JPH01124248A - Electronic component - Google Patents

Abstract

PURPOSE:To enhance resistance to a bend and to realize a thin shape by a method wherein a solid electrolytic cell element containing a plastic resin is formed collectively together with a printed-circuit board. CONSTITUTION:A solid electrolytic sheet is obtained after a solid electrolytic mixture where an ion-conductive solid electrolytic powder has been dispersed in a plastic resin is stretched. In the same manner, an electrode sheet is obtained after an electrode material mixture where an electrode material has been dispersed in an organic binder together with the solid electrolytic powder or/and a conductive material as necessity requires is stretched. The electrode sheet, the SE sheet and the electrode sheet are piled up in this order; these are molded collectively in order to form a cell element 2; this cell element is pressure- bonded onto a printed-circuit board 1 by heating as necessity requires or is bonded collectively by using an appropriate adhesive.

Description

[Detailed Description of the Invention] Industrial Application Field The present invention is a solid electrolyte battery in which all battery components are solid materials, and is formed integrally with a printed circuit board on which battery parts such as an IC chip, a capacitor, and a resistor are provided. Regarding electronic parts. More specifically, the present invention relates to an electronic component in which a power storage/power generation element is integrated, which can be used as is in an IC card or the like without requiring an external power source such as a conventional button battery.

BACKGROUND OF THE INVENTION In recent years, the integration of semiconductors has progressed, leading to the emergence of electronic devices that have various functions on a single IC chip, such as pocket calculators, electronic watches, and IC cards. Research and development efforts are underway to develop energy storage and power generation devices such as small, thin batteries and solar cells as a source of electricity.

These ICs or electronic devices (hereinafter referred to as one-chip IC devices) are IC chips equipped with functions necessary for calculation, storage, etc., resistors, capacitors, display panels such as liquid crystal display boards, and electricity storage/power generation elements. It consists of a solar cell or regular battery and a plastic container to house them.

Furthermore, as we pursue the miniaturization and thinness of these one-chip IC devices, external resistors and capacitors have come to be incorporated into the IC chip, and batteries are no exception (they are packaged in the same package as the IC chip). is about to be incorporated within.

However, since normal batteries use a liquid electrolyte, a special sealed container of a certain size is required to prevent the liquid from flowing out, and it is difficult to integrate the bare battery element, which is not in a container, with an IC chip. is extremely difficult. Further, the heat resistance of normal battery elements is limited to about 86° C., and IC chip packages are usually made at temperatures of 100° C. or higher, making it difficult to integrate them in the assembly process.

On the other hand, solid electrolyte batteries, in which all of the battery components are solid, do not require a special container to house the battery elements, and depending on the materials used, they can have sufficient heat resistance of 100°C or more. , for example, JP-A-60-0
A nonvolatile memory element, such as No. 12679, which is integrally sealed with a solid electrolyte battery element and an IC chip, has been proposed. Furthermore, an all-solid-state power generation/storage device in which a solid electrolyte battery element and a solar cell are integrated has been proposed as in Japanese Patent Application Laid-Open No. 60-264060.

Problems to be Solved by the Invention In all of these cases, solid electrolyte battery elements are used on rigid substrates such as glass plates, or embedded in rigid bodies such as epoxy resin molds. Constructed to resist mechanical shock.

This is because solid electrolyte battery elements obtained by press-molding solid electrolytes and electrode materials that are solid inorganic powders are extremely brittle and easily damaged by mechanical impact.

If a solid electrolyte battery element can be integrated with other electronic components on a printed wiring board, which is commonly used in the field of electronic devices, we can expect thinner electronic components with even greater diversity and multifunctionality. However, solid electrolyte battery elements are fragile and it is extremely difficult to integrate them with printed wiring boards that are subject to bending stress. No attempt had been made before.

Means for Solving the Problems The present invention solves the above problems by providing an electronic component in which a solid electrolyte battery element containing a plastic resin is integrally formed on a printed circuit board, and electronic components such as IC chips are provided on this board. This can be solved by doing this.

Preferably, a film-like printed circuit board,
An electronic component is provided in which a flexible film-like solid electrolyte battery element is integrally formed. Furthermore, an electronic component is provided in which film-like solid electrolyte battery elements are integrally formed on almost the entire surface of a film-like printed circuit board. Also,
An electronic component is provided in which a part of a printed wiring part is used as a positive electrode or negative electrode of a solid electrolyte battery element.

Function: In the electronic component of the present invention, since the solid electrolyte battery element containing the plastic resin is integrally formed with the printed circuit board, it can withstand bending stress.

By integrating a film-like printed circuit board and a film-like solid electrolyte battery element, it is possible to create an electronic component with even better bending resistance, and by integrating the solid electrolyte battery element over almost the entire surface of the printed circuit board. By forming
Furthermore, the thickness can be reduced. In addition, by using a part of the printed wiring part as the positive electrode or negative electrode of the solid electrolyte battery element, an electronic component can be created in which the printed circuit board and the battery element are firmly bonded, which simplifies the integration process. Can be done.

EXAMPLES Hereinafter, examples of the present invention will be generally explained, and specific examples will be explained.

A solid electrolyte sheet (hereinafter referred to as an SE sheet) is obtained by stretching a solid electrolyte mixture in which ion-conductive solid electrolyte powder is dispersed in a plastic resin. Similarly, a stain electrode sheet is obtained by stretching an electrode material mixture in which the electrode material is dispersed in an organic binder together with a solid electrolyte powder and/or a conductive material if necessary.

Then, the electrode sheet, SE sheet, and electrode sheet are stacked in this order, and these are integrally molded to form a battery element, and this battery element is bonded onto a printed circuit board by pressing while heating as necessary, or by bonding with a suitable adhesive. Unify.

Alternatively, an appropriate solvent can be added to a solid electrolyte mixture or an electrode material mixture to form a solid electrolyte mixture slurry or an electrode mixture slurry, and this can be applied directly onto a printed circuit board to form an electronic device in which the battery element and the printed circuit board are integrated. It can also be used as a component.

Note that the solid electrolyte battery element can be integrally formed on both sides of the printed circuit board, on either surface, or embedded in the printed circuit board. The solid electrolyte battery element may occupy almost the entire surface of the printed circuit board, or may occupy a portion thereof.

Further, a plurality of solid electrolyte battery elements having different voltages or the same voltage can be integrally formed on a plurality of printed circuit boards.

Solid electrolyte powders include LiI, LiI・H2O, Li
3N, Li ion conductive solid electrolyte such as L14Slo4-Li3Po4, RbAg4I, Ag3SI.

AgI-Ag20-Mob3if Russ et al. (DAq ion conductive solid electrolyte, RbCu4l2-xC13+x(
I=0.2~~0.6), CuI-Cu20-MoO2
Cu” ion conductive solid electrolyte, H3Mo
12Po4゜・29H2o, H3W12PO40・29
H ion conductive solid electrolyte such as H2O, or sodium beta alumina (Na-β-A1203), N
A Na ion conductive solid electrolyte represented by a1+aZr2P2-aSiao1□ (a=o to 3) or the like can be used.

Among the solid electrolytes mentioned above, RbCu4 "1.75"3.
25.

RbCu4I4. , CI! 3.6. RbCu4I,
, 2s C13,76 etc. FLbCu412-xC%+
, (X=0.2-0.6) is the most preferable Cu-on conductive solid electrolyte having a high ionic conductivity of 1O-2S/c111 at room temperature.

Electrode materials include graphite, carbon materials such as acetylene-Branna activated carbon, titanium sulfide, and niobium sulfide.

Sulfides such as molybdenum sulfide, copper sulfide, silver sulfide, lead sulfide, silver Chebrel, copper Chebrel, iron sulfide, tungsten oxide, vanadium oxide, chromium oxide.

Molybdenum oxide, titanium oxide, iron oxide, silver oxide.

Oxides such as copper oxide, halides such as silver chloride and iodized steel,
Copper, silver, lithium, gold, platinum, titanium, alloys of these,
Alternatively, there are metal materials such as stainless steel. In particular, copper shuvrels are most preferred because they have heat resistance of 200° C. or higher.

A solid secondary battery element can be constructed by combining the solid electrolyte with an electrode material that electrochemically transfers ions to and from the solid electrolyte, such as titanium disulfide or copper shuvrel.

Although the solid electrolyte does not exchange ions with the solid electrolyte, a solid electric double layer capacitor can be constructed by using an electrode material that forms an electric double layer at the interface with the solid electrolyte, such as activated carbon. The solid electrolyte battery element of the present invention also includes an electric double layer capacitor having the above configuration.

Examples of the plastic resin include 1,4-polybutadiene, natural rubber, polyisoprene, and SBR.

NBR, EPDM, EPM, urethane rubber, polyester rubber, chloroprene rubber, epichlorohydrin rubber, silicone rubber, nutyrene-butadiene-styrene block copolymer (SBS).

Styrene-isoprene-styrene block copolymer (S
IS), butyl rubber, phosphazencom.

Polyethylene, polypropylene, polyethylene oxide, polypropylene poxide, polystyrene.

Vinyl chloride, ethylene-ethyl acetate copolymer, 1゜2-
Polybutadiene, epoxy resin, phenolic resin, cyclized polybutadiene, cyclized polyisoprene, polymethac IJ
) Methyl phosphate and mixtures thereof.

In the SE sheet made of a mixture of plastic resin and solid electrolyte powder, the volume fraction of the solid electrolyte powder is 56 to 96%.
, preferably 75 to 92%. When the volume fraction is less than 65%, the ionic conductivity decreases to 1/1000 to 10000 times compared to the powder state, and even in the Rb Cu 4I2-xcls +8 system, which has the highest conductivity, 13C1
If it is less than 0-6, it becomes unsuitable for practical use.

Furthermore, if the volume fraction exceeds 95%, the resulting SE sheet becomes brittle and easily falls off when formed into a sheet.

In an electrode sheet composed of a mixture of a plastic resin, an electrode material powder, and, if necessary, a solid electrolyte powder and/or a conductive material powder, the volume fraction of these powders is preferably 75 to 96%. When the volume fraction is less than 76%, the contact efficiency between the electrode material powder and the solid electrolyte powder in the electrode layer decreases, making it impossible to obtain sufficient polarization characteristics as an electrode, and when the volume fraction exceeds 96%. When formed into a sheet, it becomes brittle and easily falls off.

There are no particular limitations on the method of dispersing solid electrolyte powder, electrode material powder, or both in a plastic resin to obtain a mixture for SE sheets or electrode sheets. A method of kneading a dissolved plastic resin solution, solid electrolyte powder, electrode material powder, etc. using a ball mill or the like may be mentioned.

Examples of solvents used in this case include non-water-absorbing solid electrolyte powders such as n-hexane, n-hebutane, n-octane, cyclohexane, benzene, toluene, xylene, ethyl acetate, and torculene.

It is preferable to use a saturated hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, or an ester solvent that does not react with the electrode material powder.

Next, the printed circuit board used in the present invention is not particularly limited, but is made of copper, silver, Kovar, nickel, carbon, or gold on a polyester film or polyimide film on a normal phenol resin or epoxy resin laminate. A plated printed circuit can be used. Printed circuit boards with multilayer wiring can also be used.

(Example 1) FIG. 1 shows a specific example of the present invention, in which a printed circuit board 1
FIG. 2 is a diagram schematically showing the configuration of an electronic component in which a solid electrolyte battery element 2 and a solid electrolyte battery element 2 are integrally formed. 3 is a copper wiring pattern obtained by etching the copper foil of a copper-clad glass epoxy board (size: 50 x 80 mm, thickness: o, ss+s). 4 is an LSI chip equipped with an arithmetic unit and a storage unit, and 6 is an I
IC chip for C drive, 6 is chip capacitor,
7 is a chip resistor.

A solid electrolyte battery element 2 was integrally formed by screen printing on a printed circuit board 1 on which a copper wiring pattern 3 had been formed in advance.

Nylenenibutadiene-styrene block copolymer (S
A sephorimer solution was obtained by dissolving 0.1 part by weight of BS, specific gravity 0.96) in toluene, and this was added with RbCu4I, 6CI!
Copper ion conductive solid electrolyte powder expressed by 3.5 (specific gravity:
4.5) was added and mixed in a ball mill to obtain a solid electrolyte mixture slurry. In addition, a similar polymer solution was mixed with a similar solid electrolyte powder and a copper shuvrel compound, which is an electrode material represented by Cu3Mo6S8, at a weight ratio of 1:1.
(specific gravity: about 4.7) were mixed to obtain an electrode material mixture slurry.

The electrode material slurry is printed in a size of 18 x 18 m on a predetermined copper wiring pattern on a printed circuit board through a 200 mesh Silk Nuclean, and the solvent is dissipated at 80°C to form an electrode layer that acts as a negative electrode. Similarly, a solid electrolyte mixture slurry is printed in a size of 19×19 so as to completely cover this electrode layer to form a solid electrolyte layer. Further, add 20x20m of electrode material mixture slurry.
An electrode layer that functions as a positive electrode is formed by printing to cover the solid electrolyte layer to a size of . Furthermore, carbon paint (manufactured by Nippon Acheson Co., Ltd., ED423SSA)
After printing and baking, the same printing process is repeated to form a solid electrolyte battery element with a thickness of approximately 0.0 mm, in which two solid electrolyte battery elements are connected in series.
A 18JEI battery was integrally formed.

By charging the battery obtained in this way with an external power source, an average voltage of 1.0 volts and a current of 3 μA can be generated at 20 volts.
It can be supplied to the LSI chip 4 and IC chip 6 for 0 hours.

The electronic components obtained in this way can be used as is as an IC card, and an IC card using an LSI chip incorporating SRAM memory (see 4) can retain data for about 1.5 months on a single charge. was.

When the obtained electronic component was subjected to a bending resistance test at a radius of 80181, it operated normally even after repeated testing 500 times.

Note that copper turns (carbon, nickel, silver, etc. instead of turns) may be used as the printed circuit pattern; By also serving as the lead-out electrode of a battery using a solid electrolyte, the flint board and battery element can be more firmly integrated, and the printed circuit board and battery element can be made into electronic components that are less likely to separate from each other due to mechanical shock. can.

It is thought that some of the copper in the wiring pattern dissolves into the electrode layer of the battery element and acts to chemically and firmly bond the printed circuit board and the battery element.

(Example 2) A battery with a thickness of 0.28 m in which three cells are connected in series as a solid electrolyte battery element is integrated with a printed circuit board,
Furthermore, a solar cell module 8 with a thickness of 0.3M, in which 3 amorphous Si solar cells of size 10x10all are connected in series, is pasted on a polyimide film with a thickness of 0.1j11. In this case, the battery element is fully charged in about 10 minutes and can provide an average voltage of 1.5 volts and a current of 3 μA for 200 hours.

The reason why charging is possible in such a short time is because the polarization material is Cu.
This is thought to be due to the use of a copper shuvrel compound, which has a high rate of + ion transfer.

When the obtained electronic component was subjected to the same bending resistance test as in Example 1, it operated normally even after 5000 repeated tests.

(Example 3) A polyimide film carrier with a thickness of 0.1 M and a width of 20 mm was used as a printed circuit board, and a film-like printed circuit board 9 and a film-like solid electrolyte battery element 10, whose configuration is schematically shown in FIG. 3, were integrated. formed electronic components. In Fig. 3, (3a) is one side of the film-like printed circuit board 9, and on this side is a film-like solid with a thickness of Q and 15 m. [The electrolyte battery element 1o is integrally formed. (3b) is another surface, on which copper wiring 12
Gafu.

The electronic watch LSI chip 11 is integrally formed. (3C) is a schematic diagram showing the cross-sectional structure.

Film-shaped solid electrolyte battery element 1o is obtained as follows. A solid electrolyte mixture slurry similar to that used in Example 1 was cast on a Teflon plate and the solvent was dissipated to obtain a thickness of 0.050 JCI SE receipt, electrode material mixture used in Example 1. I Cm per second through Clary
After forming electrode layers on both sides of the SE receipt, the SE receipt was passed through carbon paint diluted with a solvent (ED423SSA, manufactured by Acheson Japan Co., Ltd.) at the same speed to obtain a battery sheet. Two of the obtained battery sheets were stacked and roller-plained so that the thickness was about 0.15 mm, and then cut into the shape shown in 3a (1 ox 1 sm) to obtain a film-like solid electrolyte battery element.

The obtained battery has an average power of 1 when charged by an external source.
A voltage of 0 volts and a current of 0.6 μA can be supplied for about 200 hours.

When the obtained film-like electronic component was subjected to the same bending resistance test as in Example 1, it operated normally even after 10,000 repeated tests.

(Example 4) A film-like printed circuit board 13゜16 and a film-like solid electrolyte battery whose configuration is shown schematically in FIG. Elements 15 and 17 were integrally formed with a film-like noamorphous silicon film [Ml 4] to constitute an electronic component. In FIG. 4, (4a) is one surface of the film-like printed circuit board 13, and this surface has a thickness o,
Three 001M amorphous silicon solar cells 14 are integrally formed. (4b) On the other side, a solid electrolyte battery element 15 in the form of a film with a thickness of 0.15111 mm is integrally formed, on which two cells with a thickness of 0.07 mm are connected in series. has been done. (4c) is one side of the film-like printed circuit board 16, and on this is a film-like solid electrolyte battery element 17 with a thickness of 0.15 m on which two cells of a thickness of 0.07 aag are connected in series. are integrally formed. (4d) is another surface of the film-like printed circuit board 16, on which a copper wiring 19 is printed and an LSI chip 18 for a calculator is integrally formed. (4e) is a cross section of a film-like electronic component obtained by integrating the film-like printed circuit board 13 and the film-like printed circuit board 16 using a heated press roller so that the stain pond elements 15 and 17 are connected in series. It shows the structure of

Solid electrolyte battery elements 15 and 17 were obtained in the same manner as in Example 3. The resulting cell can be fully charged in about 10 hours under a 200 lux fluorescent light and can provide an average voltage of 2.0 volts and a current of 6 μA for about 20 hours. Further, when the obtained film-like electronic component was subjected to the same bending resistance test as in the example, it operated normally after 10,000 repeated tests.

Effects of the Invention The electronic component of the present invention integrates a printed circuit board and a solid electrolyte battery element containing a plastic resin, that is, it has a built-in dedicated power supply, so it is an active multi-function device that can operate on its own. It is a functional component, and it is flexible and can be formed into an extremely thin shape, so when used in electronic equipment, it can be made thinner and more compact, and it is resistant to external mechanical shock. It can be a device.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of an electronic component according to one embodiment of the present invention, and FIGS. 2 to 4 are schematic diagrams of electronic components according to different embodiments of the present invention. 1.9,13,16...Printed circuit board, 2,1
0゜14.15.17...Solid electrolyte battery element, 4゜11.18...LSI chip, 8,14...
...Solar cells. Name of agent: Patent attorney Toshio Nakao and 1 other person No. 1
Figure-2 Figure 3 Collection Figure 4 Colon battery/BLs etedde

Claims (5)

[Claims] (1) An electronic component characterized in that a solid electrolyte battery element containing a plastic resin is integrally formed on a printed circuit board, and an electronic component such as an IC chip is provided on the printed circuit board. (2) The electronic component according to claim 1, characterized in that a film-like substrate is used as the printed circuit board, and a flexible film-like element is used as the solid electrolyte battery element. (3) The electronic component according to claim 1 or 2, characterized in that a film-like solid electrolyte battery element is provided over almost the entire surface of the printed circuit board. (4) The electronic component according to claim 1, characterized in that a solar cell for charging a solid electrolyte battery element is integrally formed. (5) A part of the wiring section provided on the printed circuit board for electrically connecting electronic components such as IC chips provided on the printed circuit board also serves as the positive electrode or negative electrode of the solid electrolyte battery element. An electronic component according to any one of claims 1 to 4, characterized in that: