JP2012209048A - Printed battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flexible zinc/manganese dioxide printed battery with high electromotive force and long battery life, and to provide a manufacturing method therefor.SOLUTION: The printed battery is constructed by layering a cathode which is formed by printing an anode prepared by printing manganese oxide paste and zinc paste, through a separator impregnated with electrolyte. The electrolyte includes phosphoric acid of 2-25wt%.

Description

  The present invention relates to an electrochemical cell used as a battery power source by converting chemical energy into electrical energy, more particularly a primary cell manufactured by a printing method, i.e. all active elements are printed, The present invention relates to a thin and flexible battery, in particular, a flexible zinc / manganese dioxide-based printed battery having a large electromotive force and a long battery life.

  With the diversification of electronic devices, battery-powered portable electric appliances such as mobile phones, video and still image / sound recorders, liquid crystal displays, calculators, watches, hearing aids, and the like are spreading in the market. Also, medical devices such as greeting cards, postcards, book packages, consumer products such as calendars, information parts such as electronic tags, and medical thermometers or medical patches that are attached to the body and read information such as body temperature and pulse. As a power source suitable for use in various low power consumption products, development of a relatively low-cost, thin, flexible, and environmentally friendly disposable low-energy density battery is in progress.

Such a printed battery is provided with a characteristic battery depending on what kind of material is used for the negative electrode and the positive electrode. Currently, a zinc / manganese dioxide-based primary battery is in a commercial stage, and lithium / manganese dioxide. Primary batteries and lithium ion secondary batteries are under development.
Several patents can be given for zinc / manganese dioxide primary batteries using conventional printing methods. For example, Patent Document 1 discloses a non-woven fabric separator placed between a negative electrode printed with zinc paste and a positive electrode printed with manganese dioxide paste. Thus, a paste-like electrolyte solution composed of zinc perchlorate as an electrolyte, hydroxyethyl cellulose as a binder, and water as a solvent is screen-printed on the negative electrode and used. This battery is characterized in that the reactivity of the negative electrode with zinc is suppressed as compared with the case where a known zinc chloride or ammonium chloride system is used as the electrolyte, so that the utilization efficiency of zinc is improved and the battery life is long.

  Patent Document 2 proposes a new process (structure) for obtaining an integrated thin battery composed of a plurality of battery cells with the same thickness as a single battery cell and with a simple manufacturing process. The current collector is made of a plastic paste such as polyethylene terephthalate (PET) with carbon paste, the negative electrode material is zinc dust / polyvinyl alcohol (PVA) paste, the positive electrode material is manganese dioxide paste, and the separator is non-woven fabric. An example in which zinc chloride / ammonium chloride is used as an electrolytic solution is disclosed.

  Patent Document 3 discloses a zinc / manganese dioxide battery characterized by printing a zinc anode directly on a first portion of a flexible non-conductive substrate material without using a current collector. Screen-printed anode ink (zinc dust / zinc acetate / water / polyvinylpyrrolidone) on anode substrate of flexible polymer-metal laminate package material, dried at 70 ° C. for 5 minutes, then created anode tab, Cathode collector ink and carbon ink (commercially available) as cathode tab printed on cathode substrate of flexible polymer-metal laminate package material, dried under vacuum at 50 ° C for 16 hours, then cathode ink (manganese dioxide) / Graphite / polyvinylpyrrolidone / water), cured at 70 ° C. for 5-10 minutes. Kraft separator paper coated with a mixture comprising starch / natural guar gum / polyvinylpyrrolidone / surfactant additive / water, battery electrolyte (containing 1000 ppm cetyltrimethylammonium bromide, with 600 ppm lead chloride added, 28 A mass% zinc chloride solution), the separator is oriented to face the zinc anode and heat sealed at the periphery.

  Patent Document 4 discloses a base selected from the group consisting of acrylic, alkyd, alginate, latex, polyurethane, linseed oil, and hydrocarbon emulsions as binders for conductive ink, positive ink, and negative ink used in printed batteries. It is characterized by using. For example, the conductive ink suspension has 79 wt% conductive carbon (particle size <0.1 μm) dispersed in an acrylic binder, and the positive ink suspension has 96 wt% manganese dioxide (acrylic binder in an acrylic binder). An example is disclosed in which the particle size <0.4 μm) is dispersed, and the negative electrode ink suspension is prepared by dispersing 96 wt% zinc powder (particle size <0.3 μm) in an acrylic binder.

  Patent Document 5 relates to a zinc polymer thick film composition as a negative electrode material. In an organic medium containing a solvent and a polymer selected from polyhydroxy ether, polyurethane, acrylonitrile / vinylidene chloride copolymer, and a mixture thereof. A zinc polymer thick film composition comprising dispersed zinc particles is disclosed.

  In addition, although it is not a printing battery, in the alkaline battery using the zinc alloy containing aluminum as a negative electrode active material, phosphoric acid which consists of phosphoric acid or the alkali salt of phosphoric acid as electrolyte solution of the gelatinous zinc negative electrode containing this negative electrode active material There is an example using an electrolytic solution containing ions (Japanese Patent No. 2609609). However, this phosphate ion is added as an ion in which aluminum contained in the negative electrode active material interferes with the formation of a unique crystal of zinc under specific discharge conditions. The amount added is 10 to 100 ppm per 1 g of zinc. It is supposed to be contained in the electrolyte. It was confirmed that the addition of phosphate ions eliminates the deterioration of discharge performance at a specific load resistance. The mechanism of action is the formation of unique crystals of zinc due to the presence of phosphate ions. It is presumed that the internal short circuit phenomenon due to the crystal is eliminated, but the patent discloses a trace amount in the alkaline electrolyte of the zinc negative electrode of an alkaline battery using an alkali such as KOH as the electrolytic solution. Phosphoric acid is added, not a substantial amount of phosphoric acid added to the zinc chloride or zinc chloride / ammonium chloride electrolyte of zinc / manganese dioxide primary batteries, and the improvement of electromotive force by the addition of phosphoric acid Is not described at all.

JP-A 61-55866 JP-A-5-54895 JP 2005-518074 gazette JP 2005-527093 A JP 2004-022548 A

  In these zinc / manganese dioxide-based batteries, the electromotive force is about 1.5 V, and the necessity of a battery with a higher electromotive force has been recognized, and if this is obtained, the battery life is extended, which is extremely advantageous. An object of the present invention is to provide a flexible zinc / manganese dioxide printed battery having a large electromotive force and a long battery life and a method for producing the same.

  The present inventor assumed that the electromotive force of the battery depends on the composition of the electrolytic solution to be used, and as a result of examining the electrolytic solution impregnated in the separator of the printing method, as a result of using an aqueous phosphoric acid solution as the electrolytic solution, Although the no-load discharge characteristics are not satisfied, the initial electromotive force has reached about 2V, and further research has made it possible to add phosphoric acid to zinc chloride / ammonium chloride electrolytes and zinc chloride electrolytes. As a result, it was found that a printed battery having a remarkable effect of improving electromotive force and good no-load discharge characteristics can be obtained, and the present invention has been completed. That is, in order to achieve the above-mentioned problems, the invention claimed in the present application is as follows.

(1) A printed battery in which an anode prepared by printing a manganese oxide paste and a cathode formed by printing a zinc paste are laminated via a separator impregnated with an electrolyte solution, the electrolyte solution being 2 A printed battery comprising ˜25 wt% phosphoric acid.
(2) The printed battery according to (1), wherein the electrolytic solution is an ammonium chloride / zinc chloride / phosphoric acid system or a zinc chloride / phosphoric acid system.
(3) The ammonium chloride / zinc chloride / phosphoric acid electrolyte solution is composed of ammonium chloride / zinc chloride / phosphoric acid / water, ammonium chloride 25-28 wt%, zinc chloride 2-12 wt%, phosphoric acid 2-25 wt%, The printed battery according to (2), wherein the water content is 40 to 65 wt%.
(4) The zinc chloride / phosphate electrolyte is composed of zinc chloride / phosphoric acid / water, and is characterized by zinc chloride 50-80 wt%, phosphoric acid 5-25 wt%, and water 15-25 wt% ( The printed battery as described in 2).
(5) The manganese oxide paste and the zinc paste are one or more polymers selected from the group consisting of hydroxyalkyl celluloses, polyvinyl butyral (PVB) and acrylic polyol resins as a binder ( The printed battery according to any one of 1) to (4).
(6) A method for producing a printed battery in which a printed battery is formed by laminating an anode produced by printing a manganese oxide paste and a cathode formed by printing a zinc paste via a separator impregnated with an electrolytic solution. The method for producing a printed battery, wherein the electrolytic solution contains 2 to 25 wt% phosphoric acid.
(7) The method for producing a printed battery according to (6), wherein the electrolytic solution is an ammonium chloride / zinc chloride / phosphoric acid system or a zinc chloride / phosphoric acid system.

  According to the present invention, a flexible manganese oxide / zinc-based printed battery with high electromotive force and low self-discharge property can be obtained.

Sectional drawing which shows the structure of the printed battery of this invention. Explanatory drawing which shows the flowchart of the manufacturing method of the printed battery of this invention. The figure which shows the electromotive force (no load) time-dependent change of the printed battery using various electrolyte solution. The figure which shows the electromotive force (no load) time-dependent change of Examples 1, 2 and Comparative Examples 1, 2. The figure which shows the electromotive force (no load) time-dependent change of Examples 3 and 4 and Comparative Examples 1 and 2. The figure which shows the electromotive force (no load) time-dependent change of Examples 5 and 6 and Comparative Examples 1 and 2. The figure which shows the load discharge characteristic in the printed battery of Example 2. FIG. The figure which shows the electromotive force (no load) time-dependent change of the printing battery from which an electrode binder differs. The figure which shows the influence of an ammonium chloride / zinc chloride / phosphoric acid type electrolyte composition on electromotive force (no load) time-dependent change of a printed battery. The figure which shows the influence of a zinc chloride / phosphate type electrolyte solution composition which exerts on electromotive force (no load) time-dependent change of a printed battery.

  FIG. 1 is a cross-sectional view showing a configuration of a printed battery according to the present invention. This printed battery 10 includes an anode part 1 and a cathode part 2 arranged with a separator 3 sandwiched between a pair of substrates. The anode part 1 is formed by printing and thermosetting a carbon paste or the like on a substrate 4. It consists of a collector electrode 5 and an anode 6 formed by printing and drying a manganese oxide powder paste on the surface of the collector electrode 5, while the cathode portion 2 prints carbon paste or the like on the substrate 4 and the substrate 7. A current collecting electrode 5 formed by thermosetting and a cathode 7 formed by printing and drying a zinc powder paste on the surface of the current collecting electrode 5.

(1) Anode section 1
On a flexible electrically insulating substrate 4 such as a PET (polyethylene terephthalate) film, a carbon paste or the like is printed and thermally cured to form a current collecting electrode (also used as a lead electrode) 5, and manganese oxide as an anode 6 on the surface A paste containing powder (manganese oxide paste) formed by printing and drying.
(2) Cathode part 2
On a flexible substrate such as PET (polyethylene terephthalate), carbon paste is printed and heat-cured to form a collecting electrode (also used as a lead electrode). ) By printing.
(3) Separator 3
It is a porous substance that serves as a spacer for preventing direct contact between the above (1) and (2) and a role for holding an electrolyte solution. The porous body is impregnated with an electrolyte solution. Used.

  In the printed battery of the present invention, as the flexible electrically insulating substrate, in addition to the above-mentioned PET, films such as polyethylene naphthoate (PEN), polyimide (PI), polycarbonate (PC), polysulfone (PS), and aluminum laminate film ( A multilayer film in which an aluminum foil and a sealant layer are laminated on a film such as PET can be used.

A carbon paste is suitably used for the current collecting electrode of the present invention. The carbon paste has good screen printability, forms a flexible film by a curing reaction at a relatively low temperature after printing, has good adhesion with PET, and has an electric resistance of at least lower than 10 ⁻² Ω · cm. What can form a film is preferable.

  In order to form the anode of the present invention, a manganese oxide paste composed of manganese oxide powder, carbon or graphite powder, a binder, an electrolytic solution, a binder solvent, and the like is printed and dried on the current collecting electrode. .

  As the manganese dioxide powder used in the manganese oxide paste of the present invention, those having a purity of> 80%, preferably> 85%, and an average particle size of about 5 to 15 μm can be used as a reagent. Further, carbon or graphite powder may be added to increase the conductivity in the anode. For example, scaly graphite having a particle size of about 5 to 15 μm is preferably used.

  As the electrolytic solution of the manganese oxide paste, ammonium chloride / zinc chloride is used. Moreover, as binder of manganese oxide paste, hydroxyalkyl celluloses such as hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxyethyl methyl cellulose (HEMC), hydroxypropyl methyl cellulose (HPMC), polyvinyl butyral (PVB), polyol Acrylic resin is preferred. Further, as the binder solvent for the manganese oxide paste, a solvent having an evaporation property suitable for screen printing and suitable for the binder to be used is appropriately selected and used, and examples thereof include ethyl carbitol acetate and butyl cellosolve.

  As the zinc powder used in the zinc paste of the present invention, those having a purity of> 99% and an average particle diameter of about 5 to 15 μm are preferably used. As binder of zinc paste, hydroxyalkylcelluloses such as hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxyethylmethylcellulose (HEMC), hydroxypropylmethylcellulose (HPMC), polyvinylbutyral (PVB), acrylic polyol resin, etc. Is preferred. Moreover, the solvent suitable for screen printing is used as a binder solvent for the zinc paste, and a solvent suitable for the binder to be used is appropriately selected and used. Examples thereof include ethyl carbitol acetate and butyl cellosolve.

  As the separator of the present invention, a porous body having affinity for an electrolytic solution and chemical stability is suitable, and examples thereof include cotton (cotton for makeup) and rayon / polyester nonwoven fabric. In addition, as the electrolytic solution used by impregnating the separator in the present invention, ammonium chloride / zinc chloride / phosphoric acid / aqueous electrolytic solution or zinc chloride / phosphoric acid / aqueous electrolytic solution is preferably used.

  In the ammonium chloride / zinc chloride / phosphoric acid / water-based electrolyte of the present invention, ammonium chloride is 25 to 28 wt%, zinc chloride is 2 to 12 wt%, phosphoric acid is 2 to 25 wt% (particularly 5 to 10 wt%), and water is 40 to 65 wt%. The composition of the following is preferable. If the concentration of phosphoric acid does not reach 2 wt%, the effect of improving electromotive force due to the addition of phosphoric acid is poor, and if it exceeds 25 wt%, the effect tends to be saturated. On the other hand, if the concentration of ammonium chloride is too small, a sufficient electromotive force cannot be obtained, and if it is too large, the solubility of the electrolytic solution is deteriorated. If the concentration of zinc chloride is too small, the effect of suppressing electromotive force reduction due to sufficient no-load standing cannot be obtained, and if it is too large, the effect is saturated.

  In the zinc chloride / phosphoric acid / water-based electrolytic solution of the present invention, a composition of zinc chloride 50-80 wt%, phosphoric acid 5-25 wt% (particularly 5-20 wt%), and water 15-25 wt% is preferable. The concentration of zinc chloride is 80 wt% or less, preferably 75 wt% or less, because of its solubility in water. Further, if the concentration of phosphoric acid does not reach 5 wt%, the effect of improving electromotive force due to the addition of phosphoric acid is poor, and if it exceeds 25 wt%, the effect tends to be saturated.

  Next, an example of the method for producing the printed battery of the present invention will be described with reference to FIG. First, a conductive paste is screen-printed to form a collecting electrode (also used as a tab electrode) 5 on a flexible electrically insulating substrate 4A such as PET. Next, a manganese oxide paste for anode is screen-printed so as to cover the current collecting electrode 5 of the substrate 4B with current collecting electrode, and dried to produce a substrate 4C on which the anode 6 is formed. Separately, a substrate 4B with a collecting electrode is prepared in the same manner, and a zinc paste for cathode is screen-printed so as to cover the collecting electrode 5, and dried to produce a substrate 4E on which the cathode 7 is formed. Next, parts of these substrates 4C and 4E are cut out to produce assembly substrates 4D and 4F from which the tab electrodes T1 and T2 protrude. Here, the spacer 3 is allowed to stand on the substrate 4D on which the anode 6 is formed so as to cover the anode portion, and after impregnating a predetermined amount of the electrolytic solution thereon, the cathode 7 is formed on the substrate 4G. The printed substrates 10 of the present invention are completed by stacking the substrates 4F and sealing the periphery with a sealing material or an adhesive.

In addition, although FIG. 2 shows an example of sheet-fed manufacturing, it is possible to mass-produce printed batteries by introducing screen printing multi-sided printing method and continuous printing method by roll-to-roll method. Needless to say.
A specific embodiment of the printed battery according to the present invention according to the flowchart of FIG. 2 will be described below.

[Example 1]
First, a conductive carbon paste (trade name: FTU-16F from Asahi Chemical Laboratory) is screen printed (polyester plate 150 mesh) on a PET substrate (thickness 100 μm, 60 × 60 mm) 4A, current collecting unit 30 × 30 mm, lead A 5 × 15 mm pattern was printed, and heat treatment was performed at 80 ° C. for 15 minutes to form a substrate 4B with a collecting electrode. Here, the carbon paste has good screen printability, forms a flexible film by a curing reaction at a relatively low temperature after printing, has good adhesion with PET, and is at least lower than 10 ⁻² Ω · cm. What can form a film of electrical resistance is preferable. By using such a paste, the conductive film can be formed by heat treatment at 80 ° C. for 15 minutes after printing.

  Next, a manganese oxide paste for anode was screen-printed with a size of 30 × 30 mm so as to cover the current collecting electrode of the substrate 4B with current collecting electrode, and dried to produce a substrate 4C on which an anode was formed. Similarly, the cathode paste was screen-printed with a size of 30 × 30 mm and dried so as to cover the current collecting electrode of the produced current collecting substrate 4B. Thus, a substrate 4E on which the cathode was formed was produced. For screen printing of the electrode paste, a polyester plate 80 mesh was used. Moreover, as an electrode paste, the anodized manganese paste shown in Table 1 (composition examples A1 to A4) and the cathode zinc paste shown in Table 2 (composition examples B1 to B4) were used, both of which were heat-treated at 80 ° C. for 15 minutes after printing. Went.

Next, parts of these substrates 4C and 4E were cut (trimmed) to produce assembly substrates 4D and 4F with protruding lead electrodes.
Furthermore, on the substrate 4B on which the anode is formed, a cotton sheet (manufactured by Avon Products, trade name: Avon Cotton Pad) size 30 × 30 mm and a thickness of 100 to 200 μm is left as a spacer so as to cover the anode portion. This was impregnated with 0.6 to 0.8 g of an electrolytic solution (composition examples C1 to C7) shown in Table 3. A substrate 4F having a cathode formed thereon was overlaid on this substrate 4G, and the periphery was sealed with an adhesive tape to complete the printed battery 10 of the present invention.
The details of the manganese oxide paste for anode, the zinc paste for cathode, and the electrolytic solution are as follows.

(Manganese oxide paste for anode)
The manganese oxide paste for anode is composed of manganese dioxide powder, graphite powder, electrolytic solution, binder and solvent. First grade reagent was used as manganese dioxide powder, and scaly graphite (manufactured by Chuetsu Graphite Industry Co., Ltd., trade name CDF-3) was used as graphite powder. As the electrolytic solution, ammonium chloride (reagent grade 1) / zinc chloride (reagent grade 1) was used. As a binder, hydroxypropyl cellulose (HPC, manufactured by San-Ei Gen F.S.I., trade name KluceNutra W), ethyl cellulose (first grade reagent), polyvinyl butyral (PVB, manufactured by Sekisui Chemical Co., Ltd., trade name S-REC BL-2, solid 23 wt% butyl cellosolve solution), acrylic polyol resin liquid (copolymer of hydroxyl group-containing acrylic monomer and acrylate ester, Toei Kasei, trade name Acrynal # 15-85 (solid content 55 wt%, hydroxyl group equivalent 55 mg KOH / g) Was used.

  The ratio of binder to manganese oxide powder varies depending on the type and molecular weight of the binder used, and it is necessary to select the optimum ratio for each binder. However, the paste has excellent printability and battery characteristics. Manganese oxide powder / binder (resin solid content) = 100/1 to 10 (weight ratio). Further, ethyl carbitol acetate (first grade reagent) and water were used as the solvent, and the addition amount was adjusted so as to obtain a viscosity with good printability.

(Zinc paste for cathode)
The zinc paste for cathode was composed of zinc powder, binder and solvent. As the zinc powder, a commercially available product having a purity of 99% or more and an average particle diameter of 5 to 12 μm was used. Hydroxypropylcellulose (HPC, manufactured by Saneigen FSI, Inc., trade name KluceNutra W), ethylcellulose (first grade reagent), polyvinyl butyral (PVB, manufactured by Sekisui Chemical Co., Ltd., tradename SREC BL-2, solid content as a binder 23 wt% butyl cellosolve solution), acrylic polyol resin liquid (copolymer of hydroxyl group-containing acrylic monomer and acrylate ester, manufactured by Toei Kasei Co., Ltd., trade name Acrynal # 15-85 (solid content 55 wt%, hydroxyl group equivalent 55 mg KOH / g) ) Was confirmed to be extremely effective.
The ratio of binder to zinc powder varies depending on the type and molecular weight of the binder used, and it is necessary to select the optimum ratio for each binder. It is in the range of powder / binder (resin solid content) = 100/1 to 10 (weight ratio).
As the solvent, ethyl carbitol acetate (first grade reagent) and butyl cellosolve (first grade reagent) were used, and the addition amount was adjusted so that the printing property had a good viscosity.

(Electrolyte)
As the electrolytic solution, seven kinds of compositions shown in Table 3 were used. Here, composition example C1 is an ammonium chloride single aqueous solution, composition C2 is a combination of ammonium chloride and diammonium hydrogen phosphate, composition C3 is an ammonium chloride / zinc chloride system, composition C5 is a zinc chloride single aqueous solution, composition The product C7 is a phosphoric acid single aqueous solution, which is used as an electrolytic solution in the comparative examples shown below. Compositions C4 and C6 are electrolytic solutions according to examples of the present invention, the former being an ammonium chloride / zinc chloride / phosphate system, and the latter being a zinc chloride / phosphate composition. The reagent grade 1 was used for all of ammonium chloride, zinc chloride, phosphoric acid, and diammonium hydrogen phosphate.

[Comparative Examples 1-5]
In order to test the characteristics of the electrolytic solution, the printed battery of Comparative Examples 1 to 7 in which the anode paste and the zinc paste were made the same and only the electrolytic solution was changed as follows by the manufacturing process of the printed battery shown in FIG. did.
Comparative Example 1: Electrolytic Solution Composition C3: Ammonium Chloride / Zinc Chloride System Comparative Example 2: Electrolytic Solution Composition C5: Zinc Chloride Only Comparative Example 3: Electrolytic Solution Composition C1: Ammonium Chloride Only Comparative Example 4: Electrolytic Solution Composition C7: Phosphoric Acid Independent Comparative Example 5: Electrolyte composition C2: Ammon chloride / diammonium hydrogen phosphate

Table 4 and FIG. 3 show the results of measuring the initial electromotive force of the printed battery, further allowing it to stand at room temperature, and measuring the electromotive force over time.
From these results, it was found that the ammonium chloride single electrolyte (C1) and phosphoric acid alone (C7) had a severe voltage drop over time in an unloaded state. In addition, those using an electrolytic solution other than the electrolytic solution C7 (Comparative Examples 1 to 3 and 5) have an initial electromotive force level of 1.5V, but those using the electrolytic solution C7 have an initial electromotive force of 1.95V. A peculiar phenomenon that a high voltage appears was discovered.

  Comparative Example 5 is a compound (C2) obtained by adding diammonium hydrogen phosphate to ammonium chloride, which shows similar discharge characteristics to an electrolyte solution (C3) obtained by adding zinc chloride to ammonium chloride. It shows that diammonium hydrogen phosphate has the effect of zinc (electromotive force decrease suppression effect by leaving it unloaded), but the initial electromotive force is at 1.5V level, and the effect of improving the initial electromotive force is It was confirmed that the effect was unique. In addition to diammonium hydrogen phosphate as a phosphate, we tried to prepare an electrolytic solution by combining aluminum phosphate, zinc phosphate, and zinc phosphate with ammonium chloride. However, these metal phosphates have poor water solubility. , Could not be used as an electrolyte.

[Examples 1 to 6]
The printed batteries of Examples 1 to 6 were manufactured by the printed battery manufacturing process described in FIG.
Here, Examples 1 and 2 use PVB as the binder of the electrode paste, Examples 3 and 4 use acrylic polyol, Examples 5 and 6 use HPC, and Examples 1, 3, and 5 use electrolysis. The solution was ammonium chloride / zinc chloride / phosphoric acid / water system, and Examples 2, 4 and 6 used zinc chloride phosphoric acid / water system.

  The initial electromotive force of the printed battery was measured, and this was allowed to stand at room temperature. The results of confirming changes in electromotive force over time are summarized in Table 5 and FIGS. In addition, in FIGS. 4-6, the comparative example was added and it was made easy to understand the effect of this invention.

As is apparent from Table 5 and FIGS. 4 to 6, the printed batteries of Examples 1 to 6 in which ammonium chloride / zinc chloride / phosphoric acid / water system and ammonium chloride / zinc chloride / phosphoric acid / water system were used as the electrolyte were as follows. In both cases, the initial electromotive force shows a very high value of about 1.9 V, and although the value is lowered by natural discharge, it is clear that the electromotive force has a stable electromotive force of 1.4 V or more over a long period of time. Here, when the electrolyte is ammonium chloride / zinc chloride / phosphoric acid / water system (C4) and zinc chloride / phosphoric acid / water system (C6), ammonium chloride / zinc chloride / water system containing no phosphoric acid ( It is clear that a higher initial electromotive force is obtained as compared with the case of C3) and the case of the zinc chloride / phosphoric acid / water system (C5), and the electromotive force in a stable state with time is large.
Moreover, in the printed battery using the electrolyte solution of the present invention containing phosphoric acid, it is clear that there is a difference in discharge characteristics due to no load depending on the type of polymer used for the electrode binder.

The results of the load discharge test of the printed battery of Example 2 are shown in Table 6 and FIG.
The test condition was a room temperature with a load resistance of 10 kΩ. When a resistor of 10 kΩ is connected to a 1.5 V battery, a current of 0.15 mA flows, so that 0.1 to 0.2 mA electronic devices (greeting cards, postcards, book packages, calendars and other consumer products, electronic tags) And other information components such as a medical thermometer or a medical device such as a medical patch that reads information such as body temperature by attaching to the body or reading the information on the body.
From this result, it was found that the printed battery of Example 2 has an effect of large initial electromotive force, and can continuously discharge over an extremely long time.

[Comparative Examples 6 and 7]
In Examples 1 to 6, in the printed battery using the electrolytic solution of the present invention containing phosphoric acid, although there is a slight difference in discharge characteristics due to no load depending on the type of polymer used for the electrode binder, In the PVBs of Examples 1 and 2, the acrylic polyols of Examples 3 and 4, and the HPCs of Examples 5 and 6, the no-load discharge characteristics up to 6 months were good.

  On the other hand, as compared with Examples 5 and 6 (using HPC as the binder) shown as comparative examples, the printed batteries using ethyl cellulose as the electrode binder as Comparative Examples 6 and 7 showed initial startup. While there was almost no difference in power, the electromotive force in the no-load state was greatly reduced over time, and the utility was low (see Table 7 and FIG. 8). From this, it is clear that in the printed battery of the present invention, the type of the electrode binder greatly affects the battery characteristics.

[Examples 7 and 8]
Composition liquids C8 and C9 described in Table 8 were newly prepared as an ammonium chloride / zinc chloride / phosphoric acid / water-based electrolyte, and a printed battery was produced in the same manner as in Example 7. Table 9 and FIG. 9 summarize the results of measuring the initial electromotive force of these printed batteries, further allowing this to stand at room temperature, and confirming changes in electromotive force over time. In addition, in FIGS. 4-6, the comparative example 1 and Example 1 were added and it was made easy to understand the effect of this invention.
From these results, the desired characteristics of the present invention are obtained in a printed battery using an electrolytic solution composition in the range of ammonium chloride / zinc chloride / phosphoric acid / water = 26 wt% / 8 wt% / 2-10 wt% / 56-64%. It became clear that it was obtained.

[Examples 9 and 10]
Composition liquids C10 and C11 shown in Table 10 were newly prepared as zinc chloride / phosphoric acid / water based electrolytes, and printed batteries were produced in the same manner as in Example 2. The initial electromotive force of these printed batteries was measured, and this was left still at room temperature. The results of confirming changes in electromotive force over time are summarized in Table 11 and FIG. In Table 11 and FIG. 10, Comparative Example 2 and Example 2 were added to facilitate understanding of the effects of the present invention.
From these results, it is clear that the desired characteristics of the present invention can be obtained with a printed battery using an electrolytic solution composition in the range of zinc chloride / phosphoric acid / water = 60 to 75 wt% / 5 to 20 wt% / 20%. became.

1: Anode part 2: Cathode part 3: Separator 4: Substrate 5: Current collecting electrode 6: Anode 7: Cathode

Claims (7)

A printed battery in which an anode prepared by printing a manganese oxide paste and a cathode formed by printing a zinc paste are laminated via a separator impregnated with an electrolyte, wherein the electrolyte is 2 to 25 wt% A printed battery comprising phosphoric acid. The printed battery according to claim 1, wherein the electrolytic solution is an ammonium chloride / zinc chloride / phosphate system or a zinc chloride / phosphate system. The ammonium chloride / zinc chloride / phosphate electrolyte is composed of ammonium chloride / zinc chloride / phosphoric acid / water. Ammon chloride 25-28 wt%, zinc chloride 2-12 wt%, phosphoric acid 2-25 wt%, water 40- It is 65 wt%, The printed battery of Claim 2 characterized by the above-mentioned. The zinc chloride / phosphoric acid electrolyte is composed of zinc chloride / phosphoric acid / water, and is 50 to 80 wt% zinc chloride, 5 to 25 wt% phosphoric acid, and 15 to 25 wt% water. The printed battery described. 2. The manganese oxide paste and the zinc paste are one or more polymers selected from the group consisting of hydroxyalkyl celluloses, polyvinyl butyral (PVB) and acrylic polyol resins as binders. 5. The printed battery according to any one of 4 above. A method for producing a printed battery comprising a printed battery comprising a positive electrode formed by printing a manganese oxide paste and a negative electrode formed by printing a zinc paste via a separator impregnated with an electrolytic solution. A method for producing a printed battery, wherein the liquid contains 2 to 25 wt% phosphoric acid. The method for producing a printed battery according to claim 6, wherein the electrolytic solution is an ammonium chloride / zinc chloride / phosphoric acid system or a zinc chloride / phosphoric acid system.