TWI749511B - Graphene electrode manufacturing method and manufacturing device - Google Patents

Abstract

The present invention provides a process method for a graphene electrode and a manufacturing device thereof. The method includes (1): taking a liquid polyimide and infiltrating it into a porous substrate with multiple pores in an ultrasonic spray manner, and thus forming A porous coating substrate; (2): the porous coating substrate moves in a tunnel kiln, and a plurality of carbon dioxide laser irradiators continuously irradiate the porous coating substrate passing through the tunnel kiln with carbon dioxide lasers , Forming the porous graphene substrate into a porous graphene substrate; (3): subjecting the porous graphene substrate to a lithiation procedure to form the porous graphene substrate into a lithiated graphene electrode; Therefore, a new process method for graphene electrode can be provided, and the lithiated graphene electrode can be used as a negative electrode of a lithium ion battery or a negative electrode of a supercapacitor lithium battery, and its porous graphene substrate can be used as a negative electrode of a lithium ion battery. An electrode plate of a supercapacitor.

Description

Graphene electrode manufacturing method and manufacturing device

The invention relates to a process method and a manufacturing device for graphene electrodes, in particular to a process method and a manufacturing device that can produce graphene electrodes by using ultrasonic spray, combined with porous substrates, and carbon dioxide laser irradiation.

Graphite is a crystalline structure composed of multiple layers of graphene, while graphene is a single-layered graphite structure. Each carbon atom forms a bond with three adjacent ^{carbon atoms in an sp 2 crystalline structure and extends.} A honeycomb hexagonal two-dimensional structure, graphene has been widely used in semiconductors, touch panels or solar cells and other fields, and is expected to be widely used in photovoltaics, green energy power generation, environmental biomedical sensing, composite The development of many industrial fields such as sexual functional materials.

On the other hand, current electric vehicles and smart phones require batteries with higher capacity and faster charging, and the industry needs to find solutions. Therefore, in view of this, the inventor set out to develop and conceive its solution, hoping to develop a graphene electrode manufacturing process and its manufacturing device to promote the development of this industry, and after many years of thinking, the present invention was developed. The production.

The purpose of the present invention is to provide a graphene electrode manufacturing method and manufacturing device, which can achieve the extremely economic benefits of graphene electrode manufacturing, and the lithiated graphene electrode can be used as the negative electrode of a lithium ion battery ; Its porous graphene substrate can be used as an electrode plate of a supercapacitor; its lithiated graphene electrode can be used as a negative electrode of a supercapacitor lithium battery.

In order to achieve the above-mentioned object, the technical method adopted by the present invention includes: Step 1: Take liquid polyimide, form the liquid polyimide into mist particles by ultrasonic spraying method, and then infiltrate it into a Porous porous substrate, so that the porous substrate in the pores A polyimide layer is attached to the periphery to form a porous coating substrate;

Step 2: The porous coating substrate is moved in a tunnel kiln by a conveyor belt. The tunnel kiln is provided with a plurality of carbon dioxide laser irradiators, and the carbon dioxide laser irradiators are used with carbon dioxide lasers. Continuous irradiation of the porous coating substrate through the tunnel kiln causes the polyimide layer of the porous coating substrate to form a high-purity porous graphene layer, thus forming a porous graphene substrate.

In the foregoing method, step 3 can be further performed after step 2: the porous graphene substrate is subjected to a lithiation process, so that the porous graphene substrate forms a lithiated graphene electrode.

In the aforementioned method, the liquid polyimide is formed by ultrasonic spraying to form mist particles and then penetrated into a porous substrate with multiple pores. At least one or more ultrasonic sprayers are used to disperse the liquid polyimide. The mist particles penetrate into a porous substrate, and the at least one or a plurality of ultrasonic sprayers are arranged on the inner side, upper inner or lower inner of the tunnel kiln.

In the aforementioned method, the porous substrate is a rolled substrate and has a first surface and a second surface, the porous substrate is disposed on a first rotating shaft, and the porous substrate is exposed upward from the first surface. The conveyor belt is transported into the tunnel kiln to move, so that the first surface of the porous substrate receives the plurality of ultrasonic sprayers to spray the mist particles of liquid polyimide into the porous substrate, and then move it in the tunnel The kiln receives the carbon dioxide laser irradiator continuously with the carbon dioxide laser, so that the polyimide layer of the porous coating substrate forms a high-purity porous graphene layer, which is then rolled and placed on a second rotating shaft superior;

Next, move the second rotating shaft to roll the porous substrate on the second rotating shaft through a turning idler, so that the porous substrate is exposed upward with the second surface, and is transported by the conveyor belt into the porous substrate. Move in the tunnel kiln to make the second surface of the porous substrate receive the plurality of ultrasonic sprayers to spray the mist particles of liquid polyimide into the porous substrate, and then receive the plurality of ultrasonic sprays in the tunnel kiln The carbon dioxide laser irradiator continuously irradiates the carbon dioxide laser, so that the polyimide layer of the porous coating substrate forms a high-purity porous graphene layer, which is then rolled on a third rotating shaft to form a polyimide layer. Porous graphene substrate.

In the aforementioned method, the liquid polyimide is a liquefied Katpon ^® .

In the aforementioned method, wherein the porous substrate is selected from one of the following: porous carbon material substrate, porous graphite, and porous metal substrate.

In the foregoing method, after the formation of the lithiated graphene electrode in step 2, multiple lithiated graphene electrodes can be stacked to form a multilayer lithiated graphene electrode.

In the foregoing method, the porous graphene substrate is used as an electrode plate of a super capacitor.

In the foregoing method, the lithiated graphene electrode is used as a negative electrode of a lithium ion battery.

In the foregoing method, the lithiated graphene electrode is used as a negative electrode of a supercapacitor lithium battery.

The technical means of the present invention include: a tunnel kiln with a conveyor belt; a plurality of ultrasonic sprayers are arranged in the tunnel kiln; a plurality of carbon dioxide laser irradiators are arranged in the tunnel kiln; In the foregoing configuration, the ultrasonic sprayer is used to set the liquid polyimide and spray the liquid polyimide into mist particles, and the carbon dioxide laser irradiator is used to provide continuous irradiation of the carbon dioxide laser.

In order to enable your reviewer to have a better understanding and understanding of the technology, method features and achieved effects of the present invention, a preferred embodiment diagram and detailed description are provided. The description is as follows:

11: Polyimide

12: Ultrasonic sprayer

20: Porous substrate

201: Step 1

202: Step 2

203: Step 3

205: Porosity

207: Surface 1

208: Surface 2

21: Polyimide layer

22: Porous coating substrate

28: Conveyor belt

29: Steering idler

30: Tunnel Kiln

302: 1st shaft

304: 2nd shaft

306: 3rd shaft

32: CO2 laser irradiator

34: Porous graphene layer

36: Porous graphene substrate

38: Lithated graphene electrode

39: Multilayer lithiated graphene electrode

40: Super capacitor

42: Electrode plate

46: 2nd electrode plate

50: Lithium-ion battery

52: negative electrode

54: Diaphragm

56: positive electrode

Figure 1 is a schematic flow diagram of the manufacturing method of the present invention.

Figure 2 is a schematic diagram of the present invention infiltrating liquid polyimide into a porous substrate by means of ultrasonic spray.

Figure 2-1 is a partial enlarged view of the porous substrate of the present invention.

Figure 3 is a schematic diagram of the porous coating substrate of the present invention.

Figure 3-1 is a partial enlarged view of the porous coating substrate of the present invention.

Figure 4 is one of the porous coating substrates irradiated with carbon dioxide laser in the present invention Schematic diagram of the embodiment.

Figure 5 is a schematic diagram of the porous graphene substrate of the present invention.

Figure 5-1 is a partial enlarged view of the porous graphene substrate of the present invention.

Figure 6 is a schematic diagram of the infiltration of liquid polyimide into a porous substrate and carbon dioxide laser irradiation in a tunnel kiln using ultrasonic spray.

Figure 7-1 is a schematic diagram of ultrasonic spray and carbon dioxide laser irradiation on the first surface of a roll of porous substrate in a tunnel kiln according to the present invention.

Figure 7-2 is a schematic diagram of ultrasonic spray and carbon dioxide laser irradiation on the second surface of a roll of porous substrate in a tunnel kiln according to the present invention.

Figure 8 is a cross-sectional view of the multilayer lithiated graphene electrode of the present invention.

Figure 9 is a schematic diagram of the supercapacitor of the present invention.

Figure 10 is a schematic diagram of the lithium ion battery of the present invention.

Please refer to Figures 1-10), which are preferred embodiments of the manufacturing method and manufacturing device of the graphene electrode of the present invention. The basic structure, and the displayed composition drawing is not limited to the same shape and size ratio in actual implementation. The shape and size ratio in actual implementation is an optional design.

As shown in Figure 1, the present invention provides a process method of graphene electrode, the process method (including the manufacturing device) includes:

Step 1 (201): As shown in Figure 2, take the liquid polyimide 11 (Polyimide, PI for short), use ultrasonic spray to form the liquid polyimide 11 into mist particles and then infiltrate it into a On the porous substrate 20 with a plurality of pores 205, the porous substrate 20 is attached with a polyimide layer 21 on the periphery of the pores 205, thus forming a porous coating substrate 22. A schematic diagram of the porous coating substrate 22 is shown in Figure 3;

The aforementioned liquid polyimide 11 is operated by ultrasonic spray, which is The liquid polyimide 11 can be input into an ultrasonic sprayer 12, which uses a piezoelectric crystal oscillator (piezoelectric oscillator/oscillator) to generate high-frequency shock waves (ultrasonic waves) to act on the liquid polyimide The polyimide 11 is used to shake the liquid polyimide 11 into very small mist particles, and the nozzle shape, wind flow or pressure difference of the ultrasonic sprayer 12 can be used to make it continuously and stably spray the polyimide 11 to form the polyimide layer 21 by attaching the peripheries of the pores 205 of the porous substrate 20 to the mist-like particles.

As shown in Figure 2-1, it is a partial enlarged view of the porous substrate 20, showing that there are countless pores 205 in the porous substrate 20;

Step 2 (202): As shown in Figure 4, the porous coating substrate 22 is moved in a tunnel kiln 30 by a conveyor belt 28. Below) a plurality of carbon dioxide laser irradiators 32 are provided. The carbon dioxide laser irradiators 32 continuously irradiate the porous coating substrate 22 passing through the tunnel kiln 30 with the carbon dioxide laser to make the porous coating The polyimide layer 21 of the substrate 22 forms a high-purity porous graphene layer 34, so that the porous coating substrate 22 forms a porous graphene substrate 36. The porous graphene substrate 36 is as shown in the fifth As shown in the figure. As shown in Figure 5-1, it is a partial enlarged view of the porous graphene substrate, showing that there are countless pores 205 in the porous graphene substrate, and a high-purity porous graphene layer is attached around the pores 205 34.

Optionally, the process method further includes a step 3 (203): subject the porous graphene substrate 36 to a lithiation process, so that the porous graphene substrate 36 forms a lithiated graphene electrode 38 (lithiated graphene electrode) .

In this way, a new process method for graphene electrodes can be provided, and excellent production economic efficiency can be achieved.

Wherein the step 1 (201) of the liquid line 11 to the polyimide liquefaction of Katpon ^®, Katpon ^® is the trade name of the U.S. company DuPont polyimide (PI) film material, can be purchased commercially , Polyimide can be obtained quickly and at low cost by using this product.

Wherein, the porous substrate 20 of step 1 (201) can be selected from one of the following: porous carbon material substrate, porous graphite, porous metal substrate, but not limited to this; the porous The gap 205 of the substrate 20 can increase the surface area of the entire substrate.

Wherein, in step 1 (201), the liquid polyimide 11 is sprayed by ultrasonic spray to spray the mist particles of the polyimide 11 into a porous substrate 20, as shown in Figure 2, the system One or more ultrasonic sprayers 12 are used to infiltrate the mist particles of liquid polyimide 11 into a porous substrate 20; optionally, as shown in Figure 6, at least one or more ultrasonic sprayers 12 Is installed inside the tunnel kiln 30 (including the inner side, upper inner or lower inner). When the porous substrate 20 moves on the conveyor belt 28, the ultrasonic sprayers 12 are arranged from various angles The porous substrates 20 are fully sprayed with the mist particles of the liquid polyimide 11 after atomization, so that the porous substrates 20 are attached with a polyimide layer 21 around the pores 205. A porous coating substrate 22 is formed. As shown in Figure 3-1, which is a partial enlarged view of the porous coating substrate 22, it shows that there are countless pores 205 in the porous coating substrate 22, and a polyamide is attached to the periphery of the pores 205 Imine layer 21.

In another embodiment, as shown in FIG. 7-1, the porous substrate 20 is a roll substrate and has a first surface 207 and a second surface 208. The porous substrate 20 is disposed on a second surface. On a rotating shaft 302, the porous substrate 20 is exposed upward with the first surface 207, and is transported by the conveyor belt 28 into the tunnel kiln 30 to move, so that the first surface 207 of the porous substrate 20 receives the plurality of The ultrasonic sprayer 12 sprays the mist particles of the liquid polyimide 11 into the porous substrate 20, and then receives a plurality of carbon dioxide laser irradiators 32 in the tunnel kiln 30 to continuously irradiate the carbon dioxide laser to make The polyimide layer 21 of the porous coating substrate 22 forms a high-purity porous graphene layer 34, which is then rolled on a second rotating shaft 304;

As shown in Fig. 7-2, continue, move the second shaft 304 to roll the porous substrate 20 on the second shaft 304, and pass a turning idler 29 to make the porous substrate 20 The second surface 208 is exposed upward, and is transported by the conveyor belt 28 into the tunnel kiln 30 to move, so that the second surface 208 of the porous substrate 20 receives the plurality of ultrasonic sprayers 12 to remove the liquid polyimide 11 The mist particle spray penetrates into the porous substrate 20, and then receives a plurality of carbon dioxide laser irradiators 32 in the tunnel kiln 30 to continuously irradiate the carbon dioxide laser to make the polyimide of the porous coating substrate 22 The layer 21 forms a high-purity porous graphene layer 34, which is then placed in a roll on a third rotating shaft 306, and is thus shaped A porous graphene substrate 36 is formed.

The plurality of carbon dioxide laser irradiators 32 of step 2 (202) above are continuously irradiated with carbon dioxide lasers to the porous coating substrate 22 passing through the tunnel kiln 30, so that the polypore of the porous coating substrate 22 The imine layer 21 forms the high-purity porous graphene layer 34 because the polyimide layer 21 is irradiated by carbon dioxide laser and absorbs energy, causing the atomic lattice of the polyimide 11 to vibrate, breaking its molecular The C=O and NC bond to make the atoms rearrange the aromatic compounds (Aromatic compounds) to form the porous graphene layer 34; because polyimide 11 contains aromatic and imide (aromatic and imide), so polyimide The imine 11 can finally form the porous graphene layer 34.

Wherein, in step 3 (203), the porous graphene substrates 36 are subjected to a lithiation process, so that the porous graphene substrates 36 form a plurality of lithiated graphene electrodes 38, and the lithiation refers to the lithiation of lithium ions. It is embedded in the gap between the graphene layer and the layer of the porous graphene substrate 36 to facilitate the reaction of lithium ion deintercalation during discharge and lithium ion insertion during charging when it is a negative electrode. The method of lithiation is not limited. All lithiation methods are applicable.

In addition, as shown in FIG. 8, after forming the lithiated graphene electrode 38 in step 3 (203), a plurality of lithiated graphene electrodes 38 can be stacked to form a multilayer lithiated graphene electrode 39.

The lithiated graphene electrode 38 has many advantages. For example, its ultra-thin thickness can accelerate the speed of lithium ions between the positive and negative electrodes; in addition, it has sufficient gaps and pores to increase the charging and discharging rate. It can provide a buffer space for the volume expansion and contraction changes of the electrode during charging and discharging, and avoid damage to the electrode.

As shown in Figure 9, in one embodiment, after the porous graphene substrate 36 is formed in step 2 (202), the porous graphene substrate 36 can be used as an electrode plate 42 of a supercapacitor 40; Parallel plate capacitance formula:

C=ε A/D,

Where C is the capacitance, A is the area of the parallel plates, D is the distance between the parallel plates, ε is the permittivity of the medium between the parallel plates,

Because the porous graphene substrate 36 has more gaps and pores than ordinary electrodes, it has a larger surface area. From the above formula, it can be seen that the larger the surface area, the larger the capacitance, so it can be used as The electrode plate 42 of the supercapacitor 40 has a larger capacitance.

Furthermore, the second electrode plate 46 of the supercapacitor 40 can also be made of a porous graphene substrate 36 as the second electrode plate 46. The surface area of the second electrode plate 46 is also large, which can also increase the capacitance of the supercapacitor 40. big.

As shown in Figure 10, in one embodiment, after the lithiated graphene electrode 38 is formed in step 3 (203), the lithiated graphene electrode 38 can be used as the negative electrode 52 of a lithium ion battery 50; The lithiated graphene electrode 38 has a plurality of graphene layers and gaps between the layers, allowing more lithium ions to be inserted into the gaps, so that the negative electrode 52 of the lithium ion battery 50 has a greater power storage capacity. The lithium ion battery 50 in Figure 10 is illustrated by taking a polymer lithium ion battery as an example. The polymer lithium ion battery is also a general lithium ion battery 50, but the electrolyte of the polymer lithium ion battery is a solid electrolyte. Generally, the lithium ion battery 50 is mainly composed of a positive electrode 56, a negative electrode 52, a separator 54 and the like. The polymer lithium ion battery is also composed of a positive electrode 56, a negative electrode 52, a separator 54 (separator), etc., and the separator 54 is made of solid electrolyte.

To further illustrate, after the foregoing multiple lithiated graphene electrodes 38 are stacked into a multi-layer lithiated graphene electrode 39, the multi-layer lithiated graphene electrode 39 is better than a single-layer lithiated graphene electrode 38, and its graphene layer There are more gaps with the layers, allowing more lithium electrons to be inserted into the gaps, so that the electrode plate 42 of the lithium ion battery 50 has a greater power storage capacity.

In one embodiment, after the formation of the lithiated graphene electrode 38 in step 3 (203), the lithiated graphene electrode 38 can be used as a negative electrode of an Ultracapacitor Lithium Battery, because the lithiated graphene electrode 38 The graphene electrode 38 has a plurality of graphene layers and gaps between the layers, allowing more lithium ions to be inserted into the gaps, so that it can be used as a negative electrode of a supercapacitor lithium battery and has a greater storage capacity.

The manufacturing process method of the graphene electrode plate of the present invention is designed by the aforementioned structure, which can make the porous graphene substrate 36 and the lithiated graphene electrode 38 have the feasibility of mass production; the lithiated graphene electrode 38 can be used as a The negative electrode 52 of the lithium-ion battery 50 can be used as the electrode plate 42 of the lithium-ion battery 50 to have a greater storage capacity; the porous graphene substrate 36 can be used as an electrode plate 42 of a supercapacitor 40, so that it can be used as a supercapacitor The electrode plate 42 of 40 has a larger capacity; its lithiated graphene electrode 38 can be used as The negative electrode of a supercapacitor lithium battery enables the production and application of the process method of the graphene electrode of the present invention to achieve excellent economic benefits.

In summary, the present invention is indeed an excellent creative idea, and an invention patent application was filed in accordance with the law; however, the content of the above description is only a preferred embodiment of the present invention, and everything extended by the technical means of the present invention Changes should fall within the scope of the patent application of the present invention.

201: Step 1

202: Step 2

203: Step 3

Claims (10)

A manufacturing process method of graphene electrode, which includes: Step 1: Take liquid polyimide, form mist particles from the liquid polyimide by ultrasonic spray, and then infiltrate a porous substrate with multiple pores, so that the porous substrate is placed on the porous substrate. A polyimide layer is attached to the periphery of the pores, thus forming a porous coating substrate; Step 2: The porous coating substrate is moved in a tunnel kiln by a conveyor belt. The tunnel kiln is provided with a plurality of carbon dioxide laser irradiators, and the carbon dioxide laser irradiators are used with carbon dioxide lasers. Continuous irradiation of the porous coating substrate through the tunnel kiln causes the polyimide layer of the porous coating substrate to form a high-purity porous graphene layer, thus forming a porous graphene substrate. For the process method of the graphene electrode described in the first item of the patent application, step 2 can be followed by a step 3: the porous graphene substrate is subjected to a lithiation process to form the porous graphene substrate A lithiated graphene electrode. As described in the first item of the scope of patent application, the process method of graphene electrode, wherein the liquid polyimide is formed into mist particles by ultrasonic spraying method and then penetrated into a porous substrate with multiple pores. At least one or a plurality of ultrasonic sprayers infiltrate the mist particles of liquid polyimide into a porous substrate, and the at least one or a plurality of ultrasonic sprayers are arranged on the inner side, upper inner or lower inner of the tunnel kiln. As described in item 3 of the scope of patent application, the method for manufacturing a graphene electrode, wherein the porous substrate is a roll substrate and has a first surface and a second surface, and the porous substrate is disposed on a first surface. On the rotating shaft, the porous substrate is exposed upward with the first surface, and is transported by the conveyor belt into the tunnel kiln to move, so that the first surface of the porous substrate receives the plurality of ultrasonic sprayers to disperse the liquid polyimide The mist particles sprayed into the porous substrate, and then received the carbon dioxide laser irradiator in the tunnel kiln to continuously irradiate the carbon dioxide laser to form the polyimide layer of the porous coating substrate The high-purity porous graphene layer is then placed in a roll on a second rotating shaft; Next, move the second rotating shaft to roll the porous substrate on the second rotating shaft through a turning idler, so that the porous substrate is exposed upward with the second surface, and is transported by the conveyor belt into the porous substrate. Move in the tunnel kiln to make the second surface of the porous substrate receive the plurality of ultrasonic sprayers to spray the mist particles of liquid polyimide into the porous substrate, and then receive the plurality of ultrasonic sprays in the tunnel kiln The carbon dioxide laser irradiator continuously irradiates the carbon dioxide laser to make the polyimide layer of the porous coating substrate form a high-purity porous graphene layer, which is then rolled on a third rotating shaft to form a polyimide layer. Porous graphene substrate. The process method of graphene electrode as described in the first item of the patent application, wherein the liquid polyimide is a liquefied Katpon®, and the porous substrate is selected from one of the following: porous carbon material Substrate, porous graphite, porous metal substrate. As described in the first item of the scope of patent application, a method for manufacturing a graphene electrode can also be used to stack a plurality of lithiated graphene electrodes into a multilayer lithiated graphite after forming the lithiated graphene electrode in step 2 Olefin electrode. The method for manufacturing a graphene electrode as described in the first item of the scope of patent application, wherein the porous graphene substrate is used as an electrode plate of a supercapacitor. As described in item 2 of the scope of patent application, the method for manufacturing a graphene electrode, wherein the lithiated graphene electrode is used as a negative electrode of a lithium ion battery. As described in item 2 of the scope of patent application, the method for manufacturing a graphene electrode, wherein the lithiated graphene electrode is used as the negative electrode of a supercapacitor lithium battery. A manufacturing device for graphene electrodes, which includes: A tunnel kiln with a conveyor belt inside; Multiple ultrasonic sprayers are installed in the tunnel kiln; Multiple carbon dioxide laser irradiators are installed in the tunnel kiln; In the foregoing configuration, the ultrasonic sprayer is used to set the liquid polyimide and spray the liquid polyimide into mist particles, and the carbon dioxide laser irradiator is used to provide continuous irradiation of the carbon dioxide laser.

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