Primary battery

Abstract

This primary battery comprises a positive electrode containing 2,5-dimethoxy-1,4-benzoquinone, a negative electrode, and an electrolyte disposed between the positive electrode and the negative electrode. The electrolyte contains a C18-22 alkyl glucoside.

Description

primary battery

[0001] The present disclosure relates to primary batteries.

[0002] Conventionally, disposable primary batteries and rechargeable secondary batteries such as alkaline batteries, manganese batteries, high-performance coin-type lithium primary batteries, nickel-cadmium batteries, nickel-metal hydride batteries, and lithium-ion batteries have been widely used in small devices, sensors, mobile equipment, etc. Furthermore, with the recent development of the Internet of Things (IoT), development is also progressing on scattered sensors that can be installed throughout nature, such as in soil or forests.

[0003] However, disposable batteries currently in common use are often made from materials based on important minerals such as nickel, manganese, and cobalt, posing a resource depletion problem. Furthermore, because they use strong alkaline or organic electrolytes, such as sodium hydroxide aqueous solution, final disposal is difficult. For example, when used as a power source for sensors buried in the soil, there are concerns about the impact on the surrounding environment.

[0004] To solve these problems, metal-air batteries are a potential candidate for batteries with a low environmental impact. Because air batteries use oxygen and water as the positive electrode active material and metals such as magnesium, aluminum, and zinc as the negative electrode, they have low impacts on soil contamination and ecosystems. Furthermore, these materials are abundant and less expensive than rare metals. Research and development of such metal-air batteries is underway as batteries with a low environmental impact (see Patent Document 1).

[0005] International Publication No. 2018 / 003724

[0006] MADeyab, “Decyl glucoside as a corrosion inhibitor for magnesium air battery”, Journal of Power Sources, vol. 325, pp. 98-103, 2016. Salah Eid, “Measurement of Hydrogen Produced during Magnesium Corrosion in Hydrochloric Acid and the Effect of the TritonX-100 Surfactant on Hydrogen Production”, J Surfact Deterg, vol. 22, pp. 153-160, 2019.

[0007] However, the negative electrode of a metal-air battery is constantly consumed by corrosion reactions, and only a portion of the negative electrode can be used for the battery reaction. There is also concern about the cessation of the electrochemical reaction due to the evaporation of the electrolyte. Research has been reported on suppressing metal corrosion reactions by adding surfactants to the electrolyte (Non-Patent Documents 1 and 2), but this issue of the cessation of the electrochemical reaction due to the evaporation of the electrolyte has not been taken into consideration.

[0008] The present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a primary battery that can be used for a long period of time by suppressing the corrosion reaction of the negative electrode and the volatilization of the electrolyte.

[0009] A primary battery according to one embodiment of the present disclosure includes a positive electrode containing 2,5-dimethoxy-1,4-benzoquinone, a negative electrode, and an electrolyte solution disposed between the positive electrode and the negative electrode, the electrolyte solution including an alkyl glucoside having 18 to 22 carbon atoms.

[0010] According to the present disclosure, it is possible to provide a primary battery that can be used for a long period of time by suppressing the corrosion reaction of the negative electrode and the volatilization of the electrolyte.

[0011] Fig. 1 is a basic schematic diagram of a primary battery according to this embodiment, and Fig. 2 is a schematic cross-sectional view showing the structure of a coin-type primary battery.

[0012] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings.

[0013] [Configuration of Primary Battery] Fig. 1 is a diagram showing the configuration of a primary battery according to an embodiment of the present disclosure. This primary battery includes a positive electrode 101 containing 2,5-dimethoxy-1,4-benzoquinone, a negative electrode 103, and an electrolyte solution 102 (electrolyte) disposed between the positive electrode 101 and the negative electrode 103. The electrolyte solution 102 preferably contains an alkyl glucoside having 18 to 22 carbon atoms. The electrolyte solution 102 is preferably an aqueous electrolyte.

[0014] In the present embodiment described below, 2,5-dimethoxy-1,4-benzoquinone is used as the positive electrode active material, magnesium, zinc, or aluminum is used as the negative electrode active material, and an aqueous electrolyte solution containing an alkylglycoside having 18 to 22 carbon atoms is used as the electrolyte. As a result, the primary battery of this embodiment is expected to be a battery with a low environmental impact. However, the primary battery of this embodiment is merely an example and is not limited to this.

[0015] Each component of the primary battery of this embodiment will be described below.

[0016] (1) Positive Electrode The positive electrode contains at least 2,5-dimethoxy-1,4-benzoquinone as a positive electrode active material, and may contain a conductive additive or a current collector as needed. The positive electrode is preferably formed on a porous current collector containing at least one selected from the group consisting of aluminum and iron, or a nonwoven current collector containing carbon, and does not contain a binder.

[0017] The positive electrode is preferably formed without a binder into a co-continuum (copolymer) having a three-dimensional network structure in which multiple nanostructures are integrated. The co-continuum has a three-dimensional network structure due to the branches of multiple nanostructures integrated by non-covalent bonds.

[0018] In this embodiment, the positive electrode is preferably formed without a binder. Conventional positive electrode fabrication methods use a binder to stabilize the positive electrode structure (ensuring discharge stability), but the binder has the disadvantage of increasing internal resistance. In contrast, in this embodiment, 2,5-dimethoxy-1,4-benzoquinone is directly supported on a network structure such as a nonwoven current collector or a co-continuous structure. This enables the positive electrode structure to be stabilized without the use of a binder, and is expected to reduce the internal resistance of the battery compared to conventional fabrication methods that use a binder.

[0019] Specific examples of the binder include styrene butadiene rubber, ethylene propylene diene rubber, natural rubber, etc. Polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF) are also commonly used binders, but these are fluorine compounds and therefore have a high environmental impact.

[0020] As described above, by fabricating a cathode containing 2,5-dimethoxy-1,4-benzoquinone as a cathode active material, it is possible to obtain a cathode that is highly active in the discharge reaction. Furthermore, by fabricating a cathode for a primary battery with the above configuration, it is possible to fully utilize the electrochemical activity of 2,5-dimethoxy-1,4-benzoquinone as a cathode active material.

[0021] (1-1) Positive Electrode Active Material The positive electrode active material of this embodiment contains at least 2,5-dimethoxy-1,4-benzoquinone. 2,5-Dimethoxy-1,4-benzoquinone can be obtained, for example, as a commercially available product, a known synthetic product, or a plant extract. Furthermore, because plant extracts are biomass resources, they are expected to be sustainable positive electrode active materials. Plant extracts can be used as positive electrode active materials in either solid or liquid form.

[0022] Moso bamboo is a preferred plant containing 2,5-dimethoxy-1,4-benzoquinone. Moso bamboo is rich in 2,5-dimethoxy-1,4-benzoquinone, and also contains components such as tannins, 1,4-benzoquinone, and chlorophyll that are expected to be electrochemically active.

[0023] (1-2) Preparation of Positive Electrode Using Conductive Aid In this embodiment, the positive electrode may contain a conductive aid. Examples of the conductive aid include carbon. Specific examples include carbon blacks such as ketjen black and acetylene black, activated carbons, graphites, and carbon fibers. To ensure sufficient reaction sites in the positive electrode, carbon with small particles is preferred. Specifically, a particle diameter of 1 μm or less is desirable. These carbons can be obtained, for example, as commercially available products or by known synthesis.

[0024] The positive electrode can be prepared by mixing powder of 2,5-dimethoxy-1,4-benzoquinone, which is a positive electrode active material, the conductive additive, and the binder, and then bonding this mixture to a conductive material.

[0025] Alternatively, a positive electrode can be prepared by mixing a powder containing 2,5-dimethoxy-1,4-benzoquinone extracted from plants such as moso bamboo, the conductive additive, and the binder, and then bonding this mixture to a conductive material. Alternatively, a positive electrode can be prepared by adding dropwise a liquid containing 2,5-dimethoxy-1,4-benzoquinone extracted from plants such as moso bamboo to a mixture of the conductive additive and the binder, and then bonding the mixture to a conductive material.

[0026] (1-3) Preparation of Positive Electrode Using Current Collector The positive electrode is formed on a porous current collector containing at least one selected from the group consisting of aluminum and iron, or a nonwoven current collector containing carbon, and the positive electrode may not contain a binder. For example, the positive electrode active material may be directly supported on the porous current collector or the nonwoven current collector. Direct support means that the positive electrode active material is finely bonded to the three-dimensional structure of the current collector. This can increase conductivity. The porous current collector or nonwoven current collector described above can be obtained, for example, as a commercially available product.

[0027] Alternatively, a positive electrode may be formed on a co-continuum of a three-dimensional network structure in which multiple nanostructures are integrated by non-covalent bonds. For example, a positive electrode active material may be supported on the co-continuum. Here, the co-continuum has a deformable bond between the nanostructures, forming an elastic, integrated structure. The co-continuum preferably has an average pore size of 0.1 μm to 50 μm, for example.

[0028] Nanostructures include nanosheets, nanofibers, and the like, and are characterized by their electrical conductivity. Examples of nanosheets include graphene. Graphene nanofibers include iron oxide, silicon, and carbonized cellulose, which are fibrous materials with diameters of 1 nm to 1 μm and lengths 100 times or more their diameters. Carbonized cellulose can be produced by producing a gel in which cellulose nanofibers are dispersed and then heating and carbonizing the gel in an inert gas atmosphere.

[0029] The method for producing the co-continuum includes the steps of freezing a sol or gel in which a plurality of nanostructures are dispersed to obtain a frozen body, and drying the frozen body in a vacuum to obtain the co-continuum. That is, the co-continuum can be produced by freezing a sol or gel in which nanostructures such as nanosheets or nanofibers are dispersed to obtain a frozen body, and then drying the frozen body in a vacuum.

[0030] Specifically, the dispersion medium for the sol is an aqueous medium such as water, or an organic medium such as carboxylic acid, methanol, ethanol, propanol, n-butanol, isobutanol, n-butylamine, dodecane, unsaturated fatty acid, ethylene glycol, heptane, hexadecane, isoamyl alcohol, octanol, isopropanol, acetone, or glycerin, and two or more of these may be mixed.

[0031] The dispersion medium of the gel is specifically water (H ２ O), or carboxylic acids, methanol (CH ３ OH), ethanol (C ２ H ５ OH), propanol (C ３ H ７and organic solvents such as methyl hydroxybenzoates, methyl ...

[0032] The degree of vacuum in the drying step varies depending on the dispersion medium used, but is not particularly limited as long as it is a degree of vacuum that allows the dispersion medium to sublimate. For example, when water is used as the dispersion medium, a degree of vacuum of 0.06 MPa or less is required. However, since heat is lost as latent heat of sublimation, drying takes time. For this reason, the degree of vacuum is set to 1.0 × 10 ―６ to 1.0 x 10 ―２ Preferably, the pressure is in the range of 100 Pa. Furthermore, heat may be applied during drying using a heater or the like.

[0033] This co-continuum can have a larger specific surface area than commercially available conductive porous bodies or nonwoven fabric current collectors. The specific surface area of ​​this co-continuum is 200 m ２ / g or more is preferred.

[0034] The positive electrode active material can be supported on the porous current collector, nonwoven fabric current collector, and co-continuous body by a physical method such as vapor deposition, sputtering, or planetary ball mill; a method in which a liquid or dissolved positive electrode active material is dropped onto or impregnated into the porous current collector, nonwoven fabric current collector, or co-continuous body; a chemical method such as a sol-gel method; or a known method.

[0035] For the simple formation of a high-quality positive electrode, a method of impregnating a porous current collector, a nonwoven current collector, or a co-continuous body with a liquid or molten positive electrode active material is preferred. Here, by applying cold pressing or hot pressing to the electrode, the strength of the electrode can be increased, resulting in a positive electrode with superior stability.

[0036] In the primary battery of this embodiment, since the electrochemical reaction proceeds on the surface of the positive electrode, it is considered preferable to generate a large number of reaction sites inside the positive electrode. In the case of a positive electrode formed using the above-mentioned conductive additive and binder, when the specific surface area is increased, the binding strength between the conductive additives decreases, the structure deteriorates, making it difficult to discharge stably, and the discharge capacity decreases. Furthermore, polytetrafluoroethylene (PTFE) and the like used as the binder are fluorine compounds, so they have a high environmental impact.

[0037] In contrast, in a positive electrode formed using the aforementioned porous current collector, nonwoven fabric current collector, or co-continuous body, the positive electrode active material is directly supported on the current collector or co-continuous body, making it possible to stabilize the positive electrode structure without using a binder, and a reduction in the internal resistance of the battery can be expected.

[0038] Furthermore, positive electrodes molded using these current collectors or co-continuum materials can secure a large number of reaction sites, thereby solving the aforementioned conventional problems and enabling high discharge capacity. In particular, the co-continuum materials have a high bulk density and can support a larger amount of positive electrode active material, thereby improving battery efficiency. Furthermore, since the positive electrode does not contain binders such as polytetrafluoroethylene (PTFE), which have a high environmental impact, a reduction in environmental impact can be expected.

[0039] As described above, by fabricating a cathode containing 2,5-dimethoxy-1,4-benzoquinone as a cathode active material, it is possible to obtain a cathode that is highly active in the discharge reaction. Furthermore, by fabricating a cathode for a primary battery with the above configuration, it is possible to fully utilize the electrochemical activity of 2,5-dimethoxy-1,4-benzoquinone.

[0040] (2) Negative Electrode The negative electrode of this embodiment contains at least one selected from the group consisting of magnesium, zinc, and aluminum. That is, the negative electrode contains at least magnesium (Mg), zinc (Zn), and aluminum (Al) as the negative electrode active material. The negative electrode active material may contain magnesium (Mg), zinc (Zn), and aluminum (Al) as main components, and may also be an alloy containing one or more other elements (components). The negative electrode may also contain a conductive additive in addition to the negative electrode active material.

[0041] (3) Electrolyte In this embodiment, the electrolyte is an electrolyte in which an alkyl glycoside having 18 to 22 carbon atoms is dissolved. The concentration of the alkyl glycoside is 1×10 －１ ~1 x 10 －６ mol / L is preferred. Alkyl glucosides with 18 to 22 carbon atoms are believed to have a greater corrosion inhibition effect than alkyl glucosides with 16 or fewer carbon atoms or the commercially available compound Triton-X100. The HLB (Hydrophile-Lipophile Balance Value) values, which indicate the degree of hydrophilicity, are 16 and 13.4 for alkyl glycosides with 16 carbon atoms and Triton-X100, respectively. The HLB values ​​for alkyl glycosides with 18, 20, and 22 carbon atoms are 9, 7, and 5, respectively, indicating greater lipophilicity than alkyl glycosides with 16 carbon atoms and Triton-X100. The greater the lipophilicity, the greater the adsorption force to the metal surface, allowing for a larger coverage area on the negative electrode surface. From this, it is believed that the greater the lipophilicity, the greater the corrosion inhibition effect.

[0042] However, the greater the lipophilicity, the lower the solubility in water. Low solubility in water also has the effect of reducing the number of molecules in the aqueous solution and reducing the coverage area. Note that alkyl glycosides with 24 or more carbon atoms have low hydrophilicity and a saturation concentration of 1 × 10 －６ mol / L, the corrosion inhibition effect is not considered to be significant.

[0043] The electrolyte is a solution containing an electrolyte that allows ions to move and is used in the negative electrode. The ionic conductors that make up the electrolyte include, for example, magnesium salts, zinc salts, and aluminum salts, which are abundant on Earth. Mixtures of two or more of these salts can also be used.

[0044] The ionic conductor can be dissolved in ion-exchanged water at a concentration of 0.1 to 10 mol / L, preferably 0.1 to 2 mol / L. Finally, the electrolyte is prepared by adding 1×10 alkylglucoside having 18 to 22 carbon atoms to the above solution. －５ It was dissolved at a concentration of 1 mol / L.

[0045] In this embodiment, an aqueous electrolyte solution is used as the electrolyte, but a solid electrolyte such as a gel or solid may also be used. That is, the electrolyte may be in any form such as a liquid, cream, gel, or solid.

[0046] (4) Other Elements In addition to the above components, the primary battery of this embodiment can include structural members such as a separator and a battery case, as well as other elements required for a primary battery. These elements may be conventionally known, but from the viewpoint of environmental impact and waste disposal, they preferably do not contain hazardous substances, precious metals, etc. Furthermore, it is more preferable that these other elements are biologically derived and biodegradable materials.

[0047] (5) Method for Manufacturing Primary Battery As described above, the primary battery of this embodiment includes at least a positive electrode, a negative electrode, and an electrolyte, and the electrolyte is disposed between the positive electrode and the negative electrode so as to be in contact with the positive electrode and the negative electrode, as illustrated in Fig. 1. A primary battery having such a configuration can be prepared in the same manner as a conventional primary battery.

[0048] For example, a primary battery can be produced by assembling the components of a positive electrode containing 2,5-dimethoxy-1,4-benzoquinone as a positive electrode active material, a negative electrode containing magnesium, zinc, or aluminum, and an aqueous electrolyte solution disposed so as to be in contact with the positive electrode and the negative electrode according to conventional techniques.

[0049] As an embodiment of the method for manufacturing a primary battery, for example, a coin-type primary battery can be manufactured.

[0050] 2 is a schematic cross-sectional view showing the structure of a coin-type primary battery. Specifically, first, a separator (not shown) is placed on a positive electrode case 201 in which a positive electrode 101 is placed, and an electrolyte solution 102 is poured into the placed separator. Next, a negative electrode 103 is placed on the electrolyte solution 102, and the negative electrode case 202 is placed over the positive electrode case 201. Next, the peripheral portions of the positive electrode case 201 and the negative electrode case 202 are crimped using a coin cell crimping machine, thereby making it possible to fabricate a coin-type primary battery including a propylene gasket 203.

[0051] The coin-type primary battery shown in the figure uses 2,5-dimethoxy-1,4-benzoquinone as the positive electrode active material. Therefore, unlike air batteries that use oxygen in the air as the positive electrode active material, there is no need to provide an air intake port in the positive electrode case 201 of this embodiment. In other words, this embodiment can produce a sealed battery. Therefore, the primary battery of this embodiment can be stored for a long period of time without the electrolyte volatilizing through the air intake port.

[0052] Furthermore, in the primary battery of this embodiment, the progress of the corrosion reaction of the negative electrode 103 can be suppressed by the presence of alkyl glucoside having 18 to 22 carbon atoms in the electrolyte solution.

[0053] Examples of the primary battery according to this embodiment will be described in detail below. In the primary batteries of Examples 1-1 and 1-2, magnesium, zinc, and aluminum were used for the negative electrode, respectively. In the primary battery of Examples 1-2, magnesium was used for the negative electrode. In each example, an alkyl glucoside was added to the electrolyte.

[0054] The present disclosure is not limited to the examples shown below, and can be implemented with appropriate modifications within the scope that does not change the gist of the present disclosure.

[0055] Example 1-1 In Example 1-1, the coin-type primary battery (FIG. 2) described above was fabricated by the following procedure. In this example, an alkyl glucoside having 18 carbon atoms was added to the aqueous electrolyte. In this example, three primary batteries were fabricated using magnesium, zinc, and aluminum as the negative electrodes. The electrolyte salts for the aqueous electrolyte were MgCl ２ , ZnCl ２ , AlCl ３ was used.

[0056] (Preparation of Positive Electrode) 2,5-dimethoxy-1,4-benzoquinone (Tokyo Chemical Industry Co., Ltd.) was dropped onto the co-continuum. Then, this 2,5-dimethoxy-1,4-benzoquinone-containing co-continuum was cut into a circle with a diameter of 16 mm to obtain a positive electrode.

[0057] To produce the co-continuum, bacterial cellulose gel produced by the acetic acid bacterium Acetobacter xylinum was placed in a test tube and immersed in liquid nitrogen for 30 minutes to completely freeze the bacterial cellulose gel. The frozen bacterial cellulose gel was then transferred to an eggplant flask and dried in a freeze dryer (Tokyo Rikakikai Co., Ltd.) at a vacuum of 10 Pa or less. The gel was then carbonized by firing at 1200°C for 2 hours in a nitrogen atmosphere to produce a co-continuum.

[0058] (Preparation of Negative Electrode) Negative electrodes were obtained by cutting out a circle having a diameter of 17 mm from each of magnesium foil (thickness 150 μm), zinc foil (thickness 150 μm), and aluminum foil (thickness 150 μm).

[0059] (Preparation of aqueous electrolyte) Three electrolytic salts (MgCl ２ , ZnCl ２ , AlCl ３ ) were dissolved in pure water at a concentration of 1 mol / L to obtain aqueous solutions. Five mg or more of alkyl glucoside having 18 carbon atoms per mL was dissolved in each of these aqueous solutions at room temperature, and the saturated alkyl glucoside aqueous solutions were used as aqueous electrolytes.

[0060] (Preparation of Primary Battery) A coin-type primary battery shown in Fig. 2 was fabricated using a coin battery case (Hosensha). A cellulose-based separator (Nippon Kodoshi Kogyo Co., Ltd.) cut to a diameter of 18 mm was placed on the positive electrode case 201 containing the positive electrode 101 prepared by the above method, and an aqueous electrolyte corresponding to the placed separator was poured into each.

[0061] Magnesium foil, zinc foil, and aluminum foil were placed as negative electrodes on the aqueous electrolyte, and the negative electrode case 202 was placed over the positive electrode case 201. The peripheral edges of the positive electrode case 201 and the negative electrode case 202 were crimped using a coin cell crimping machine to obtain a coin-type primary battery including a propylene gasket 203. The combinations of the positive electrode, negative electrode, and electrolyte in this example are as shown in Table 1.

[0062] Example 1-2 In Example 1-2, the coin-type primary battery (FIG. 2) described above was fabricated by the following procedure. In this example, four primary batteries were fabricated by adding alkyl glucosides with different carbon numbers to an aqueous electrolyte. In this example, magnesium was used for the negative electrode.

[0063] The preparation of the positive electrode and the preparation of the primary battery in this example were carried out in the same manner as in Example 1-1.

[0064] (Preparation of Negative Electrode) A magnesium foil (thickness: 150 μm) was cut into a circle having a diameter of 17 mm to obtain a negative electrode.

[0065] (Preparation of Aqueous Electrolyte Solution) In this example, four types of aqueous solutions were prepared, each containing an alkyl glucoside having 18 carbon atoms, 20 carbon atoms, 22 carbon atoms, or 24 carbon atoms.

[0066] Specifically, MgCl ２ The electrolyte salt was dissolved in pure water at a concentration of 1 mol / L to obtain an aqueous solution. In this example, four such aqueous solutions were prepared to fabricate four primary batteries. At room temperature, 5 mg or more of alkyl glucosides with carbon numbers of 18, 20, 22, and 24 were dissolved per mL in each aqueous solution, respectively, to obtain saturated alkyl glucoside aqueous solutions.

[0067] In this example, four primary batteries were prepared in the same manner as in Example 1 using four types of aqueous electrolyte solutions to which alkyl glucosides with different carbon numbers were added.

[0068] Comparative Example 1 As a comparative example to Example 1-1, a primary battery was fabricated without adding an alkyl glucoside having 18 carbon atoms. In this comparative example, three primary batteries were fabricated using magnesium, zinc, and aluminum in the negative electrode, respectively, as in Example 1-1.

[0069] In this comparative example, the preparation of the positive electrode, the preparation of the negative electrode, and the preparation of the primary battery were carried out in the same manner as in Example 1-1.

[0070] (Preparation of aqueous electrolyte) In this comparative example, an aqueous electrolyte was prepared without adding alkyl glucoside. ２ , ZnCl ２, AlCl ３ ) were each dissolved in pure water at a concentration of 1 mol / L to obtain an aqueous electrolyte solution.

[0071] <Battery Performance of Examples 1-1, 1-2, and Comparative Example 1> (Discharge Test Method) The battery performance of the primary batteries of Examples 1-1, 1-2, and Comparative Example 1 prepared by the above procedure was measured. The battery discharge test was carried out using a discharge measurement system (manufactured by Bio Logic) at a current density of 0.1 mA / cm per effective area of ​​the positive electrode. ２ A current was applied to the battery, and the discharge voltage was measured until the battery voltage decreased from the open circuit voltage to 0.50 V (discharge cut-off voltage). The battery discharge test was conducted under normal living conditions. The discharge capacity was expressed as a value per unit weight of the positive electrode active material (mAh / g). Here, the discharge voltage was defined as the discharge voltage at half the total discharge capacity.

[0072] (Battery Performance) The discharge voltages and discharge capacities of the primary batteries of Example 1-1, Example 1-2, and Comparative Example 1 are shown in Table 1. The average discharge voltages of the primary batteries of Example 1-1 using magnesium, zinc, and aluminum in the negative electrodes were 1.6 V, 1.4 V, and 0.9 V, respectively, and the discharge capacities were 240 mAh / g, 220 mAh / g, and 200 mAh / g, respectively.

[0073] On the other hand, the primary batteries of Comparative Example 1 using magnesium, zinc, and aluminum for the negative electrode had average discharge voltages of 1.6 V, 1.4 V, and 0.9 V, respectively, and discharge capacities of 140 mAh / g, 120 mAh / g, and 100 mAh / g, respectively.

[0074] In Example 1-1, there is no significant change in the average discharge voltage compared to Comparative Example 1, but the discharge capacity is increased by 100 mAh / g compared to Comparative Example 1. As described above, it was confirmed that the primary battery of Example 1-1 to which the alkyl glucoside having 18 carbon atoms was added has excellent battery performance. This is presumably because the use of an electrolyte containing the alkyl glucoside suppresses the corrosion reaction of the negative electrode, preventing the consumption of the negative electrode by the corrosion reaction.

[0075] The average discharge voltage in the primary batteries of Examples 1 and 2 was 1.6 V. Regarding discharge capacity, the primary batteries to which alkyl glucosides having 18, 20, and 22 carbon atoms were added exhibited particularly excellent discharge capacity. Regarding the discharge capacity of the alkyl glucoside having 24 carbon atoms, the negative electrode of Comparative Example 1 exhibited a larger discharge capacity than that of magnesium, but the difference was not as significant as that observed for alkyl glucosides having 18 to 22 carbon atoms. Regarding this, the alkyl glucoside having 24 carbon atoms has low hydrophilicity, and the saturated concentration is 1×10 －６ It is presumed that the effect of adding the compound was small because the concentration was below mol / L.

[0076]

[0077] Example 2 In Example 2, coin-type primary batteries were fabricated in the same manner as in Example 1-1 described above. That is, in this example, three primary batteries were fabricated in which an alkyl glucoside having 18 carbon atoms was added to an aqueous electrolyte solution and magnesium, zinc, and aluminum were used in the negative electrode, respectively. The primary battery of Example 2 was the same as the primary battery of Example 1-1.

[0078] <Comparative Example 2> As a comparative example for Example 2, a primary battery without adding alkyl glucoside was fabricated in the same manner as in Comparative Example 1. In Comparative Example 2, three primary batteries were fabricated using magnesium, zinc, and aluminum in the negative electrode, respectively. The primary battery of Comparative Example 2 was the same as the primary battery of Comparative Example 1.

[0079] <Battery Performance of Example 2 and Comparative Example 2> (Discharge Test Method) Two primary batteries were prepared for each of Example 2 and Comparative Example 2 according to the above procedure. One battery was measured for battery performance immediately after preparation, and the other was measured for battery performance 30 days after preparation. The battery discharge test was carried out using a discharge measurement system (manufactured by Bio Logic) at a current density of 0.1 mA / cm per effective area of ​​the positive electrode. ２ The discharge voltage was measured from the open circuit voltage until the battery voltage decreased to 0.50 V (discharge cut-off voltage). The battery discharge test was carried out under normal living conditions. The discharge voltage was defined as the discharge voltage at half the total discharge capacity.

[0080] (Battery Performance) The average discharge voltages of the primary batteries of Example 2 and Comparative Example 2 are shown in Table 2. The average discharge voltages of the primary batteries using magnesium, zinc, and aluminum in the negative electrodes of Example 2 were 1.6 V, 1.4 V, and 0.9 V, respectively, immediately after adjustment, and 1.5 V, 1.3 V, and 0.5 V, respectively, 30 days after adjustment. In contrast, the average discharge voltage of Comparative Example 2 immediately after adjustment was similar to that of Example 2, but the average discharge voltages of the primary batteries using magnesium, zinc, and aluminum in the negative electrodes immediately after adjustment were 0.4 V, 1.2 V, and 0.1 V, respectively, which were all lower than the average discharge voltage of Example 2.

[0081] From the above results, it was confirmed that the primary battery of this example had better battery performance than a primary battery to which no alkyl glucoside was added.

[0082]

[0083] As described above, according to this embodiment, it is possible to provide a primary battery that can be used for a long period of time by suppressing the corrosion reaction of the negative electrode and the volatilization of the electrolyte. Specifically, by adding an alkyl glucoside to the electrolyte, corrosion of the negative electrode is prevented, and by using a battery that is not an open-circuit battery like a metal-air battery, volatilization of the electrolyte is avoided, thereby realizing a primary battery that can be used for a long period of time.

[0084] The present disclosure is not limited to the above-described embodiments, and various modifications and combinations are possible within the scope of the technical idea of ​​the present disclosure.

Claims

1. A primary battery comprising: a positive electrode containing 2,5-dimethoxy-1,4-benzoquinone; a negative electrode; and an electrolyte disposed between the positive electrode and the negative electrode, wherein the electrolyte contains an alkyl glucoside having 18 to 22 carbon atoms.

2. The primary battery according to claim 1, wherein the negative electrode contains at least one selected from the group consisting of magnesium, zinc, and aluminum.

3. The primary battery according to claim 1, wherein the positive electrode is formed on a porous body containing at least one material selected from the group consisting of aluminum and iron, or a nonwoven current collector containing carbon, and does not contain a binder.

4. The primary battery according to claim 1, wherein the positive electrode is formed into a bicontinuous body having a three-dimensional network structure by integrating a plurality of nanostructures and having branches, and does not contain a binder.

5. A method for producing a co-continuum according to claim 4, comprising the steps of freezing the sol or gel in which the plurality of nanostructures are dispersed to obtain a frozen body, and drying the frozen body in a vacuum to obtain the co-continuum.

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