than or equal to 300 MHz and less than or equal to 300 GHz; and (2) the microwave output power is greater than 400 W and less than 75 KW.

[0037] In some embodiments, the microwave plasma chemical vapor deposition method may include electron cyclotron resonance chemical vapor deposition (ECR-CVD), multi electron cyclotron resonance chemical vapor deposition (MECR-CVD), microwave plasma torch chemical vapor deposition (MPT-CVD), focused microwave plasma chemical vapor deposition (FMP-CVD), or a combination thereof, but the present disclosure is not limited thereto.

[0038] In the present embodiment, the microwave plasma chemical vapor deposition method includes microwave plasma torch chemical vapor deposition (MPT-CVD), which can perform the decomposition of the carbon precursor by performing the following steps, but the present disclosure is not limited thereto.

[0039] (1) using a gas supply assembly to provide a carrier gas to a processing chamber; (2) using a microwave generating assembly to generate microwaves, and providing the microwaves to the processing chamber through a microwave introducing assembly to form a microwave plasma of the carrier gas; (3) using a gas supply assembly to provide a carbon precursor gas to the processing chamber, wherein the carbon precursor gas is excited by the microwave plasma to dissociate carbon atoms, so as to grow graphene G on a substrate.

[0040] In some embodiments, the volume ratio of the carrier gas to the carbon precursor gas is 1:10-10:1. In this embodiment, the volume ratio of the carrier gas to the carbon precursor gas is 1:2-2:1, but the present disclosure is not limited thereto.

[0041] In some embodiments, the number of layers of the multilayer graphene wall included in the graphene G is greater than or equal to 2 and less than or equal to 10. For example, the number of layers of the multilayer graphene wall included in the graphene G may be 3 to 5 or 5 to 10, but the present disclosure is not limited thereto. In other embodiments, the number of layers of the multilayer graphene wall included in the graphene G is greater than 10 and less than or equal to 20.

[0042] Continuing with reference to FIG. 1 , the substrate SB including the graphene G is immersed in an electrolyte solution ES for electrochemical activation treatment so that the ions I in the electrolyte solution ES are embedded between adjacent graphene walls. In some embodiments, the electrolyte solution may include organic salts, inorganic salts, or a combination thereof. In this embodiment, the electrolyte solution includes lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), tetraethylammonium tetrafluoroborate (TEABF4), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), or a combination thereof, but the present disclosure is not limited thereto.

[0043] In some embodiments, the electrochemical activation treatment may be performed using a constant current method, a cyclic voltammetry method, or a combination thereof. For example, as described in Example A below, the graphene G may be electrochemically activated by performing multiple charge and discharge cycles using a constant current method; or, as described in Example C below, the graphene G may be electrochemically activated by performing multiple charge and discharge cycles using a cyclic voltammetry method.

[0044] In some embodiments, the operating potential interval in the electrochemical activation treatment may be greater than or equal to 0V and less than or equal to 6V; or may be greater than or equal to -6V and less than or equal to 0V. In the constant current method, the selection of the operating potential interval is based on the appearance of a charge and discharge platform. In the cyclic voltammetry method, a positive scan from a low potential to a high potential and a negative scan from a high potential to a low potential may be performed in the operating potential interval.

[0045] After the electrochemical activation treatment, the ions I in the electrolyte solution ES can be embedded between adjacent graphene walls in the graphene G by high voltage operation to form the electrode 10 of the energy storage component of the present embodiment. In some embodiments, the number of cycles of the electrochemical activation treatment is 1 or more. For example, the number of cycles of the electrochemical activation treatment can be 1 to 10 or 1 to 20, but the present disclosure is not limited thereto.

[0046] In general, in the electrode 10 of the energy storage component of the present embodiment, a microwave plasma chemical vapor deposition method is performed to form graphene G including multiple layers of graphene walls, and then an electrochemical activation treatment is performed to embed ions I in the electrolyte solution ES between adjacent graphene walls, so that the spacing between adjacent graphene walls can be increased due to the embedding of ions I. This phenomenon will increase the surface area of ​​the electrode 10 of the energy storage component of the present embodiment and improve its wettability to the electrolyte, thereby increasing the energy density of the energy storage component including the electrode 10 of the energy storage component of the present embodiment. It is worth noting that the energy density of the energy storage component can be obtained by evaluating the electrochemical behavior and specific capacitance of the electrode 10 of the energy storage component through the following examples, which will not be repeated here.

[0047] Example

[0048] The present disclosure will be described below through several embodiments, but these embodiments are only for illustrative purposes and are not intended to limit the scope of the present disclosure.

[0049] Experimental Example 1: Microwave plasma chemical vapor deposition to grow graphene on a substrate

[0050] [Example 1]

[0051] In this embodiment, first, a titanium sheet (substrate) is provided, wherein the titanium sheet is first treated by immersion in a hydrochloric acid aqueous solution to have a relatively rough surface to facilitate the growth of graphene. Then, a microwave plasma torch chemical vapor deposition method (MPT-CVD) is used to grow graphene on the titanium sheet (substrate), wherein the process conditions include: (1) the frequency of the microwave is 2.45 GHz; (2) the microwave output power is 610 W; (3) the carrier gas is argon; (4) the carbon precursor gas is methane; (5) the volume flow rate of argon (carrier gas) is 30 sccm, and the volume flow rate of methane (carbon precursor gas) is 20 sccm, that is, the volume ratio of the carrier gas to the carbon precursor gas is 3:2; (6) the reaction pressure of graphene is 0.0512 torr; (7) the reaction time of graphene is 13 minutes.

[0052] [Example 2]

[0053] In Example 2, the steps for growing graphene on a substrate are substantially the same as those in Example 1, with the main differences being: (5) the volume flow rate of argon (carrier gas) is 30 sccm, and the volume flow rate of methane (carbon precursor gas) is 30 sccm, that is, the volume ratio of the carrier gas to the carbon precursor gas is 1:1; (6) the reaction pressure of graphene is 0.0612 Torr.

[0054] [Example 3]

[0055] In Example 3, the steps for growing graphene on a substrate are substantially the same as those in Example 1, with the main differences being: (5) the volume flow rate of argon (carrier gas) is 30 sccm, and the volume flow rate of methane (carbon precursor gas) is 50 sccm, i.e., the volume ratio of the carrier gas to the carbon precursor gas is 3:5; (6) the reaction pressure of graphene is 0.0784 Torr.

[0056] The experimental data of the above Examples 1 to 3 are summarized in the following Table 1.

[0057] [Table 1]

[0058]

[0059] Figure 2 The Raman spectra of the graphenes of Examples 1 to 3 are shown, wherein the D peak represents the sp 2 Ring breathing vibration mode of carbon atoms. The G peak represents the sp 2 The in-plane vibration mode of the hybridized carbon atoms, and the 2D peak is the frequency-converting peak of the D peak. In this experimental example, a Raman spectrometer is used to measure the Raman spectra of the graphene of Examples 1 to 3, and its model is DXR2 Raman Microscope, and it is from ThermoFisher Scientific Co., Ltd. (ThermoFisher).

[0060] After carrying out Examples 1 to 3, a Raman spectrometer was used to confirm whether graphene was grown on the titanium sheet. Figure 2 It can be seen that the D peaks of the graphenes of Examples 1 to 3 are all located at 1349 cm -1 , the G peak of graphene is located at 1590cm -1 , and the 2D peaks of graphene are all located at 2689cm -1 , so it can be seen that graphene grows completely on the titanium sheet.

[0061] The Raman spectroscopy data of Examples 1 to 3 and the number of graphene wall layers are summarized in Table 2 below.

[0062] [Table 2]

[0063]

[0064] As can be seen from Table 2, the ratio of the 2D peak intensity of graphene to the peak intensity of the G peak (I 2D / I G ) can be used to calculate the number of graphene walls grown on the titanium sheet. 2D / I GIt is about 0.5 to 0.6, so it can be inferred that the number of layers of graphene walls grown on the titanium sheet in Examples 1 to 3 is about 3 to 5.

[0065] [Example 4]

[0066] In Example 4, the steps for growing graphene on a substrate are substantially the same as those in Example 1, with the main differences being: (2) the microwave output power is 1400 W; (5) the volume flow rate of argon (carrier gas) is 20 sccm, and the volume flow rate of methane (carbon precursor gas) is 20 sccm, that is, the volume ratio of the carrier gas to the carbon precursor gas is 1:1; (6) the reaction pressure of graphene is 0.06 Torr; and (7) the reaction time of graphene is 3 minutes.

[0067] As can be seen from the following Table 3, in Example 4, the ratio of the peak intensity of the 2D peak to the peak intensity of the G peak (I 2D / I G ) is less than 0.2, so it can be inferred that the number of graphene walls grown on the titanium sheet in Example 4 is at least greater than 10 layers.

[0068] [Table 3]

[0069]

[0070] [Example 5]

[0071] In Example 5, the steps of growing graphene on a substrate are substantially the same as those in Example 4, with the main difference being: (7) the reaction time of graphene is 2 minutes.

[0072] [Example 6]

[0073] In Example 6, the steps of growing graphene on a substrate are substantially the same as those in Example 5, with the main difference being that: (5) the volume flow rate of argon (carrier gas) is 20 sccm, and the volume flow rate of methane (carbon precursor gas) is 50 sccm, that is, the volume ratio of the carrier gas to the carbon precursor gas is 2:5.

[0074] [Example 7]

[0075] In Example 7, the steps of growing graphene on a substrate are substantially the same as those in Example 5, with the main difference being that: (5) the volume flow rate of argon (carrier gas) is 20 sccm, and the volume flow rate of methane (carbon precursor gas) is 80 sccm, that is, the volume ratio of the carrier gas to the carbon precursor gas is 1:4.

[0076] As can be seen from the following Table 4, in Example 5, the ratio of the peak intensity of the 2D peak to the peak intensity of the G peak (I 2D / IG ) is 0.25, so it can be inferred that the number of graphene walls grown on the titanium sheet in Example 5 is about 10 layers; in Example 6, the ratio of the peak intensity of the 2D peak to the peak intensity of the G peak (I 2D / I G ) is 0.40, so it can be inferred that the number of layers of the graphene wall grown on the titanium sheet in Example 6 is about 5 to 10 layers; in Example 7, the ratio of the peak intensity of the 2D peak to the peak intensity of the G peak (I 2D / I G ) is 0.46, so it can be inferred that the number of graphene walls grown on the titanium sheet in Example 7 is at least about 4 to 5 layers.

[0077] [Table 4]

[0078]

[0079]

[0080] [Example 8]

[0081] In Example 8, the steps of growing graphene on a substrate are substantially the same as those in Example 4, with the main difference being: (3) the carrier gas is nitrogen.

[0082] [Example 9]

[0083] In Example 9, the steps of growing graphene on a substrate are substantially the same as those in Example 8, with the main differences being: (5) the volume flow rate of nitrogen (carrier gas) is 30 sccm, and the volume flow rate of methane (carbon precursor gas) is 30 sccm.

[0084] [Example 10]

[0085] In Example 10, the steps of growing graphene on a substrate are substantially the same as those in Example 8, with the main differences being: (5) the volume flow rate of nitrogen (carrier gas) is 40 sccm, and the volume flow rate of methane (carbon precursor gas) is 40 sccm.

[0086] [Example 11]

[0087] In Example 11, the steps of growing graphene on a substrate are substantially the same as those in Example 8, with the main differences being: (5) the volume flow rate of nitrogen (carrier gas) is 50 sccm, and the volume flow rate of methane (carbon precursor gas) is 50 sccm.

[0088] [Example 12]

[0089] In Example 12, the steps of growing graphene on a substrate are substantially the same as those in Example 1, with the main differences being: (3) the carrier gas is nitrogen; (5) the volume flow rate of nitrogen (carrier gas) is 15 sccm, and the volume flow rate of methane (carbon precursor gas) is 50 sccm, that is, the volume ratio of the carrier gas to the carbon precursor gas is 3:10; and (6) the reaction pressure of graphene is 0.078 Torr.

[0090] [Example 13]

[0091] In Example 13, the steps of growing graphene on a substrate are substantially the same as those in Example 12, with the main differences being: (5) the volume flow rate of nitrogen (carrier gas) is 30 sccm, and the volume flow rate of methane (carbon precursor gas) is 50 sccm, that is, the volume ratio of carrier gas to carbon precursor gas is 3:5; (6) the reaction pressure of graphene is 0.0839 Torr.

[0092] [Example 14]

[0093] In Example 14, the steps for growing graphene on a substrate are substantially the same as those in Example 12, with the main differences being: (5) the volume flow rate of nitrogen (carrier gas) is 50 sccm, and the volume flow rate of methane (carbon precursor gas) is 50 sccm, that is, the volume ratio of the carrier gas to the carbon precursor gas is 1:1; (6) the reaction pressure of graphene is 0.0998 Torr.

[0094] The experimental data of the above Examples 12 to 14 are summarized in the following Table 5.

[0095] [Table 5]

[0096]

[0097] Figure 3A The Raman spectra of the graphenes of Examples 12 to 14 are shown, wherein the D peak represents the sp 2 Ring breathing vibration mode of carbon atoms. The G peak represents the sp 2 The in-plane vibration mode of the hybridized carbon atoms, and the 2D peak is the frequency-converting peak of the D peak. In this experimental example, a Raman spectrometer is used to measure the Raman spectra of the graphenes of Examples 12 to 14. The model is DXR2 Raman Microscope from ThermoFisher.

[0098] After carrying out Example 12 to Example 14, a Raman spectrometer was used to confirm whether graphene was grown on the titanium sheet. Figure 3AIt can be seen that the D peaks of the graphenes of Examples 12 to 14 are all located at 1340-1360 cm -1 , the G peaks of graphene are all located at 1580-1600cm -1 , and the 2D peaks of graphene are all located at 2600-2750cm -1 , so it can be seen that graphene grows completely on the titanium sheet.

[0099] In addition, X-ray photoelectron spectroscopy (XPS) was used to confirm whether nitrogen was doped in the graphene wall of Examples 12 to 14. Figure 3B as well as Figure 3C ( Figure 3C enlarge Figure 3B From the binding energy range in which the signal of N(1s) appears, it can be seen that the signal (400eV) intensity of N(1s) in Examples 12 to 14 is obvious, thus confirming that nitrogen atoms are doped in the graphene walls of Examples 12 to 14, wherein the doping rate of nitrogen atoms is approximately 1%.

[0100] The Raman spectroscopy data of Examples 12 to 14 and the number of graphene wall layers are summarized in Table 6 below.

[0101] As can be seen from Table 6 below, in Examples 12 to 14, the ratio of the peak intensity of the 2D peak to the peak intensity of the G peak (I 2D / I G ) are 0.24, 0.33 and 0.21, so it can be inferred that the number of layers of the graphene wall grown on the titanium sheet in Examples 12 to 14 is at least greater than 10 layers.

[0102] [Table 6]

[0103]

[0104] Experimental Example 2: Electrochemical Activation of Graphene

[0105] [Example A]

[0106] First, the titanium sheet with graphene grown in Example 3 is immersed in an electrolyte solution, wherein the electrolyte in the electrolyte solution is lithium hexafluorophosphate (LiPF6), and the solvent is composed of ethylene carbonate (EC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) in a volume ratio of 1:1:1. Afterwards, the titanium sheet with graphene grown in Example 3 is subjected to a constant current method for multiple charge and discharge cycles to evaluate its electrochemical behavior and specific capacitance value, wherein the operating potential range in the constant current method is 0V to 5.0V, and the current density is 0.5A / g.

[0107] from Figure 4A It can be seen that during the first charging process, the potential instantly rises to about 4.7V and then shows an obvious slope change. This potential can be regarded as the starting embedding potential of the ions, that is, the ions begin to embed into the adjacent graphene walls on the titanium sheet and establish active points for adsorption and desorption, and a platform area is generated in the potential range of 4.7V to 5.0V.

[0108] After the first charge is completed, the first discharge is performed, wherein Figure 4A The discharge curve shown has a slope change but no platform region is formed. The slope change can be regarded as the ions no longer being embedded in the graphene wall. Figure 4A The discharge curve shown can be divided into two curves, the first curve is the potential range of 5.0V to 4.0V, and the second curve is the potential range of 4.0V to 2.2V. In the first curve, in addition to the ion desorption behavior of the electric double layer, there is also a part of the ion embedding in the graphite layer, while in the second curve, there is only the ion desorption behavior of the electric double layer, so the first curve and the second curve have different slopes.

[0109] During the second and third charge-discharge cycles, it can be seen that it has gradually approached the ion desorption behavior of the typical electrical double layer, that is, fewer and fewer ions are embedded in the adjacent graphene walls on the titanium sheet, which means that the ion embedding behavior should have caused irreversible effects.

[0110] In addition, from Figure 4B It can be seen that after the titanium sheet with graphene grown thereon is electrochemically activated using the constant current method to form an electrode, the specific capacitance of the electrode increases from 12.9F / g to 22.2F / g. This indicates that after the electrochemical activation treatment, the spacing between the graphene walls in the electrode increases, thereby increasing the active sites in the graphene that allow anions to be adsorbed and desorbed, thereby achieving the purpose of improving the specific capacitance.

[0111] [Example B]

[0112] The electrode of Example A was subjected to cyclic voltammetry for multiple charge-discharge cycles to evaluate its electrochemical behavior and specific capacitance value, wherein the electrode was scanned at a scan rate of 25 mV / s.

[0113] from Figure 5It can be seen that the maximum potential of the electrode of Example B can withstand about 4.2V and shows a relatively square charge-discharge curve. If the upper limit potential is further increased to more than about 4.8V, although the specific capacitance of the electrode will increase with the increase of the operating potential, it will produce an irreversible phenomenon, which is due to the oxidation reaction of the titanium sheet at this potential and / or the decomposition reaction of the electrolyte at this potential. Based on this, Figure 5 The balance between the specific capacitance value and the collapse of the electrode of Example B is shown. Figure 5 It can be seen that setting the operating potential used in cyclic voltammetry to about 5 V can reduce the possibility of electrode collapse while achieving a relatively large specific capacitance value.

[0114] [Example C]

[0115] The titanium sheet with graphene grown in the above-mentioned Example 4 is immersed in an electrolyte solution, wherein the electrolyte in the electrolyte solution is tetraethylammonium tetrafluoroborate (TEABF4), the solvent is propylene carbonate, and the electrolyte concentration is 1 M. Afterwards, the titanium sheet with graphene grown in Example 4 is subjected to cyclic voltammetry for three charge and discharge cycles to form an electrode by electrochemical activation treatment, and its electrochemical behavior and specific capacitance value are evaluated. In the cyclic voltammetry of Example C, a three-electrode system is used, wherein the working electrode is the electrode of Example C, the counter electrode is a platinum (platinum) wire, the operating potential range is -2.0V to 0V, and the electrochemical activation is performed for 1600 seconds at a scanning speed of 25mV / s.

[0116] Figure 6 The cyclic voltammogram of the electrode of Example C after the third charge-discharge cycle is shown. Figure 6 It can be seen that the electrode of Example C exhibits a square charge-discharge curve and shows good electrochemical behavior. In addition, although irreversible redox peaks can be seen at the upper and lower limit potentials of the charge-discharge curve after electrochemical activation, they will slowly disappear with the increase in the number of scan cycles. It can be speculated that this is due to the pseudo-capacitive behavior caused by the adsorption of ions in the electrolyte solution on the electrode surface or the embedded ions during the electrochemical activation process. The above-mentioned irreversible behavior also indirectly shows that some ions and solvent molecules will be captured in graphene during the embedding process to form molecular pillars. In addition, the specific capacitance value data of Example C are summarized in the following Table 7. From Figure 6 As can be seen from Table 7, after electrochemical activation, the specific capacitance of the electrode of Example C increased significantly, with the specific capacitance increasing by about 105%.

[0117] [Table 7]

[0118]

[0119] [Example D]

[0120] The titanium sheets with graphene grown thereon in Examples 5 to 7 were immersed in an electrolyte solution. Then, the titanium sheets with graphene grown thereon in Examples 5 to 7 were subjected to cyclic voltammetry for three charge-discharge cycles to perform electrochemical activation treatment to form electrodes of Examples D1 to D3, respectively, wherein the steps and conditions of the cyclic voltammetry performed in Example D were the same as those in Example C.

[0121] The specific capacitance data of the electrodes of Example D1 to Example D3 are summarized in the following Table 8. As can be seen from Table 8, after electrochemical activation, the specific capacitance values ​​of the electrodes of Example D1 to Example D3 all increased, wherein the specific capacitance value of the electrode of Example D1 had the largest increase rate, while the specific capacitance value of the electrode of Example D3 had the smallest increase rate.

[0122] [Table 8]

[0123]

[0124] [Example E]

[0125] The titanium sheets with graphene grown in the above-mentioned Examples 8, 9 and 11 were immersed in an electrolyte solution, wherein the electrolyte in the electrolyte solution was tetraethylammonium tetrafluoroborate (TEABF4), the solvent was propylene carbonate, and the electrolyte concentration was 1 M. Afterwards, the titanium sheets with graphene grown in Examples 8, 9 and 11 were subjected to cyclic voltammetry to perform three charge and discharge cycles to form electrodes of Examples E1, E2 and E4, respectively, and their electrochemical behaviors and specific capacitance values ​​were evaluated. In the cyclic voltammetry of Example E, the operating potential range was -2.4V to 0V and 0V to 1.5V, and the scanning was performed at a scanning speed of 25mV / s.

[0126] Fig. 7A The cyclic voltammograms of the titanium sheets with graphene grown in Examples 8, 9 and 11 are shown when the operating potential range is -2.4V to 0V and the charge and discharge cycles are performed. Figure 7B The cyclic voltammograms of the titanium sheets with graphene grown thereon in Examples 8, 9 and 11 are shown when the charge and discharge cycles are performed in the operating potential range of 0V to 1.5V. Fig. 7A It can be seen that the electrodes of Example E1, Example E2 and Example E4 all exhibited square charge-discharge curves and showed good electrochemical behavior. Therefore, the electrodes of Example E1, Example E2 and Example E4 are suitable as the negative electrode of the supercapacitor. Figure 7BIt can be seen that when the operating potential is about 0.8 V, the current density begins to rise sharply. This is because the nitrogen-containing functional groups exist in the organic phase of the electrolyte solution, and the electrolyte solution begins to decompose when the operating potential is about 0.8 V, and the color of the solution changes from colorless to light yellow. Therefore, the electrodes of Example E1, Example E2 and Example E4 are not suitable as the positive electrode of the supercapacitor.

[0127] also, Fig. 8A The cyclic voltammograms of the electrodes (titanium sheets with graphene grown in Examples 8 to 11) that were not electrochemically activated and were subjected to charge and discharge cycles in the operating potential range of -2.4V to 0V are shown, and Figure 8B The cyclic voltammogram of the electrochemically activated electrode (electrodes of Examples E1 to E4, wherein the electrode of Example E3 is formed by performing cyclic voltammetry on the titanium sheet with graphene grown thereon of Example 10 to perform three charge and discharge cycles) subjected to charge and discharge cycles in the operating potential range of -2.4V to 0V is shown.

[0128] The specific capacitance data of the electrodes of Example E1 to Example E4 are summarized in the following Table 9. FIG. 8A to FIG. 8B As can be seen from Table 9, after electrochemical activation, the specific capacitance values ​​of the electrodes of Examples E1 to E4 increased significantly.

[0129] In addition, from FIG. 8A to FIG. 8B As can be seen from Table 9, as the volume flow rates of nitrogen and methane increase, the specific capacitance of the electrode will also increase. When the volume flow rates of nitrogen and methane are 40 sccm respectively, the specific capacitance of the electrode is close to the upper limit.

[0130] [Table 9]

[0131]

[0132] In summary, the present disclosure first grows graphene including multiple layers of graphene walls by performing microwave plasma chemical vapor deposition, and then performs electrochemical activation treatment to embed ions between adjacent graphene walls. Therefore, the spacing between adjacent graphene walls can be increased due to the embedding of ions, which will increase the surface area of ​​the electrode of the energy storage component of the embodiment of the present disclosure and improve its wettability to the electrolyte, thereby increasing the energy density of the energy storage component including this electrode. Furthermore, the manufacturing method of the electrode of the energy storage component provided by the present disclosure does not use a relatively complicated process, so it can consume relatively less process time and process cost.

[0133] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present disclosure, rather than to limit them. Although the present disclosure has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the various embodiments of the present disclosure.

Claims

1. A method for manufacturing an electrode of an energy storage component, characterized in that: include: Providing a substrate in a microwave plasma device; Introducing a carrier gas and a carbon precursor gas into the microwave plasma device; forming a multi-layer graphene wall on the substrate by microwave plasma chemical vapor deposition; as well as immersing the substrate containing the multilayer graphene walls in an electrolyte solution for electrochemical activation treatment, so that ions in the electrolyte solution are embedded between adjacent graphene walls, The volume ratio of the carrier gas to the carbon precursor gas is 1:10-10:

1. 2 . The method for manufacturing an electrode of an energy storage component according to claim 1 , wherein the number of cycles of the electrochemical activation treatment is more than 1. 3 . The method for manufacturing an electrode of an energy storage component according to claim 1 , wherein the carbon precursor gas comprises a hydrocarbon gas.

4. The method for manufacturing an electrode of an energy storage component according to claim 1, wherein the microwave plasma chemical vapor deposition method comprises electron cyclotron resonance chemical vapor deposition (ECR-CVD), multi-source electron cyclotron resonance chemical vapor deposition (MECR-CVD), microwave plasma torch chemical vapor deposition (MPT-CVD), focused microwave plasma chemical vapor deposition (FMP-CVD) or a combination thereof. 5 . The method for manufacturing an electrode of an energy storage component according to claim 1 , wherein the frequency of the microwaves used in the microwave plasma chemical vapor deposition method is greater than or equal to 300 MHz and less than or equal to 300 GHz.

6. The method for manufacturing an electrode of an energy storage component according to claim 1, wherein the microwave output power used in the microwave plasma chemical vapor deposition method is greater than 400 W and less than 75 KW. 7 . The method for manufacturing an electrode of an energy storage component according to claim 1 , wherein the volume ratio of the carrier gas to the carbon precursor gas is 1:2-2:

1. 8 . The method for manufacturing an electrode of an energy storage component according to claim 1 , wherein the number of layers of the multilayer graphene wall is greater than or equal to 2 and less than or equal to 10. 9 . The method for manufacturing an electrode of an energy storage component according to claim 1 , wherein the number of layers of the multilayer graphene wall is greater than 10 and less than or equal to 20. 10 . The method for manufacturing an electrode of an energy storage assembly according to claim 1 , wherein the material of the substrate comprises a metal material, wherein the metal material is selected from copper, gold, silver, titanium, nickel, tin, platinum, palladium, aluminum or a combination thereof. 11 . The method for manufacturing an electrode of an energy storage component according to claim 1 , wherein the material of the substrate comprises a conductive polymer material, wherein the conductive polymer material is selected from polyaniline, polyacetylene, poly(p-phenylene), poly(p-phenylene), polypyrrole, polythiophene or a combination thereof.

12. The method for manufacturing an electrode of an energy storage component according to claim 1, wherein the electrolyte solution comprises LiPF6, LiBF4, TEABF4, LiFSI, LiTFSI or a combination thereof. 13 . The method for manufacturing an electrode of an energy storage component according to claim 1 , wherein the electrochemical activation treatment comprises performing a constant current method, a cyclic voltammetry method or a combination thereof.

14. The method for manufacturing an electrode of an energy storage component according to claim 1, wherein an operating potential interval in the electrochemical activation treatment is greater than or equal to 0V and less than or equal to 6V; or greater than or equal to -6V and less than or equal to 0V. 15 . The method for manufacturing an electrode of an energy storage assembly according to claim 1 , wherein the carrier gas comprises argon or nitrogen.

16. An electrode of an energy storage component, characterized in that: The electrode of the energy storage component is formed by the manufacturing method of the electrode of the energy storage component according to claim 1, and the electrode of the energy storage component comprises: the substrate; and The graphene is arranged on the substrate and includes the multi-layer graphene wall. 17 . The electrode of the energy storage assembly according to claim 16 , wherein the number of layers of the multi-layer graphene wall is greater than or equal to 2 and less than or equal to 10. 18 . The electrode of the energy storage assembly according to claim 16 , wherein the number of layers of the multi-layer graphene wall is greater than 10 and less than or equal to 20. 19 . The electrode of the energy storage assembly according to claim 16 , wherein the material of the substrate comprises a metal material, wherein the metal material is selected from copper, gold, silver, titanium, nickel, tin, platinum, palladium, aluminum or a combination thereof. 20 . The electrode of the energy storage assembly according to claim 16 , wherein the material of the substrate comprises a conductive polymer material, wherein the conductive polymer material is selected from polyaniline, polyacetylene, poly(p-phenylene), poly(p-phenylene), polypyrrole, polythiophene or a combination thereof. 21 . The electrode of the energy storage assembly according to claim 16 , wherein the graphene is doped with nitrogen, silicon or sulfur.

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