JPH11185815A - Battery and manufacture of battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a battery that includes a solid electrolytic layer excellent in a mechanical strength characteristic while maintaining high conductivity, and has an excellent capacity characteristic and discharging rate characteristic, and also provide a manufacturing method of the battery. SOLUTION: This battery includes: a negative electrode active material 3 formed from an alkaline metal, an alloy of an alkaline metal and a II or III group metal, or carbon capable of occluding alkaline metal ions; a positive electrode active material 1 formed from a metal oxide capable of intercalating lithium, a conductive high polymer having oxidation-reduction capability or a complex of them; an unwoven fabric placed in between the positive electrode active material 1 and the negative electrode active material 3; and a solid electrolytic layer 2 comprised a solid electrolyte 2 formed by infiltrating a solid electrolytic precursor solution in the unwoven fabric and thereafter polymerizing the precursor solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a battery which can be repeatedly charged and used, and more particularly to a negative electrode composed of an alkali metal or an alkali metal / alkaline earth metal alloy, a metal oxide or a highly conductive metal oxide. The present invention relates to a battery having a positive electrode composed of molecules or a composite thereof, and a solid electrolyte layer, and a method for manufacturing a battery.

[0002]

2. Description of the Related Art In recent years, with the remarkable progress of microelectronics, especially semiconductor device manufacturing technology, highly integrated and highly functional devices represented by large-scale integrated circuits (VLSI) have been realized. By adopting this in the control system of various devices, electronic devices have achieved a tremendous miniaturization and contributed not only to various industrial devices but also to the miniaturization and multifunctionalization of home appliances in ordinary households. ing.

[0003] Many of miniaturized electronic devices are operable without relying on a commercial power supply or the like, and are moving toward a so-called cordless direction. As a power source for this kind of electronic equipment,
Generally, a battery is used. Among them, a so-called secondary battery, which can be repeatedly charged and used, can be used at a very low cost per use, and thus is useful as a power source for portable information devices such as mobile phones and handheld personal computers.

[0004] In recent years, polymer solid electrolytes have attracted attention as electrolytes for batteries used in these electronic devices.
The polymer solid electrolyte does not have the problem of liquid leakage, which is a problem inherent to batteries, and has lower flammability compared to solution-based batteries, thereby improving safety and improving the productivity of the polymer solid electrolyte. The battery has many advantages, such as improved workability of the battery itself and realization of a thin and free-form battery.
As such a secondary battery, a battery using lithium is widely known.

[0005] In a secondary battery using lithium,
As a polymer solid electrolyte, polyethylene oxide, polyacrylonitrile, polyvinyl pyridine, polyvinyl chloride, polyvinyl alcohol, or a derivative obtained by introducing a reactive functional group such as an acrylic group, a vinyl group, or an epoxy group into these polymer matrix materials, A system is used in which an organic solvent having a large polarization is added as an electrolyte component to a polymer matrix having a relatively high dielectric constant to give a large ionic conductivity as a whole. That is, the lithium ions that are charge carriers are derived from lithium salts such as lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, and lithium tetrafluorosulfonate, and these salts are sufficiently contained in the electrolyte. This is because lithium ions must dissociate and move at a sufficient speed in order to eliminate the polarization accompanying the charge and discharge of the battery.

In order to satisfy these conditions, a system in which a non-aqueous solvent such as propylene carbonate (propylene carbonate) is added to polyethylene oxide, and 1 to 3 M of lithium hexafluorophosphate is added (dissolved) to the solvent. Can be used. The system realized by this configuration has an advantage that a thin sheet-shaped battery can be configured and the shape is highly arbitrary.

[0007] The battery of the above configuration has the advantage of having a high degree of arbitrariness in the shape, but has the disadvantage of low mechanical strength. That is, as a solid electrolyte, conventionally, polyethylene oxide, polyacrylonitrile, polyvinyl pyridine, polyvinyl chloride, polyvinyl alcohol,
In a polymer matrix such as polyvinylidene fluoride, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, an inorganic salt containing lithium as a cation such as lithium trifluoromethanesulfonate, propylene carbonate, ethylene carbonate,
A so-called polymer electrolyte containing an organic solvent such as diethyl carbonate, dimethyl carbonate, dimethoxyethane, and γ-butyrolactone is used.
In particular, it is important to increase the content of the organic solvent component and to stably maintain the content in order to improve conductivity and improve capacity characteristics and discharge rate characteristics of the battery. However, such a solid electrolyte having high conductivity generally has low mechanical strength. In order to increase the mobility of ions while maintaining the mechanical strength, it is necessary to impart flexibility to the matrix polymer constituting the solid electrolyte.

In view of such a problem, Japanese Patent Application Laid-Open No. 5-674
No. 76, JP-A-5-290614, JP-A-5-227
In Japanese Patent Publication No. 24, there is provided an electrolyte having a structure in which a nonwoven fabric is impregnated with an electrolyte, or a nonwoven fabric is impregnated with an electrolyte and then a nonaqueous solvent is evaporated.

[0009]

However, the nonwoven fabric itself does not have ionic conductivity and does not contribute to the conductivity of the electrolyte. Therefore, in a conventional battery having a structure in which an electrolyte is simply held in a nonwoven fabric, there is a problem that although the mechanical strength increases, the conductivity decreases. An object of the present invention is to provide a battery having a solid electrolyte layer having excellent mechanical strength characteristics while maintaining high conductivity, and having good capacity characteristics and discharge rate characteristics, and a method of manufacturing a battery.

[0010]

An object of the present invention is to provide a negative electrode comprising an alkali metal, an alloy of an alkali metal and a Group II or Group III metal, or a carbon having an alkali metal ion-absorbing ability, and a lithium intercalator. A positive electrode composed of a conductive metal oxide or a conductive polymer having a redox ability, or a composite thereof,
A non-woven fabric disposed between the positive electrode and the negative electrode, and a solid electrolyte layer including a solid electrolyte formed by impregnating the non-woven fabric with a precursor solution of a solid electrolyte and then polymerizing the precursor solution. The problem is solved by a battery having:

[0011] Further, the above-mentioned problem is to impregnate a non-woven fabric with a precursor solution of a solid electrolyte and then polymerize the precursor solution to form a solid electrolyte layer;
An alloy of an alkali metal and a group II or group III metal, or a negative electrode composed of carbon having an alkali metal ion-absorbing ability, and a metal oxide capable of lithium intercalation or a conductive polymer having an oxidation-reduction ability, Or a step of sandwiching the solid electrolyte layer with a positive electrode composed of a composite thereof.

The operation of the present invention will be described below. In the battery of the present invention, the solid electrolyte layer is formed by impregnating the nonwoven fabric with the precursor solution of the solid electrolyte and then polymerizing the precursor solution. Since the nonwoven fabric is impregnated with the precursor solution of the solid electrolyte and then polymerized, the solid electrolyte is firmly held by the nonwoven fabric. Thereby, the mechanical characteristics are improved, and a solid electrolyte layer having high ionic conductivity is obtained.

Accordingly, a battery having a solid electrolyte layer having excellent mechanical strength characteristics while maintaining high conductivity and having good capacity characteristics and discharge rate characteristics can be obtained. Also, by polymerizing and holding the solid electrolyte component on the nonwoven fabric,
The uniformity of the thickness of the electrolyte layer is improved than that of evaporating the non-aqueous solvent component, the variation in characteristics can be reduced, the risk of liquid leakage can be more reliably prevented, and the energy required for polymerization is small, The time is short, and the cost and the process can be reduced.

Further, the density of the nonwoven fabric is 1.0 g / cm ³ or less,
Alternatively, the non-woven fabric has a substantial filling factor of 0.5 or less, and contains a low-molecular solvent component of 40% or more, more preferably 60% or more of the weight of the precursor solution of the solid electrolyte, thereby maintaining mechanical strength. The effect of ensuring ion transportability is further increased. This is to use a non-woven fabric with low density and high aperture ratio for non-woven fabric not involved in ionic conductivity,
By the synergistic effect of both containing a large amount of low molecular solvent components,
This is because high ionic conductivity can be ensured.

Examples of the material of the nonwoven fabric include polyester polymer materials, rayon polymer materials, aliphatic polyamide polymer materials, aromatic polyamide polymer materials, polyolefin polymer materials, and chlorinated polyolefin polymer materials. And a fluorinated polyolefin polymer. In the method for producing a battery according to the present invention, a step of impregnating a nonwoven fabric with a precursor solution of a solid electrolyte, polymerizing the precursor solution to form a solid electrolyte layer, an alkali metal, an alkali metal and a group II or III group A negative electrode composed of an alloy with a metal, or carbon having an alkali metal ion-absorbing ability, and a metal oxide capable of lithium intercalation or a conductive polymer having an oxidation-reduction ability, or a composite thereof. The battery is manufactured through the steps of sandwiching the solid electrolyte layer with the positive electrode.

Therefore, a solid electrolyte layer having high ionic conductivity and improved mechanical properties can be obtained by the nonwoven fabric. In addition, since the nonwoven fabric is impregnated with the precursor solution of the solid electrolyte and polymerized, the solid electrolyte is firmly held by the nonwoven fabric. As a result, the mechanical properties are further improved, a solid electrolyte layer having high ionic conductivity is obtained, and the risk of liquid leakage can be more reliably prevented. Further, by holding the solid electrolyte in the nonwoven fabric, the uniformity of the thickness of the electrolyte layer is improved, and the effect of reducing the variation in characteristics can be obtained. Accordingly, a battery having a solid electrolyte layer having excellent mechanical strength characteristics while maintaining high conductivity and having good capacity characteristics and discharge rate characteristics can be obtained.

[0017]

Embodiments of the present invention will be described below with reference to the accompanying drawings. FIG. 1 is a sectional view showing a battery according to an embodiment of the present invention, and FIG. 2 is a plan view showing the same battery. In the battery according to the embodiment of the present invention, the positive electrode active material 1 (positive electrode) and the negative electrode active material 3 (negative electrode) are arranged on both surfaces of the solid electrolyte layer 2. Positive electrode active material 1 (positive electrode)
And a positive electrode current collector 5 outside the negative electrode active material 3 (negative electrode).
A negative electrode current collector 6 is disposed, and a positive electrode terminal 7 and a negative electrode terminal 8 are bonded to the outside of the positive electrode current collector 5 and the negative electrode current collector 6. The positive electrode current collector 5, the negative electrode current collector 6, the positive electrode terminal 7, and the negative electrode terminal 8 are configured to be covered with the exterior material 4, and the positive electrode terminal 7 and the negative electrode terminal 8 extend from the exterior material 4. It has a broken structure.

The positive electrode active material 1 is composed of a metal oxide capable of lithium intercalation, a conductive polymer having a redox ability, or a composite thereof. Metal oxides capable of lithium intercalation include cobalt oxide, vanadium oxide, manganese oxide, nickel oxide, and the like. In addition, materials capable of binding to these materials, for example, polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, fluorinated polymers such as polyvinylidene fluoride, polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, etc. A material sheet formed of a mixture such as a thermoplastic polymer may be used as the positive electrode active material 1. At this time, a carbon-based conductive agent such as acetylene black or graphite may be mixed for the purpose of increasing the contact between the positive electrode active material 1 and the positive electrode current collector 5.

Examples of the conductive polymer having a redox ability include polyaniline, polypyrrole, polythiophene, and polyacetylene. These use an electrochemical potential based on redox behavior. As the negative electrode active material 3, a substance having a large reducing property, that is, a substance having a property of being easily oxidized, is used. Alloy or carbon having the ability to occlude alkali metal ions.

The solid electrolyte layer 2 is composed of a solid electrolyte and a non-woven fabric. The solid electrolyte is formed by mixing a polymer matrix and a low-molecular solvent. As the polymer matrix, a polyethylene oxide-based, polyacrylonitrile-based, polyacryl-based, polymethacryl-based, polysaccharide polymer-based, or the like, or a mixture thereof is used. The low molecular solvent is formed with an inorganic salt, an organic solvent, or an organic solvent obtained by mixing these at an appropriate ratio.
As the inorganic salt, those containing lithium as a cation, such as lithium perchlorate, lithium tetrafluoroborate, and lithium tetrafluorosulfonate are used. As the organic solvent, propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, dimethoxyethane, γ-butyrolactone, or the like is used.

Then, a curing agent is added to a solution obtained by mixing a polymer matrix and an organic solvent, and this solution (precursor solution)
Is impregnated into the nonwoven fabric. Thereafter, the polymer is polymerized by light irradiation or heating to be solidified, whereby the solid electrolyte layer 2 is formed. With this nonwoven fabric, a solid electrolyte layer 2 having high ionic conductivity and improved mechanical properties can be obtained.

As the non-woven fabric, a material having a density of 1.0 g / cm ³ or less or a substantial filling rate of 0.5 or less, that is, a material having a high porosity is used.
%, Preferably 60% or more of a low molecular solvent component. As a material for nonwoven fabric,
Polymer materials such as polyester, rayon, aliphatic polyamide, aromatic polyamide, polyolefin, chlorinated polyolefin, and fluorinated polyolefin may be used. Further, a nonwoven fabric obtained by compounding the above materials may be used.

Here, the reason why a non-woven fabric having a density of 1.0 g / cm ³ or less, that is, a high porosity, is used will be described. The density of the nonwoven fabric is obtained by the following equation. Density of nonwoven fabric = density of material × substantial filling ratio (1) The substantive filling ratio is a ratio of a material constituting the nonwoven fabric to a unit volume.

[0024]

[Table 1]

From the experiment of the present inventor, it has been found that the effective filling rate is preferably 0.5 or less in order to obtain good ionic conductivity. The density of the material is about 2 g / cm ³ or less as shown in Table 1 above. In this case, the density of the nonwoven fabric is 2.0 g / cm ³ × from the formula (1).
0.5 = 1.0 g / cm ³ . Therefore, the nonwoven is
Use a material having a density of 1.0 g / cm ³ or less.

As a solid electrolyte material, a weight ratio of 4
The reason why a polymer electrolyte containing 0% or more of a low molecular solvent component is used will be described. FIG. 3 is a diagram showing the relationship between the organic solvent content of the solid electrolyte material and the ionic conductivity, with the horizontal axis representing the organic solvent content of the solid electrolyte material and the vertical axis representing the ionic conductivity. Since the data plotted in FIG. 3 is not data relating to a single material, it does not necessarily have a unique relationship, but indicates an approximate tendency. From this figure, when the organic solvent content is about 40%,
It can be seen that the ionic conductivity changes. It is considered that some mechanism related to ionic conductivity has changed in the vicinity of this, and when it is 40% or less, the conductivity sharply decreases. That is, it is understood that a low molecular solvent content of at least about 40%, preferably 60% or more is required to obtain a solid electrolyte having stable electric conductivity.

FIG. 4 is a graph showing the relationship between the ionic conductivity and the capacitance appearance ratio, with the ordinate being the ionic conductivity and the ordinate being the capacitance appearance ratio. The capacitance appearance rate is a ratio of the actual capacity obtained with respect to the theoretical capacity of the material (active material) charged in the electrode. Again, the data plotted in FIG. 4 uses representative data of different systems, but in order for the capacity appearance rate to be 80% or more, the ionic conductivity is about 1 × 10 ⁻³ S. / cm ² or more is considered necessary. Then, referring to FIG. 3, approximately 1 × 10
^In order to obtain an ionic conductivity of ^-3 S / cm ² or more, the content of the organic solvent must be 40% or more. In particular, the content of the organic solvent is preferably about 60%.

Hereinafter, a method for manufacturing the above battery will be described. An aluminum plate is attached as the positive electrode current collector 5 on the positive electrode active material 1 made of the above-described material, and the positive electrode terminal 7 is joined on the positive electrode current collector 5. Further, a copper plate is attached as the negative electrode current collector 6 on the negative electrode active material 3 made of the above-described material,
A negative electrode terminal 8 is bonded on the negative electrode current collector 6.

Next, on the surface of the negative electrode active material 3 opposite to the surface on which the negative electrode current collector 6 is formed, a nonwoven fabric which has been damaged by the above-described solution (precursor solution) is placed. The solid electrolyte layer 2 is obtained by polymerizing and solidifying the polymer. The positive electrode active material 1 is provided on the surface of the solid electrolyte layer 2 opposite to the surface on which the negative electrode active material 3 is formed.
The surface opposite to the surface on which the positive electrode current collector 5 is formed is joined.

Finally, the exterior material 4 covers the positive electrode terminal 7, the positive electrode current collector 5, the positive electrode active material 1, the solid electrolyte layer 2, the negative electrode active material 3 and the negative electrode current collector 6. Thereby, the battery according to the embodiment of the present invention is completed. Hereinafter, effects of the battery of the embodiment of the present invention will be described. In the embodiment of the present invention, a curing agent is added to a solution obtained by mixing a polymer matrix and an organic solvent, and this solution (precursor solution) is impregnated into the nonwoven fabric. Thereafter, the polymer is polymerized by light irradiation or heating to be solidified, whereby the solid electrolyte layer 2 is formed.

Since the nonwoven fabric is formed by impregnating and polymerizing a polymer matrix containing a curing agent, the polymer matrix is firmly held by the nonwoven fabric. Thereby, a solid electrolyte layer 2 having high mechanical strength and high ion conductivity can be obtained. Further, by polymerizing and holding the solid electrolyte component in the nonwoven fabric, the uniformity of the thickness of the electrolyte layer is improved, the variation in the characteristics can be reduced, and the risk of liquid leakage can be more reliably prevented and the polymerization is performed. The required energy is small, the time is short, and the cost and the process can be reduced. Further, by using a non-woven fabric having a density of 1.0 g / cm ³ or less, and using a polymer electrolyte containing an organic solvent component in a weight ratio of 40% or more, preferably 60% or more as a solid electrolyte material. In addition, ion transportability can be ensured. For this reason, the effect of reducing battery characteristics, especially internal resistance, can be obtained.

Hereinafter, the effect of improving the characteristics of the battery according to the embodiment of the present invention will be shown by comparing the internal resistance and the short-circuit pressure using an example of actually manufacturing the battery according to the embodiment of the present invention. (Example 1) In the solid electrolyte layer 2, a cyanoethylated derivative of pullulan which is a kind of polysaccharide (polymer matrix)
Was used. Among them, 100 parts by weight of cyanoethylated bullane (CR-S manufactured by Shin-Etsu Chemical Co., Ltd.) is dissolved in 900 parts by weight of propylene carbonate (organic solvent) containing 1 M lithium tetrafluoroborate, and further, polyethylene oxide acrylate ( (Kyoeisha Chemical Light Acrylate 9EG-A)
50 parts by weight were mixed. Then, 1 part by weight of riboflavin and 1 part by weight of benzoyl peroxide (polymerization initiator) were mixed and dissolved to obtain a solid electrolyte precursor solution. A polyester-based nonwoven fabric having a density of 0.4 g / cm ³ was immersed in this solution, and the precursor solution was filled in the eyes of the fibers.

For the positive electrode active material 1, 2 parts by weight of a 20: 1 mixed powder of lithium cobaltate and acelenium black was used.
One part by weight of a 10% solution of polyvinylidene fluoride in N-methylpyrrolidone was mixed and kneaded to form a positive electrode current collector 5 (30 μm
Thick aluminum foil) to a thickness of 150 μm
It dried at 30 degreeC for 30 minutes, and was produced. In the negative electrode active material 3, 1 part by weight of graphite-based carbon was mixed and kneaded with 1 part by weight of a 10% N-methylpyrrolidone solution of polyvinylidene fluoride, and 100 μm on a negative electrode current collector 6 (30 μm thick copper foil).
It was prepared by applying it thickly and drying it at 150 ° C. for 30 minutes.

A non-woven fabric impregnated with a precursor solution of a solid electrolyte is placed on the negative electrode active material 3 and irradiated with ultraviolet light (1 mW / cm ² ) of an ultra-high pressure mercury lamp for 1 minute, polymerized and gelled. An electrolyte film (solid electrolyte layer 2) was formed. Further, the positive electrode active material 1 was connected to the solid electrolyte layer 2 to obtain a battery of Example 1. The positive and negative voltages correspond to the positive electrode current collector 5 and the negative electrode current collector 6 supporting the corresponding electrode active material, respectively.
Can be obtained from

Example 2 A battery of Example 2 was obtained in exactly the same manner as in Example 1 except that the material of the nonwoven fabric was replaced with a rayon-based polymer. (Example 3) Except that the material of the nonwoven fabric was replaced with an aliphatic polyamide polymer material,
A battery of Example 2 was obtained.

Example 4 A battery of Example 4 was obtained in exactly the same manner as in Example 1 except that the material of the nonwoven fabric was replaced with an aromatic polyamide-based polymer material. Example 5 A battery of Example 5 was obtained in exactly the same manner as in Example 1 except that the material of the nonwoven fabric was replaced with a polyolefin-based polymer material.

Example 6 A battery of Example 6 was obtained in exactly the same manner as in Example 1 except that the material of the nonwoven fabric was replaced with a chlorinated polyolefin polymer material. (Example 7) A battery of Example 7 was obtained in exactly the same manner as in Example 1 except that the material of the nonwoven fabric was replaced with a fluorinated polyolefin polymer material.

(Comparative Example 1) As a nonwoven fabric, the density was 1.2 g /
A battery of Comparative Example 1 was obtained in the same manner as in Example 1 except that a rayon-based polymer material of cm ³ was used. Comparative Example 2 Acrylic-modified polyethylene oxide (molecular weight of about 1 after reaction)
A battery of Comparative Example 2 was obtained in the same manner as in Example 1 except that the composition used was 100,000 (ethylene carbonate-diethyl carbonate content 30%).

The open voltages and capacities of the batteries of Examples 1 to 7 and Comparative Examples 1 and 2 were measured. As a result, Examples 1 to
In 7, the open-circuit voltage is 3.6 to 3.7 V and the capacity is 2.5 mAh / cm.
^{Was 2} . On the other hand, in Comparative Example 1, the open-circuit voltage was 3.6 V,
The capacity was 2.0 mAh / cm ² , and in Comparative Example 2, the open-circuit voltage was 3.6 V and the capacity was 2.2 mAh / cm ² . The internal resistance and short-circuit pressure of the batteries of Examples 1 to 7 and Comparative Examples 1 and 2 were measured. Table 2 below shows the experimental results of the internal resistance and the short-circuit pressure. The internal resistance of these batteries was examined by an AC method, which is a general measuring method. Further, the short-circuit pressure was examined by a compression test using a spherical compressor. FIG.
It is a figure showing a compression test method. In this compression test, a battery composed of the positive electrode active material 1, the negative electrode active material 3, and the solid electrolyte layer 2 disposed between the positive electrode active material 1 and the negative electrode active material 3 was subjected to a spherical compression with a radius of 10 mm. Contact child 9
Pressure was applied to the battery from above, and the pressure when the battery was short-circuited, that is, the pressure when the output voltage became 0, was defined as the short-circuit pressure.

[0040]

[Table 2]

As a result, Table 2 shows that the internal resistances of Comparative Examples 1 and 2 are 3.2Ω and 4.1Ω, respectively, while Examples 1 to 7 are 1.5Ω to 1.7Ω. It can be seen that it has been reduced to In addition, the short-circuit pressure of each of Examples 1 to 7 is 110 kg / cm ² or more. Since the short-circuit pressure required for practical use is about several tens of kg / cm ³ , it can be seen that the batteries of Examples 1 to 7 can maintain short-circuit pressure characteristics sufficient for practical use.

[0042]

As described above, according to the present invention, since the nonwoven fabric is formed by impregnating the precursor solution of the solid electrolyte and then polymerizing the solid electrolyte, the solid electrolyte is firmly held by the nonwoven fabric. Thereby, the mechanical characteristics are improved, and a solid electrolyte layer having high ionic conductivity is obtained. Also, by polymerizing and holding the solid electrolyte component on the nonwoven fabric, the uniformity of the thickness of the electrolyte layer is improved as compared with the case of evaporating the non-aqueous solvent, the variation in characteristics can be reduced, and the risk of liquid leakage is more reliable. In addition, the energy required for the polymerization is small, the time is short, and the cost can be reduced and the process can be shortened.

Further, the density of the nonwoven fabric is 1.0 g / cm ³ or less, or the substantial filling rate of the nonwoven fabric is 0.5 or less, and a low molecular solvent component of 40% or more of the weight of the precursor solution of the solid electrolyte is contained. Thereby, the effect that the effect of securing the transportability of ions is further increased while maintaining the mechanical strength is obtained. Therefore, according to the present invention, it is possible to obtain a battery having a solid electrolyte layer having excellent mechanical strength characteristics while maintaining high conductivity, and having excellent capacity characteristics and discharge rate characteristics.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a battery according to an embodiment of the present invention.

FIG. 2 is a plan view showing the battery of the embodiment.

FIG. 3 is a diagram showing the relationship between the organic solvent content of a solid electrolyte material and ionic conductivity.

FIG. 4 is a diagram showing a relationship between ionic conductivity and a capacitance appearance rate.

FIG. 5 is a diagram showing a compression test method.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 positive electrode active material (positive electrode), 2 solid electrolyte layer, 3 negative electrode active material (negative electrode), 4 exterior material (case), 5 positive electrode current collector, 6 negative electrode current collector, 7 positive electrode terminal, 8 negative electrode terminal, 9 sphere Compressor.

Claims (5)

[Claims] 1. A negative electrode composed of an alkali metal, an alloy of an alkali metal and a Group II or Group III metal, or a carbon having an alkali metal ion-absorbing ability, and a metal oxide or oxide capable of lithium intercalation. A positive electrode composed of a conductive polymer having a reducing ability, or a composite thereof, a nonwoven fabric disposed between the positive electrode and the negative electrode, and after impregnating the nonwoven fabric with a precursor solution of a solid electrolyte, A solid electrolyte layer comprising: a solid electrolyte formed by polymerizing the precursor solution. 2. The battery according to claim 1, wherein the density of the nonwoven fabric is 1.0 g / cm ³ or less, and the precursor solution contains 40% or more of a low molecular solvent component. 3. The non-woven fabric has a substantial filling rate (a ratio of a material constituting the non-woven fabric to a unit volume) of 0.5 or less, and the precursor solution contains a low molecular solvent component of 40% or more. The battery according to claim 1, wherein: 4. The non-woven fabric is made of a polyester-based polymer, a rayon-based polymer, an aliphatic polyamide-based polymer, an aromatic polyamide-based polymer, a polyolefin-based polymer, or a chlorinated polyolefin-based polymer. The battery according to claim 1, wherein the battery is one of a molecular material and a fluorinated polyolefin-based polymer material. 5. A step of impregnating a non-woven fabric with a precursor solution of a solid electrolyte, polymerizing the precursor solution to form a solid electrolyte layer, and forming an alkali metal and an alkali metal with a group II or group III metal. An alloy, or a negative electrode composed of carbon having an ability to occlude alkali metal ions, and a positive electrode composed of a metal oxide capable of lithium intercalation or a conductive polymer having an oxidation-reduction ability, or a composite thereof, And a step of sandwiching the solid electrolyte layer.