WO2005059934A1

WO2005059934A1 - Printed board with built-in capacitor

Info

Publication number: WO2005059934A1
Application number: PCT/JP2004/018107
Authority: WO
Inventors: Takaharu Kitamura; Hideki Shiozaki
Original assignee: Hitachi Zosen Corporation
Priority date: 2003-12-16
Filing date: 2004-11-30
Publication date: 2005-06-30
Also published as: JP2005183443A

Abstract

According to the invention, a pair of electrodes (24, 25) each having numerous carbon nanotubes on one side are disposed in a case (21) in such a way that the carbon nanotubes (22) on one electrode (24) are opposed to the carbon nanotubes (23) on the other electrode (25) with a separator (26) interposed therebetween. The case (21) is filled with electrolyte, and the carbon nanotubes (22, 23) are impregnated with it. The electric double layer capacitor exhibits a capacitance of 3 mF/cm2. The electric double layer capacitor is incorporated in each of many through holes made in an insulating plate frame and arranged in a predetermined pattern. Therefore, these electric double layer capacitors can be connected near a high-speed operating element to a capacitor with a required capacitance. As a result, no special space for installing a capacitor is needed, and no long connection wiring between high-speed operation elements is needed.

Description

Technical field of printed circuit board with built-in capacitor.

The present invention relates to an electric double layer capacitor using carbon nanotubes capable of storing a large amount of electricity, a printed circuit board for an electronic circuit incorporating the electric double layer capacitor, and a printed circuit board incorporating the capacitor. Background of the Invention

When an electronic circuit is composed of high-speed electronic circuit elements (high-speed operation elements), a large current required for high-speed operation must be supplied to the high-speed operation elements on the printed circuit board. For this reason, it is necessary to arrange a storage capacitor near the element.

When a high-speed electronic circuit is configured on a printed circuit board, a capacitor is placed near the high-speed operation element to supplement the supply of necessary current, and the wiring length between the high-speed operation elements is made as short as possible. Is required. However, installing a capacitor in the vicinity of a high-speed operation element requires an installation space and increases the wiring length, which contradicts the above demand. In addition, electromagnetic radiation such as EMI (Electro Magnetic Interface) is also a problem due to the high impedance of the power supply line.

An object of the present invention is to solve the above contradictions. Disclosure of the invention

According to the first invention, a pair of electrodes having a large number of carbon nanotubes on one side face a carbon nanotube group of one electrode and a carbon nanotube group of the other electrode via a separator. An electric double-layer canopy, in which a group of carbon nanotubes is impregnated with an electrolyte. Sita.

According to a second aspect of the present invention, one internal electrode having a large number of carbon nanotubes on both sides is sandwiched by a pair of side electrodes having a large number of carbon nanotubes on one side via a separator. The pair of side electrodes are arranged so that the carbon nanotube group of one side electrode and the carbon nanotube group of the other side electrode face each other, and the carbon nanotube group is impregnated with the electrolyte. This is an electric double layer capacitor.

In the third invention, a plurality of internal electrodes having a large number of carbon nanotubes on both surfaces are arranged in a multilayer through a separator, and this multilayer internal electrode group is composed of a pair of a plurality of carbon nanotubes having a large number of carbon nanotubes on one surface. Side electrodes, with side electrodes. The pair of side electrodes are arranged so that the carbon nanotubes of one side electrode and the carbon nanotubes of the other side electrode face each other, and the pair of side electrodes are electrolyzed to the carbon nanotube group. This is an electric double layer capacitor impregnated with liquid.

According to a fourth invention, the electric double layer capacity according to any one of the first to third inventions is fitted into each through hole of an insulating plate frame having a large number of through holes in a predetermined pattern, and circuit layers are provided on both sides. This is a printed circuit board with a built-in capacitor.

According to a fifth aspect of the present invention, the electric double layer capacitor according to any one of the first to third aspects is fitted into each of the uncured insulating plate frames having a large number of through holes in a predetermined pattern. Cured, This is a method for manufacturing a printed circuit board with a built-in capacitor, in which circuit layers are laminated on both sides of a cured insulating plate frame.

In a sixth aspect, the electric double layer capacitor according to any one of the first to third aspects is fitted into each through hole of a hardened insulating plate frame having a large number of through holes in a predetermined pattern. A circuit board is built on both sides of a board frame.

Each of the electric double layer capacitors according to the first to third inventions shows a large capacitance with a small area. For example, the electric double layer capacitor according to the first invention has a large capacitance of 3 mF / cm ² .

The insulating plate frame may be a sheet obtained by impregnating a woven fabric of reinforcing fibers such as carbon fiber and glass fiber with a thermosetting resin, for example, a sheet obtained by hardening a pre-preda. As shown in FIG. 13, the pattern of the through holes (9) provided in the insulating plate frame (10) is usually a grid having a plurality of through holes (9) arranged vertically and horizontally. The plurality of through-holes (9) may be provided directly on the entire insulating plate frame (10), or may be unevenly provided on required portions of the insulating plate frame (10) as shown in FIG. Good. In the latter case, one high-speed operation element (19) can be arranged by covering the electric double-layer capacitor (8) inserted into the plurality of through holes (9).

In the present invention, by arranging the size of the basic capacitor so as to match the wiring pitch of the printed board, it is possible to simplify the arrangement of the through holes connecting the wiring layer and the capacitor layer. By connecting a plurality of capacitors in series or in parallel, a desired capacitor capacity can be realized.

The structure of the carbon nanotube may be a single-walled or single tube, or a multi-walled or concentric tube of different diameters. —It may be a group. The diameter of the carbon nanotubes is preferably 1 to: LOO nm.

A carbon nanotube is an ultra-fine tube-like substance with a hole diameter of nanometers (one nano is one billionth of a billion) formed by meshing carbon atoms. Since the electrolyte ion diameter of a normal electrolyte is about 0.4 to 0.6 nm, it is preferable for the adsorption and desorption of force ions having a hole diameter of 1 to 2 nm. In addition, by orienting the carbon nanotubes substantially vertically, the absorption and desorption of the ions are further smoothed, and even when the discharge current is increased, the capacity does not decrease much, so that it can be used for a long time.

The carbon nanotube constituting the electrode can be produced by a known method. For example, an Fe film is patterned by photolithography on at least one surface of a silicon substrate, and acetylene (C ₂ H ₂ ) gas is used to form a general chemical vapor deposition (CVD) method on this surface. Method). In this method, carbon nanotubes having a diameter of 12 to 38 nm are raised substantially vertically on a substrate in a multilayer structure. The carbon nanotubes grown in this way are transferred from the silicon substrate to a current collector provided with an adhesive and adhered. The adhesive layer is preferably made of a conductive paste. The current collector is made of a conductive material such as aluminum. The electrolyte of the electric double layer capacitor is non-printed tones such as propylene carbonate, 1-butylene carbonate, snoreholane, acetonitril, y-butyltyl lactone and dimethylformamide. Organic solvent such as tetrafluoroammonium perchlorate, tetrafluoroammonium hexafluorophosphate, and tetrachlorammonium perchlorate, or lithium, With cations such as quaternary phosphonium _{_{BF 4 -, PF 6 -,}} C 1 0 4 -ヽCF ₂ obtained by dissolving a Anio down or Ranaru inorganic solutes, such as SO ₂ and an aqueous solution-based electrolyte, such as diluted sulfuric acid containing a salt of La Ntano Lee de elements such A liquid, or a polymer type electrolytic solution obtained by adding a polymer substance to the liquid, or the like can be used. According to the present invention, the electric double-layer canister is incorporated in each of the holes of the insulating plate frame having a large number of holes in a predetermined pattern. Can be connected to Therefore, no special space is required for installing capacitors, and long connection wiring between high-speed operation elements is not required. Simple theory of drawing

FIG. 1 is a vertical sectional view schematically showing an electric double layer capacitor in Example 1.

FIG. 2 is a vertical sectional view schematically showing an electric double-layer capacitor in Example 2.

FIG. 3 is a vertical sectional view schematically showing an electric double layer capacitor according to the third embodiment.

FIG. 4 is a vertical sectional view schematically showing a first step in the fourth embodiment.

FIG. 5 is a vertical sectional view schematically showing the steps 2 1 and 3 in Example 4.

FIG. 6 is a vertical sectional view schematically showing a fourth step in the fourth embodiment.

FIG. 6 is a vertical sectional view schematically showing a sixth step in Example 4.

FIG. 8 is a vertical sectional view schematically showing a seventh step in Example 4. FIG.

FIG. 9 is a vertical sectional view schematically showing a first step and a second step in Example 5.

FIG. 10 is a vertical sectional view schematically showing a third step in Example 5.

FIG. 11 is a vertical sectional view schematically showing a fourth step in Example 5.

FIG. 12 is a vertical sectional view schematically showing a fifth step in Example 5.

FIG. 13 is a plan view schematically showing an example in which a plurality of through-holes form a grid-like pattern arranged vertically and horizontally.

FIG. 14 is a plan view schematically showing an example in which a plurality of through holes are unevenly distributed in necessary portions of the insulating plate frame. BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be specifically described based on examples. Example 1

In FIG. 1 showing the electric double layer capacitor according to the first invention, in a container (21), a pair of electrodes (24) and (25) each having a large number of carbon nanotubes on one side are connected via a separator (26). Thus, the carbon nanotube (22) of one electrode (24) and the carbon nanotube (23) of the other electrode (25) are arranged to face each other. An electrolytic solution is injected into the container (21) and impregnated in the carbon nanotubes (22) and (23). This electric double layer capacitor has a large capacitance of 3 mF / cm ² .

Example 2

In FIG. 2, which shows the electric double-layer capacity according to the second invention, in the container (21), a large number of carbon nanotubes (2 7) is sandwiched by a pair of side electrodes (24) (25) having a large number of carbon nanotubes on one side via a separator (26). ing. The pair of side electrodes (24) and (25) are arranged such that the carbon nanotube (22) of one side electrode (24) and the carbon nanotube (23) of the other side electrode (25) face each other. Are located. Electrolyte is injected into the container (21) and impregnated into the carbon nanotubes (22) (23) (27).

Example 3

The electric double layer cano according to the third invention. In FIG. 3, which shows a pit, a plurality of internal electrodes (29) having a large number of carbon nanotubes (27) on both sides are arranged in a multilayered manner via an internal separator (26) in a container (21). The multi-layered internal electrode group (30) thus configured is composed of a pair of side electrodes (24) (25) having a large number of carbon nanotubes on one side, and sandwiched via a separator (26). It has been tipped. The pair of side electrodes (24) and (25) are arranged such that the carbon nanotube (22) of one side electrode (24) and the carbon nanotube (23) of the other side electrode (25) face each other. It is arranged as follows. The electrolytic solution is injected into the container (21) and impregnated in the carbon nanotubes (22), (23) and (27).

Example 4

1st step

In FIG. 4, after patterning a Fe film by photolithography on one surface of a low-resistance N-type semiconductor silicon substrate having a thickness of l mm x l mm mm XO .5 mm, acetylene was applied. At a flow rate of 30 m 1 / min and a temperature of 700 ° C. for 15 minutes, countless carbon nanotubes were grown on the substrate in a brush-like manner by chemical vapor deposition. The obtained carbon nanotube had a multilayer structure, a diameter of 12 nm, and a length of 5 Ozm. This was carbon nanotubes grown from the silicon co emissions substrate, an aluminum two © beam thin plate subjected to adhesive layer made of conductive paste Bok made on the current collector to the surface 1 5 0 ° CZ 4 9 N cm 2 The image was transferred by heating and pressing. Thus, a pair of electrodes (1) and (2) each having a large number of carbon nanotubes (3) and (4) on one side were obtained. 2nd step

In Fig. 5, a pair of electrodes (1) and (2) each having a large number of carbon nanotubes on one side were placed in a vessel (6) in a nitrogen atmosphere under a dew point (temperature: 60 ° C, no water). The carbon nanotube (3) of one electrode (1) and the carbon nanotube (4) of the other electrode (2) are arranged so as to face each other via a separator (5). (17) was produced. Thereafter, drying was performed at 150 to 200 for 24 hours.

3rd step

Similarly, in Fig. 5, the electrolyte solution (tetracarbon ammonium trifluorocarbonate solution (concentration = 1 m01 x 1)) was placed in a glove box under a dry nitrogen atmosphere. (6), and impregnated into carbon nanotubes (3) and (4). The amount of the electrolyte was 1-3 cc / cm ² .

Thereafter, the mouth of the container (6) was swaged with a stainless steel lid (7) using a polypropylene gasket and sealed. Thus, an electric double-layer capacitor (8) having the upper electrode (1) as the anode and the lower electrode (2) as the cathode was produced.

4th step

As shown in FIG. 6, an unhardened insulating plate frame (10) having a plurality of rectangular through holes (9) was prepared. The uncured insulating plate frame (10) is composed of a prepreg. As shown in Fig. 13, the through holes (9) have a plurality of through holes (9) in a grid pattern arranged vertically and horizontally. The electric double layer capacitor (8) obtained in the previous step was fitted into each through hole (9) of the uncured insulating plate frame (10). Thus, an uncured insulating plate frame (10) with a built-in capacitor was manufactured. The thickness of the uncured insulating plate frame (10) is the same as the thickness of the electric double layer capacitor (8), so that both sides of the capacitor-embedded unhardened insulating plate frame (11) are flush with each other. And came.

Step 5

Similarly, in FIG. 6, a circuit layer (12) having an aluminum or copper circuit (13) is laminated on both sides of the insulating plate frame (11) with a built-in capacitor, and electronic components are placed on the upper circuit layer (12). The installation layer (14) was stacked.

Step 6

After that, as shown in Fig. 7, the pre-prepader constituting the uncured insulating plate frame (10) is thermally cured, the electric double layer capacitor (8) is fixed to the cured insulating plate frame (10), and the capacitor is assembled. An insulating plate frame (11) was obtained.

Step Ί

As shown in Fig. 8, the through-horn (15) penetrates the insulation board frame (11), the circuit layer (12), and the electronic component installation layer (14), and connects to the circuit (13) at the required position. Was opened. In this way, a printed board with built-in capacitors (16) was fabricated. A high-speed operation device is placed on the electronic component installation layer (14) and connected to the through hole (15).

¾

In order to increase the adhesive strength between the cured insulating plate frame (10) and the circuit layer (12), an insulating plate is interposed between the cured insulating plate frame (10) and the circuit layer (12), and the circuit (13) It may be configured to connect an electric double layer capacitor (8). Example 5

1st step

By the same operation as in the first step of Example 4, a pair of electrodes (1) and (2) each having a large number of carbon nanotubes on one surface were obtained.

2nd step

Sandwich (17) was obtained by the same operation as in the second step of Example 4. This is shown in Figure 9.

3rd step

As shown in FIG. 13, a cured insulating plate frame (20) having many rectangular through holes (1) was prepared. The hardened insulating plate frame (20) is formed by hardening a pre-preda, and the plurality of through holes (9) form a checkerboard pattern arranged vertically and horizontally.

In FIG. 10, the sand and the switch (17) obtained in the previous step are fitted into each through-hole (9) of the cured insulating plate frame (20), and the capacitor-mounted cured insulating plate frame (18) is attached. Produced. The thickness of the hardened insulating plate frame (20) was the same as the thickness of the sand switch (17), and therefore both side surfaces of the capacitor-mounted insulating plate frame (18) were flush with each other.

4th step

As shown in Fig. 11, a circuit layer (12) containing an aluminum or copper circuit (13) is laminated on both sides of the insulating plate frame (18) with a built-in capacitor, and the upper circuit layer (12) An electronic component installation layer (14) was laminated thereon, and an electrolytic solution having the same configuration as in Example 1 was injected into each through-hole (9) under a dry nitrogen atmosphere to impregnate the carbon nanotubes. . The amount of electrolyte was 1-3 cc / cm ² . Step 5

As shown in FIG. 12, a printed circuit board (16) with a built-in capacitor was produced by the same operation as in the seventh step of Example 4.

0 Industrial applicability

The present invention relates to an electric double-layer capacitor using carbon nanotubes capable of storing a large amount of electricity, a printed circuit board for an electronic circuit incorporating an electric double-layer capacitor, and a print incorporating the capacitor. A method for manufacturing a substrate is provided.

1

Claims

The scope of the claims

1. A pair of electrodes, each having a large number of carbon nanotubes on one side, are arranged so that the carbon nanotubes of one electrode and the carbon nanotubes of the other electrode face each other via a separator. An electric double-layer capacitor made by impregnating an electrolyte into a group of nanotubes.

2. One internal electrode having a large number of carbon nanotubes on both sides is sandwiched via a separator with a pair of IJ electrodes having a large number of carbon nanotubes on one side. The electrodes are arranged so that the carbon nanotube group of one side electrode and the carbon nanotube group of the other side electrode face each other, and the carbon nanotube group is impregnated with an electrolytic solution. Cap evening.

3. A plurality of internal electrodes having a large number of carbon nanotubes on both surfaces are arranged in multiple layers via a separator. The multilayer internal electrode group has a large number of carbon nanotubes on one side. The pair of side electrodes is sandwiched and sandwiched via a side separator, and the pair of side electrodes is composed of the carbon nano tube group of one side electrode and the carbon nano tube group of the other side electrode. The tuples are arranged so as to face each other, and the electrolytes are impregnated in the force nanotubes.

4. The electric double layer canister according to any one of claims 1 to 3 is fitted into each through hole of an insulating plate frame having a large number of through holes in a predetermined pattern, and circuit layers are provided on both sides. A printed circuit board with a built-in capacitor.

5. The electric double-layer capacitor according to any one of claims 1 to 3, wherein the electric double-layer capacitor has an uncured insulation having a large number of through holes in a predetermined pattern. A method of manufacturing a printed circuit board with a built-in capacitor, wherein the circuit board is fitted into each through hole of the board frame, then the insulating board frame is cured, and circuit layers are laminated on both sides of the cured insulating board frame.

6. The electric double layer capacitor according to any one of claims 1 to 3 is fitted into each of the through holes of the cured insulating plate frame having a large number of through holes in a predetermined pattern, and then the cured insulating plate frame is A method for manufacturing a printed circuit board with a built-in capacitor, in which circuit layers are stacked on both sides.