JP2015026563A - All solid secondary battery, manufacturing method thereof, and electronic equipment - Google Patents

All solid secondary battery, manufacturing method thereof, and electronic equipment Download PDF

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JP2015026563A
JP2015026563A JP2013156535A JP2013156535A JP2015026563A JP 2015026563 A JP2015026563 A JP 2015026563A JP 2013156535 A JP2013156535 A JP 2013156535A JP 2013156535 A JP2013156535 A JP 2013156535A JP 2015026563 A JP2015026563 A JP 2015026563A
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JP6194675B2 (en
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山本　保
Tamotsu Yamamoto
保 山本
肥田　勝春
Katsuharu Hida
勝春 肥田
亮治 伊藤
Ryoji Ito
亮治 伊藤
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

PROBLEM TO BE SOLVED: To improve reliability of an all solid secondary battery, relating to the all solid secondary battery, a method of manufacturing the same, and electronic equipment.SOLUTION: An all solid secondary battery includes a substrate 1, a first electrode film 3 formed on the first substrate 1, a solid electrolyte film 4 formed on the first electrode film 3, a second electrode film 5 formed on the solid electrolyte film 4, and a sealing film 6 which covers the second electrode film 5. At least one of the first electrode film 3 and the second electrode film 5 includes central parts 3x, 5x of a first film thickness T1, and peripheral parts 3y, 5y of second film thickness T2 which is thinner than the first film thickness T1.

Description

本発明は、全固体二次電池とその製造方法、及び電子機器に関する。   The present invention relates to an all-solid secondary battery, a method for manufacturing the same, and an electronic device.

二次電池には様々な種類のものがあるが、なかでも電極や電解質の全てを固体材料から形成する全固体二次電池は、電池内部に液体材料がないため安全性が高いと共に、半導体プロセスで製造できることから小型化が容易であるという利点がある。   There are various types of secondary batteries. Among them, all-solid-state secondary batteries, in which all electrodes and electrolytes are formed from solid materials, are highly safe because there are no liquid materials inside the batteries. Therefore, there is an advantage that downsizing is easy.

全固体電池の負極材料としては、金属の中で酸化還元電位が最も低いリチウムやリチウム合金を採用することが多い。   As a negative electrode material for an all solid state battery, lithium or lithium alloy having the lowest redox potential among metals is often adopted.

このような二次電池には、その信頼性を更に向上させるという点で改善の余地がある。   Such secondary batteries have room for improvement in terms of further improving their reliability.

特開２０１２−１８５９７４公報JP 2012-185974 A 特開２０００−８２４９５号公報JP 2000-82495 A

全固体二次電池とその製造方法、及び電子機器において、全固体二次電池の信頼性を向上させることを目的とする。   An object of the present invention is to improve the reliability of an all-solid-state secondary battery in an all-solid-state secondary battery, its manufacturing method, and electronic equipment.

以下の開示の一観点によれば、基板と、前記基板の上に形成された第１の電極膜と、前記第１の電極膜の上に形成された固体電解質膜と、前記固体電解質膜の上に形成された第２の電極膜と、前記第２の電極膜を覆う封止膜とを有し、前記第１の電極膜と前記第２の電極膜の少なくとも一方が、第１の膜厚の中央部と、前記第１の膜厚よりも薄い第２の膜厚の周縁部とを有する全固体二次電池が提供される。   According to one aspect of the following disclosure, a substrate, a first electrode film formed on the substrate, a solid electrolyte film formed on the first electrode film, and a solid electrolyte film A second electrode film formed thereon; and a sealing film that covers the second electrode film, wherein at least one of the first electrode film and the second electrode film is a first film. An all-solid-state secondary battery having a central portion with a thickness and a peripheral portion with a second film thickness that is thinner than the first film thickness is provided.

また、その開示の他の観点によれば、基板の上に第１の電極膜を形成する工程と、前記第１の電極膜の上に固体電解質膜を形成する工程と、前記固体電解質膜の上に第２の電極膜を形成する工程と、前記第２の電極膜を覆う封止膜を形成する工程とを有し、前記第１の電極膜と前記第２の電極膜の少なくとも一方が、第１の膜厚の中央部と、前記第１の膜厚よりも薄い第２の膜厚の周縁部とを有する全固体二次電池の製造方法が提供される。   According to another aspect of the disclosure, a step of forming a first electrode film on a substrate, a step of forming a solid electrolyte film on the first electrode film, A step of forming a second electrode film thereon, and a step of forming a sealing film covering the second electrode film, wherein at least one of the first electrode film and the second electrode film is There is provided a method for manufacturing an all-solid-state secondary battery having a central portion of a first film thickness and a peripheral portion of a second film thickness that is thinner than the first film thickness.

更に、その開示の別の観点によれば、全固体二次電池と、全固体二次電池の電力により駆動する回路とを有し、前記全固体二次電池が、基板と、前記基板の上に形成された第１の電極膜と、前記第１の電極膜の上に形成された固体電解質膜と、前記固体電解質膜の上に形成された第２の電極膜と、前記第２の電極膜を覆う封止膜とを備え、前記第１の電極膜と前記第２の電極膜の少なくとも一方が、第１の膜厚の中央部と、前記第１の膜厚よりも薄い第２の膜厚の周縁部とを備えた電子機器が提供される。   Further, according to another aspect of the disclosure, an all-solid-state secondary battery and a circuit that is driven by the power of the all-solid-state secondary battery are provided, and the all-solid-state secondary battery includes a substrate and an upper surface of the substrate. A first electrode film formed on the first electrode film, a solid electrolyte film formed on the first electrode film, a second electrode film formed on the solid electrolyte film, and the second electrode A sealing film covering the film, wherein at least one of the first electrode film and the second electrode film has a central portion of the first film thickness and a second thickness smaller than the first film thickness. An electronic device including a peripheral portion having a film thickness is provided.

以下の開示によれば、第１の電極膜と第２の電極膜の少なくとも一方において周縁部を中央部よりも薄くするので、充電時や放電時に周縁部の体積の変化が少なくなる。その結果、第１の電極膜や第２の電極膜において体積の変化量が急激に変わる部分が少なくなるため、これらの電極膜の体積変化に封止膜が追従できるようになり、封止膜に亀裂が生じるのを抑制できる。   According to the following disclosure, in at least one of the first electrode film and the second electrode film, the peripheral portion is made thinner than the central portion, so that the change in the volume of the peripheral portion during charging and discharging is reduced. As a result, in the first electrode film and the second electrode film, there are few portions where the amount of change in volume suddenly changes, so that the sealing film can follow the volume change of these electrode films. It is possible to suppress cracks from occurring.

図１は、本願発明者が検討に使用した全固体二次電池の断面図である。FIG. 1 is a cross-sectional view of an all-solid-state secondary battery used by the inventor for examination. 図２は、充電を続けたときの全固体二次電池の模式断面図である。FIG. 2 is a schematic cross-sectional view of an all-solid-state secondary battery when charging is continued. 図３は、第１実施形態に係る全固体二次電池の断面図である。FIG. 3 is a cross-sectional view of the all solid state secondary battery according to the first embodiment. 図４は、第１実施形態に係る全固体二次電池の充電時の模式断面図である。FIG. 4 is a schematic cross-sectional view of the all solid state secondary battery according to the first embodiment during charging. 図５（ａ）、（ｂ）は、第１実施形態に係る全固体二次電池の製造途中の断面図（その１）である。FIGS. 5A and 5B are cross-sectional views (part 1) in the middle of manufacturing the all-solid-state secondary battery according to the first embodiment. 図６（ａ）、（ｂ）は、第１実施形態に係る全固体二次電池の製造途中の断面図（その２）である。6A and 6B are cross-sectional views (part 2) in the middle of manufacturing the all-solid-state secondary battery according to the first embodiment. 図７は、第２実施形態に係る全固体二次電池の断面図である。FIG. 7 is a cross-sectional view of the all solid state secondary battery according to the second embodiment. 図８（ａ）、（ｂ）は、第２実施形態に係る全固体二次電池の製造途中の断面図（その１）である。8A and 8B are cross-sectional views (part 1) in the middle of manufacturing the all-solid-state secondary battery according to the second embodiment. 図９（ａ）、（ｂ）は、第２実施形態に係る全固体二次電池の製造途中の断面図（その２）である。FIGS. 9A and 9B are cross-sectional views (part 2) in the middle of manufacturing the all solid state secondary battery according to the second embodiment. 図１０は、第３実施形態に係る全固体二次電池の断面図である。FIG. 10 is a cross-sectional view of the all solid state secondary battery according to the third embodiment. 図１１は、第３実施形態に係る全固体二次電池の放電時の模式断面図である。FIG. 11 is a schematic cross-sectional view of the all solid state secondary battery according to the third embodiment during discharging. 図１２（ａ）、（ｂ）は、第３実施形態に係る全固体二次電池の製造途中の断面図（その１）である。12A and 12B are cross-sectional views (part 1) in the middle of manufacturing the all-solid-state secondary battery according to the third embodiment. 図１３は、第３実施形態に係る全固体二次電池の製造途中の断面図（その２）である。FIG. 13: is sectional drawing (the 2) in the middle of manufacture of the all-solid-state secondary battery which concerns on 3rd Embodiment. 図１４は、第４実施形態に係る全固体二次電池の断面図である。FIG. 14 is a cross-sectional view of an all solid state secondary battery according to the fourth embodiment. 図１５（ａ）、（ｂ）は、第４実施形態に係る全固体二次電池の製造途中の断面図（その１）である。15A and 15B are cross-sectional views (part 1) in the middle of manufacturing the all-solid-state secondary battery according to the fourth embodiment. 図１６（ａ）、（ｂ）は、第４実施形態に係る全固体二次電池の製造途中の断面図（その２）である。16A and 16B are cross-sectional views (part 2) in the middle of manufacturing the all-solid-state secondary battery according to the fourth embodiment. 図１７は、第５実施形態に係る電子機器の断面図である。FIG. 17 is a cross-sectional view of an electronic apparatus according to the fifth embodiment.

本実施形態の説明に先立ち、本願発明者が検討した事項について説明する。   Prior to the description of the present embodiment, items studied by the inventor will be described.

図１は、その検討に使用した全固体二次電池の断面図である。   FIG. 1 is a cross-sectional view of the all solid state secondary battery used for the study.

この全固体二次電池１０は、負極材料としてリチウムを使用したものであって、基板１の上に集電体２、正極膜３、固体電解質膜４、及び負極膜５をこの順に形成してなる。   This all-solid-state secondary battery 10 uses lithium as a negative electrode material. A current collector 2, a positive electrode film 3, a solid electrolyte film 4, and a negative electrode film 5 are formed on a substrate 1 in this order. Become.

これらのうち、集電体２は厚さが２０nm程度のプラチナ膜であり、正極膜３は厚さが１０μm程度のコバルト酸リチウム（LiCoO2）膜である。そして、固体電解質膜４としては例えばLiPON膜を２μm程度の厚さに形成し、負極膜５としては例えばリチウム膜やリチウム合金膜を５μm程度の厚さに形成する。 Among these, the current collector 2 is a platinum film having a thickness of about 20 nm, and the positive electrode film 3 is a lithium cobalt oxide (LiCoO 2 ) film having a thickness of about 10 μm. For example, a LiPON film is formed to a thickness of about 2 μm as the solid electrolyte film 4, and a lithium film or a lithium alloy film is formed to a thickness of about 5 μm as the negative electrode film 5.

固体電解質膜４は正極膜３の上面と側面とを覆うように形成されており、固体電解質４の上に形成された負極膜５の幅は正極膜３の幅よりも広い。そのため、負極膜５は、正極膜３に対向する中央部５ｘと、正極膜３に対向しない周縁部５ｙとを有することになる。   The solid electrolyte film 4 is formed so as to cover the upper surface and side surfaces of the positive electrode film 3, and the width of the negative electrode film 5 formed on the solid electrolyte 4 is wider than the width of the positive electrode film 3. Therefore, the negative electrode film 5 has a central portion 5 x that faces the positive electrode film 3 and a peripheral portion 5 y that does not face the positive electrode film 3.

ここで、負極膜５の材料であるリチウムが大気中の水分と触れると水酸化リチウムが生成され、その水酸化リチウムが原因で全固体二次電池１０を充放電するのが困難となる。   Here, when lithium which is the material of the negative electrode film 5 comes into contact with moisture in the atmosphere, lithium hydroxide is generated, and it becomes difficult to charge and discharge the all-solid-state secondary battery 10 due to the lithium hydroxide.

そのため、この例では封止膜６で負極膜５を覆うことにより、負極膜５が大気中の水分に曝されるのを防止する。その封止膜６としては、水分の透過防止能力に優れたアルミナ（Al2O3）膜や酸化シリコン（SiO2）膜等の無機酸化膜を形成するのが好ましい。 Therefore, in this example, the negative electrode film 5 is covered with the sealing film 6 to prevent the negative electrode film 5 from being exposed to moisture in the atmosphere. As the sealing film 6, it is preferable to form an inorganic oxide film such as an alumina (Al 2 O 3 ) film or a silicon oxide (SiO 2 ) film excellent in moisture permeation preventing ability.

このような全固体二次電池１０においては、充電の際に正極膜３から負極膜５に向かってリチウムイオン７が移動し、負極膜５においてそのリチウムイオン７が金属リチウム８となって析出する。   In such an all-solid secondary battery 10, lithium ions 7 move from the positive electrode film 3 toward the negative electrode film 5 during charging, and the lithium ions 7 are deposited as metallic lithium 8 in the negative electrode film 5. .

図２は、充電を続けたときの全固体二次電池１０の模式断面図である。   FIG. 2 is a schematic cross-sectional view of the all-solid-state secondary battery 10 when charging is continued.

図２に示すように、充電を続けると負極膜５に析出する金属リチウム８の量が多くなり、点線のように負極膜５の体積が増加する。   As shown in FIG. 2, when charging is continued, the amount of metallic lithium 8 deposited on the negative electrode film 5 increases, and the volume of the negative electrode film 5 increases as indicated by a dotted line.

リチウムイオン７は正極膜３の表面に対して略垂直に移動するため、正極膜３に対向する負極膜５の中央部５ｘでは上記のような体積の増大が顕著となる。一方、正極膜３に対向していない負極膜５の周縁部５ｙでは、正極膜３から移動してくるリチウムイオン７の数が少ないため体積は殆ど増加しない。   Since the lithium ions 7 move substantially perpendicular to the surface of the positive electrode film 3, the increase in volume as described above becomes significant at the central portion 5 x of the negative electrode film 5 facing the positive electrode film 3. On the other hand, in the peripheral portion 5y of the negative electrode film 5 not facing the positive electrode film 3, the volume hardly increases because the number of lithium ions 7 moving from the positive electrode film 3 is small.

中央部５ｘと周縁部５ｙとでこのように体積の増加量が異なると、充放電を繰り返すうちに各部５ｘ、５ｙの境界に接する部分の封止膜６が負極膜５の体積の増加に追従できなくなり、封止膜６に亀裂６ｘが生じることが明らかとなった。   If the amount of increase in volume is different between the central portion 5x and the peripheral portion 5y in this way, the portion of the sealing film 6 in contact with the boundary between the portions 5x and 5y follows the increase in the volume of the negative electrode film 5 while charging and discharging are repeated. As a result, it became clear that cracks 6x occurred in the sealing film 6.

このように亀裂６ｘが生じると、大気中の水分が亀裂６ｘを通じて負極膜５に至り、その水分が原因で負極膜５に水酸化リチウムが生成され、全固体二次電池１を充放電するのが難しくなってしまう。   When the crack 6x is generated in this way, moisture in the atmosphere reaches the negative electrode film 5 through the crack 6x, and lithium hydroxide is generated in the negative electrode film 5 due to the moisture, and the all-solid secondary battery 1 is charged and discharged. Becomes difficult.

本願発明者の調査によれば、この全固体二次電池１に対して充放電を６０回行ったところ、封止膜６に亀裂６ｘが発生し、それ以降の充放電容量が急激に低下した。   According to the inventor's investigation, when charging / discharging was performed on the all-solid-state secondary battery 1 60 times, a crack 6x occurred in the sealing film 6 and the subsequent charging / discharging capacity rapidly decreased. .

以下に、封止膜に上記のような亀裂が入り難くすることができる各実施形態について説明する。   In the following, each embodiment capable of making it difficult for cracks to enter the sealing film will be described.

（第１実施形態）
図３は、第１実施形態に係る全固体二次電池の断面図である。 (First embodiment)
FIG. 3 is a cross-sectional view of the all solid state secondary battery according to the first embodiment.

なお、図３において、図１や図２で説明したのと同じ要素にはこれらの図におけるのと同じ符号を付し、以下ではその説明を省略する。   In FIG. 3, the same elements as those described in FIGS. 1 and 2 are denoted by the same reference numerals as those in FIGS.

この全固体二次電池２０における正極膜３は、第１の膜厚T1の中央部３ｘと第２の膜厚T2の周縁部３ｙとを有しており、第２の膜厚T2が第１の膜厚T1よりも薄い。   The positive electrode film 3 in the all-solid-state secondary battery 20 has a central part 3x having a first film thickness T1 and a peripheral part 3y having a second film thickness T2, and the second film thickness T2 is the first film thickness T2. Is thinner than T1.

周縁部３ｙの断面形状は特に限定されないが、この例では周縁部３ｙの端３ｚに向かって第２の膜厚T2が連続的に減少するように周縁部３ｙを形成する。このような周縁部３ｙの形状に倣い、固体電解質膜４や負極膜５の上面も傾斜するようになる。なお、正極膜３と負極膜５は、それぞれ第１の電極膜と第２の電極膜の一例である。   The cross-sectional shape of the peripheral edge 3y is not particularly limited. In this example, the peripheral edge 3y is formed so that the second film thickness T2 continuously decreases toward the end 3z of the peripheral edge 3y. Following the shape of the peripheral edge 3y, the upper surfaces of the solid electrolyte membrane 4 and the negative electrode membrane 5 are also inclined. The positive electrode film 3 and the negative electrode film 5 are examples of a first electrode film and a second electrode film, respectively.

また、正極膜３の材料は例えばコバルト酸リチウムであり、負極膜５の材料は例えばリチウムやリチウム合金である。   The material of the positive electrode film 3 is, for example, lithium cobaltate, and the material of the negative electrode film 5 is, for example, lithium or a lithium alloy.

なお、全固体二次電池２０の幅は特に限定されないが、この例ではその幅を数mm〜数十mm程度とする。   The width of the all-solid-state secondary battery 20 is not particularly limited, but in this example, the width is about several mm to several tens mm.

更に、負極膜５の幅は正極膜３の幅よりも広く、負極膜５は正極膜３の端３ｚから０．１mm〜１０mm程度のはみ出し量Sだけはみ出る。これについては後述の第２〜第５実施形態でも同様である。   Further, the width of the negative electrode film 5 is wider than that of the positive electrode film 3, and the negative electrode film 5 protrudes from the end 3 z of the positive electrode film 3 by an amount of protrusion S of about 0.1 mm to 10 mm. The same applies to second to fifth embodiments described later.

図４は、充電時の全固体二次電池２０の模式断面図である。   FIG. 4 is a schematic cross-sectional view of the all solid state secondary battery 20 during charging.

前述のように、正極膜３と負極膜５の材料の組み合わせがコバルト酸リチウムとリチウム等の場合には、充電時に正極膜３から負極膜５にリチウムイオン７が移動し、これにより析出した金属リチウム８により負極膜５の体積が増大する。その体積の増大量は正極膜３から出るリチウムイオン７の量に依存する。本実施形態では上記のように正極膜３の周縁部３ｙを中央部３ｘよりも薄くしたので、周縁部３ｙに含まれるリチウムの量が減り、中央部３ｘから周縁部３ｙに向かうにつれてリチウムイオン７の量も減る。   As described above, when the material combination of the positive electrode film 3 and the negative electrode film 5 is lithium cobaltate and lithium, the lithium ions 7 move from the positive electrode film 3 to the negative electrode film 5 during charging, and the deposited metal The volume of the negative electrode film 5 is increased by the lithium 8. The increase in volume depends on the amount of lithium ions 7 coming out of the positive electrode film 3. In the present embodiment, since the peripheral edge portion 3y of the positive electrode film 3 is made thinner than the central portion 3x as described above, the amount of lithium contained in the peripheral edge portion 3y decreases, and lithium ions 7 increase from the central portion 3x toward the peripheral edge portion 3y. The amount of is also reduced.

よって、リチウムイオン７が原因の負極膜５の体積の増加量が中央部３ｘから周縁部３ｙに向かうにつれて徐々に減り、負極膜５において体積の増加量が急激に変わる部分がなくなる。その結果、負極膜５の体積増加に封止膜６が追従できるようになり、封止膜６に生じる亀裂を抑制できる。   Therefore, the amount of increase in the volume of the negative electrode film 5 caused by the lithium ions 7 gradually decreases from the central portion 3x toward the peripheral portion 3y, and there is no portion in the negative electrode film 5 where the volume increase amount changes abruptly. As a result, the sealing film 6 can follow the volume increase of the negative electrode film 5, and cracks generated in the sealing film 6 can be suppressed.

特に、この例のように周縁部３ｙの端３ｚに向かって第２の膜厚T2を連続的に減少させることで、負極膜５の体積増加も連続的に減少し、負極膜５の体積増加に封止膜６がより一層容易に追従できるようになる。   In particular, by continuously decreasing the second film thickness T2 toward the end 3z of the peripheral edge 3y as in this example, the volume increase of the negative electrode film 5 is also continuously decreased, and the volume increase of the negative electrode film 5 is increased. Thus, the sealing film 6 can follow more easily.

このように、本実施形態によれば、充放電を繰り返しても封止膜６に亀裂が入り難くなり、長期間にわたって全固体二次電池２０の信頼性を維持することが可能となる。   As described above, according to the present embodiment, the sealing film 6 is hardly cracked even after repeated charge and discharge, and the reliability of the all-solid-state secondary battery 20 can be maintained over a long period of time.

次に、本実施形態に係る全固体二次電池の製造方法について説明する。   Next, a manufacturing method of the all solid state secondary battery according to the present embodiment will be described.

図５〜図６は、本実施形態に係る全固体二次電池の製造途中の断面図である。   5-6 is sectional drawing in the middle of manufacture of the all-solid-state secondary battery which concerns on this embodiment.

まず、図５（ａ）に示すように、基板１としてシリコン基板を用意し、その基板１の上に集電体２としてプラチナ膜を２０nmの厚さにスパッタ法で形成する。なお、そのスパッタ法では不図示のメタルマスクが使用され、成膜の時点で集電体２は平面視で矩形状に整形される。   First, as shown in FIG. 5A, a silicon substrate is prepared as the substrate 1, and a platinum film as a current collector 2 is formed on the substrate 1 to a thickness of 20 nm by sputtering. In the sputtering method, a metal mask (not shown) is used, and the current collector 2 is shaped into a rectangular shape in plan view at the time of film formation.

また、基板１はシリコン基板に限定されず、マイカ基板を基板１として用いてもよい。更に、集電体２の形成前に、基板１の上に密着膜としてチタン膜等の金属膜を形成してもよい。   The substrate 1 is not limited to a silicon substrate, and a mica substrate may be used as the substrate 1. Furthermore, a metal film such as a titanium film may be formed on the substrate 1 as an adhesion film before the current collector 2 is formed.

次に、図５（ｂ）に示すように、開口２２ａを備えたメタルマスク２２を基板１の上方に配する。そして、基板１の横方向Dにメタルマスク２２を揺動させつつ、開口２２ａを通じて集電体２の上に正極膜３の電極材料３ｗとしてコバルト酸リチウムをスパッタ法で供給する。   Next, as shown in FIG. 5B, a metal mask 22 having an opening 22 a is disposed above the substrate 1. Then, while swinging the metal mask 22 in the lateral direction D of the substrate 1, lithium cobalt oxide is supplied as the electrode material 3w of the positive electrode film 3 onto the current collector 2 through the opening 22a by sputtering.

このとき、開口２２ａから常に露出している部分の集電体２には電極材料３ｗが多く供給されるため正極膜３の中央部３ｘが厚く形成される。この例では正極膜３の成膜時間を調節することにより中央部３ｘの膜厚T1を１０μm程度とする。   At this time, since a large amount of the electrode material 3w is supplied to the current collector 2 that is always exposed from the opening 22a, the central portion 3x of the positive electrode film 3 is formed thick. In this example, the film thickness T1 of the central portion 3x is set to about 10 μm by adjusting the film formation time of the positive electrode film 3.

一方、集電体２の周縁領域においては、揺動しているメタルマスク２２によって電極材料３ｗの供給が断続的に遮断されるため、端３ｚに向かって膜厚T2が連続的に薄くなる周縁部３ｙを形成することができる。   On the other hand, in the peripheral region of the current collector 2, the supply of the electrode material 3w is intermittently interrupted by the swinging metal mask 22, so that the film thickness T2 continuously decreases toward the end 3z. The portion 3y can be formed.

なお、周縁部３ｙの幅Wは、メタルマスク２２の振幅と略同一であり、この例では幅Wを１００μm〜１０mm程度とする。   Note that the width W of the peripheral edge portion 3y is substantially the same as the amplitude of the metal mask 22, and in this example, the width W is about 100 μm to 10 mm.

続いて、図６（ａ）に示すように、正極膜３の上にスパッタ法でLiPON膜を２μm程度の膜厚に形成し、そのLiPON膜を固体電解質膜４とする。   Subsequently, as shown in FIG. 6A, a LiPON film is formed on the positive electrode film 3 by sputtering to a thickness of about 2 μm, and the LiPON film is used as the solid electrolyte film 4.

更に、この固体電解質膜４の上に負極膜５としてリチウム膜を５μm程度の厚さに蒸着法で形成する。リチウム膜に代えてリチウム合金膜を負極膜５として形成してもよい。   Further, a lithium film is formed as a negative electrode film 5 on the solid electrolyte film 4 to a thickness of about 5 μm by vapor deposition. A lithium alloy film may be formed as the negative electrode film 5 instead of the lithium film.

なお、固体電解質膜４や負極膜５を形成するスパッタ法や蒸着法ではメタルマスクが用いられ、固体電解質膜４と負極膜５は成膜の時点で平面視で矩形状に整形される。   Note that a metal mask is used in the sputtering method or vapor deposition method for forming the solid electrolyte film 4 or the negative electrode film 5, and the solid electrolyte film 4 and the negative electrode film 5 are shaped into a rectangular shape in plan view at the time of film formation.

次に、図６（ｂ）に示すように、アルミナ膜や酸化シリコン膜等の無機酸化膜６ａとポリウレア膜等の樹脂膜６ｂとを負極膜５の上に交互に積層し、これらの膜６ａ、６ｂを封止膜６とする。なお、その封止膜６の無機酸化膜６ａはスパッタ法で形成され、樹脂膜６ｂは蒸着重合法により形成される。   Next, as shown in FIG. 6B, an inorganic oxide film 6a such as an alumina film or a silicon oxide film and a resin film 6b such as a polyurea film are alternately laminated on the negative electrode film 5, and these films 6a 6b is used as the sealing film 6. The inorganic oxide film 6a of the sealing film 6 is formed by sputtering, and the resin film 6b is formed by vapor deposition polymerization.

無機酸化膜６ａは、水分透過能力に優れており外部雰囲気中の水分が負極膜５に至るのを阻止する役割を担う。そして、その無機酸化膜６ａの層間に柔らかな樹脂膜６ｂを形成することにより、前述の負極膜５の体積変化に封止膜６が良好に追従し易くなり、封止膜６に亀裂が生じるのを抑制できる。   The inorganic oxide film 6 a is excellent in moisture permeability and plays a role of preventing moisture in the external atmosphere from reaching the negative electrode film 5. Then, by forming a soft resin film 6b between the inorganic oxide films 6a, the sealing film 6 can easily follow the volume change of the negative electrode film 5 and a crack is generated in the sealing film 6. Can be suppressed.

本実施形態では、この封止膜６の全体の厚さを例えば１μm 〜１００μm程度とする。   In the present embodiment, the total thickness of the sealing film 6 is, for example, about 1 μm to 100 μm.

以上により、本実施形態に係る全固体二次電池２０の基本構造が完成する。   As described above, the basic structure of the all solid state secondary battery 20 according to the present embodiment is completed.

上記した本実施形態によれば、図５（ｂ）に示したようにメタルマスク２２を揺動させることにより、膜厚T2が連続的に減少する正極膜３の周縁部３ｙを形成することができる。   According to the present embodiment described above, the peripheral portion 3y of the positive electrode film 3 in which the film thickness T2 continuously decreases can be formed by swinging the metal mask 22 as shown in FIG. it can.

中央部３ｘの膜厚T1よりも薄い膜厚T2を有する周縁部３ｙは、前述のように封止膜６に生じる亀裂の抑制に寄与する。本願発明者の調査によれば、上記のようにして作製した全固体二次電池２０は、充放電を５００回繰り返した後でも封止膜６に亀裂が入らないことが確認された。   The peripheral portion 3y having a film thickness T2 smaller than the film thickness T1 of the central portion 3x contributes to suppression of cracks generated in the sealing film 6 as described above. According to the inventor's investigation, it was confirmed that the all-solid-state secondary battery 20 produced as described above does not crack in the sealing film 6 even after 500 times of charge and discharge.

（第２実施形態）
第１実施形態では、図３に示したように、正極膜３の周縁部３ｙの膜厚T2を端３ｚに向けて連続的に薄くした。これに対し、本実施形態では正極膜３の膜厚を段階的に薄くする。 (Second Embodiment)
In the first embodiment, as shown in FIG. 3, the film thickness T2 of the peripheral edge portion 3y of the positive electrode film 3 is continuously reduced toward the end 3z. In contrast, in the present embodiment, the thickness of the positive electrode film 3 is reduced stepwise.

図７は、本実施形態に係る全固体二次電池の断面図である。なお、図７において第１実施形態で説明したのと同じ要素には第１実施形態におけるのと同じ符号を付し、以下ではその説明を省略する。   FIG. 7 is a cross-sectional view of the all solid state secondary battery according to the present embodiment. In FIG. 7, the same elements as those described in the first embodiment are denoted by the same reference numerals as those in the first embodiment, and the description thereof is omitted below.

図７に示すように、この全固体二次電池３０においては正極膜３が下側層３ａと上側層３ｂとを有する。その上側層３ｂの側面を下側層３ａの側面から後退させることで、正極膜３の中央部３ｘから周縁部３ｙにかけて階段形状を付与し、正極膜３の膜厚を端３ｚに向けて段階的に減少させる。   As shown in FIG. 7, in this all solid state secondary battery 30, the positive electrode film 3 has a lower layer 3a and an upper layer 3b. By retreating the side surface of the upper layer 3b from the side surface of the lower layer 3a, a step shape is imparted from the central part 3x to the peripheral part 3y of the positive electrode film 3, and the film thickness of the positive electrode film 3 is stepped toward the end 3z. Decrease.

なお、正極膜３の膜厚は特に限定されないが、この例では中央部３ｘの膜厚T1を１０μm程度とし、周縁部３ｙの膜厚T2を５μm程度とする。   The film thickness of the positive electrode film 3 is not particularly limited. In this example, the film thickness T1 of the central portion 3x is set to about 10 μm, and the film thickness T2 of the peripheral edge portion 3y is set to about 5 μm.

また、下側層３ａの側面からの上側層３ｂの側面の後退量Lは、例えば１００μm〜１０mm程度とする。   Further, the retraction amount L of the side surface of the upper layer 3b from the side surface of the lower layer 3a is, for example, about 100 μm to 10 mm.

これによれば、第１実施形態と同様に充電時に正極膜３から負極膜５に移動するリチウムイオンの量を周縁部３ｙにおいて低減でき、リチウムイオンが原因の負極膜５の体積の増加量を中央部３ｘから周縁部３ｙに向けて減らすことができる。その結果、負極膜５の体積増加に封止膜６が容易に追従し、封止膜６に亀裂が生じるのを抑制できる。   According to this, similarly to the first embodiment, the amount of lithium ions moving from the positive electrode film 3 to the negative electrode film 5 at the time of charging can be reduced in the peripheral portion 3y, and the increase in volume of the negative electrode film 5 caused by lithium ions can be reduced. It can reduce toward the peripheral part 3y from the center part 3x. As a result, the sealing film 6 can easily follow the volume increase of the negative electrode film 5, and cracking of the sealing film 6 can be suppressed.

次に、本実施形態に係る全固体二次電池の製造方法について説明する。   Next, a manufacturing method of the all solid state secondary battery according to the present embodiment will be described.

図８〜図９は、本実施形態に係る全固体二次電池の製造途中の断面図である。   8-9 is sectional drawing in the middle of manufacture of the all-solid-state secondary battery which concerns on this embodiment.

まず、第１実施形態の図５（ａ）の工程を行うことで、図８（ａ）のように基板１の上に集電体２が形成された構造を作製する。   First, by performing the process of FIG. 5A of the first embodiment, a structure in which the current collector 2 is formed on the substrate 1 as shown in FIG.

次いで、図８（ｂ）に示すように、集電体２と略同じ大きさの第１の開口２４ａを備えた第１のメタルマスク２４を基板１の上方に配する。そして、その第１の開口２４ａを通じて集電体２の上に正極膜３の電極材料３ｗとしてコバルト酸リチウムをスパッタ法で供給することにより、正極膜３の下側層３ａを５μm程度の厚さに形成する。   Next, as shown in FIG. 8B, a first metal mask 24 having a first opening 24 a having the same size as the current collector 2 is disposed above the substrate 1. Then, by supplying lithium cobalt oxide by sputtering as the electrode material 3w of the positive electrode film 3 onto the current collector 2 through the first opening 24a, the lower layer 3a of the positive electrode film 3 has a thickness of about 5 μm. To form.

次に、図９（ａ）に示すように、下側層３ａよりも小さい第２の開口２５ａを備えた第２のメタルマスク２５を基板１の上方に配する。その後、第２の開口２５ａを通じて下側層３ａの上に電極材料３ｗとしてコバルト酸リチウムをスパッタ法で供給し、下側層３ａの側面よりも後退した上側層３ｂを５μm程度の厚さに形成する。   Next, as shown in FIG. 9A, a second metal mask 25 having a second opening 25 a smaller than the lower layer 3 a is disposed above the substrate 1. After that, lithium cobalt oxide is supplied as the electrode material 3w onto the lower layer 3a through the second opening 25a by sputtering, and the upper layer 3b that is recessed from the side surface of the lower layer 3a is formed to a thickness of about 5 μm. To do.

ここまでの工程により、下側層３ａと上側層３ｂとを順に形成してなる正極膜３が得られる。   Through the steps so far, the positive electrode film 3 formed by sequentially forming the lower layer 3a and the upper layer 3b is obtained.

この後は、第１実施形態で説明した図６（ａ）〜（ｂ）の工程を行うことで、図９（ｂ）に示す全固体二次電池３０の基本構造を完成させる。   Thereafter, the basic structure of the all-solid-state secondary battery 30 shown in FIG. 9B is completed by performing the steps of FIGS. 6A to 6B described in the first embodiment.

その全固体二次電池３０においては、上記のように上側層３ｂの側面を下側層３ａの側面から後退させることで正極膜３の断面形状が階段状となり、これにより前述のように封止膜６に亀裂が生じるのを抑制することができる。   In the all-solid-state secondary battery 30, the cross-sectional shape of the positive electrode film 3 becomes stepped by retreating the side surface of the upper layer 3b from the side surface of the lower layer 3a as described above, thereby sealing as described above. Generation of cracks in the film 6 can be suppressed.

（第３実施形態）
第１、第２実施形態では、充電時における負極膜５の体積増加が原因で生じる封止膜６の亀裂を防止した。 (Third embodiment)
In the first and second embodiments, cracking of the sealing film 6 caused by an increase in the volume of the negative electrode film 5 during charging is prevented.

これに対し、本実施形態では、以下のようにして放電時に封止膜６に生じる亀裂を防止する。   On the other hand, in this embodiment, the crack which arises in the sealing film 6 at the time of discharge is prevented as follows.

図１０は、本実施形態に係る全固体二次電池の断面図である。なお、図１０において、第１実施形態や第２実施形態で説明したのと同じ要素にはこれらの実施形態におけるのと同じ符号を付し、以下ではその説明を省略する。   FIG. 10 is a cross-sectional view of the all solid state secondary battery according to the present embodiment. In FIG. 10, the same elements as those described in the first embodiment and the second embodiment are denoted by the same reference numerals as those in these embodiments, and the description thereof is omitted below.

この全固体二次電池４０の負極５は、第１の膜厚T1の中央部５ｘと第２の膜厚T2の周縁部５ｙとを有しており、第２の膜厚T2が第１の膜厚T1よりも薄い。そして、第２の膜厚T2は、周縁部５ｙの端５ｚに向かって連続的に減少する。   The negative electrode 5 of the all-solid-state secondary battery 40 has a central portion 5x having a first thickness T1 and a peripheral portion 5y having a second thickness T2, and the second thickness T2 is the first thickness T2. It is thinner than film thickness T1. The second film thickness T2 continuously decreases toward the end 5z of the peripheral edge portion 5y.

ここで、負極膜５の材料は、第１、第２実施形態と同様にリチウムやリチウム合金である。一方、正極膜３の材料は、第１、第２実施形態と異なり、マンガン酸リチウム（LixMnO2(0≦x＜1)）である。 Here, the material of the negative electrode film 5 is lithium or a lithium alloy as in the first and second embodiments. On the other hand, unlike the first and second embodiments, the material of the positive electrode film 3 is lithium manganate (Li x MnO 2 (0 ≦ x <1)).

このような材料の組み合わせの場合、以下のように放電時に負極膜５の体積が減少する。   In the case of such a combination of materials, the volume of the negative electrode film 5 decreases during discharge as follows.

図１１は、放電時の全固体二次電池４０の模式断面図である。   FIG. 11 is a schematic cross-sectional view of the all solid state secondary battery 40 during discharge.

上記のように正極膜３の材料としてリチウムマンガンオキサイドを使用し、かつ負極膜５としてリチウムやその合金を使用する場合、放電時にリチウムイオン７が負極膜５から正極膜３に移動し、正極膜３内に金属リチウム８が吸蔵される。そのリチウムイオン７は負極膜５に由来しているため、放電を続けると点線のように負極膜５の体積が減少する。   When lithium manganese oxide is used as the material of the positive electrode film 3 and lithium or an alloy thereof is used as the negative electrode film 5 as described above, the lithium ions 7 move from the negative electrode film 5 to the positive electrode film 3 during discharge, and the positive electrode film 3 is occluded with metallic lithium 8. Since the lithium ions 7 are derived from the negative electrode film 5, the volume of the negative electrode film 5 decreases as indicated by the dotted line when the discharge is continued.

このような負極膜５の体積の減少量は、負極膜５から出るリチウムイオン７の量に依存する。本実施形態では上記のように負極膜５の周縁部５ｙを中央部５ｘよりも薄くしたので周縁部５ｙに含まれるリチウムの量が減り、中央部５ｘから周縁部５ｙに向かうにつれてリチウムイオン７の量も減る。   The amount of decrease in the volume of the negative electrode film 5 depends on the amount of lithium ions 7 coming out of the negative electrode film 5. In the present embodiment, since the peripheral edge 5y of the negative electrode film 5 is made thinner than the central part 5x as described above, the amount of lithium contained in the peripheral part 5y decreases, and the lithium ions 7 move toward the peripheral part 5y from the central part 5x. The amount is also reduced.

したがって、負極膜５の体積の減少量が中央部５ｘから周縁部５ｙに向かうにつれて徐々に減り、負極膜５において体積の減少量が急激に変わる部分がなくなる。これにより、負極膜５の体積減少に封止膜６が追従できるようになり、負極膜５の体積減少が原因で封止膜６に亀裂が生じるのを抑制できる。   Therefore, the amount of decrease in the volume of the negative electrode film 5 gradually decreases from the central portion 5x toward the peripheral portion 5y, and there is no portion in the negative electrode film 5 where the volume decrease amount changes rapidly. As a result, the sealing film 6 can follow the volume reduction of the negative electrode film 5, and the occurrence of cracks in the sealing film 6 due to the volume reduction of the negative electrode film 5 can be suppressed.

特に、この例のように周縁部５ｙの端５ｚに向かって第２の膜厚T2を連続的に減少させることで、負極膜５の体積減少も連続的に減少し、負極膜５の体積減少に封止膜６がより一層容易に追従できるようになる。   In particular, by continuously reducing the second film thickness T2 toward the end 5z of the peripheral edge 5y as in this example, the volume reduction of the negative electrode film 5 is also continuously reduced, and the volume reduction of the negative electrode film 5 is achieved. Thus, the sealing film 6 can follow more easily.

このように、本実施形態によれば、充放電を繰り返しても封止膜６に亀裂が入り難くなり、長期間にわたって全固体二次電池４０の信頼性を維持することが可能となる。   As described above, according to the present embodiment, the sealing film 6 is hardly cracked even after repeated charge and discharge, and the reliability of the all-solid-state secondary battery 40 can be maintained over a long period of time.

次に、本実施形態に係る全固体二次電池の製造方法について説明する。   Next, a manufacturing method of the all solid state secondary battery according to the present embodiment will be described.

図１２〜図１３は、本実施形態に係る全固体二次電池の製造途中の断面図である。なお、図１２〜図１３において、第１実施形態や第２実施形態で説明したのと同じ要素にはこれらの実施形態におけるのと同じ符号を付し、以下ではその説明を省略する。   12-13 is sectional drawing in the middle of manufacture of the all-solid-state secondary battery which concerns on this embodiment. 12 to 13, the same elements as those described in the first embodiment and the second embodiment are denoted by the same reference numerals as those in these embodiments, and the description thereof is omitted below.

まず、図１２（ａ）に示すように、シリコン基板等の基板１の上にスパッタ法で集電体２としてプラチナ膜を２０nmの膜厚にスパッタ法で形成し、更にその上に正極膜３をスパッタ法で形成する。前述のように、正極膜３の材料はマンガン酸リチウムであって、例えば５μm程度の膜厚に形成し得る。   First, as shown in FIG. 12 (a), a platinum film as a current collector 2 is formed on a substrate 1 such as a silicon substrate by sputtering to a thickness of 20 nm, and further a positive electrode film 3 is formed thereon. Is formed by sputtering. As described above, the material of the positive electrode film 3 is lithium manganate, and can be formed to a thickness of, for example, about 5 μm.

次に、正極膜３の上に固体電解質膜４としてLiPON膜をスパッタ法で２μm程度の膜厚に形成する。   Next, a LiPON film as a solid electrolyte film 4 is formed on the positive electrode film 3 to a thickness of about 2 μm by sputtering.

なお、上記した集電体２、正極膜３、及び固体電解質膜４は、不図示のメタルマスクを用いて成膜され、成膜の時点で平面視で矩形状に整形される。   The current collector 2, the positive electrode film 3, and the solid electrolyte film 4 are formed using a metal mask (not shown) and shaped into a rectangular shape in plan view at the time of film formation.

続いて、図１２（ｂ）に示すように、開口２７ａを備えたメタルマスク２７を基板１の上方に配する。そして、基板１の横方向Dにメタルマスク２７を揺動させながら、開口２７ａを通じて固体電解質膜４の上に負極膜５の電極材料５ｗとしてリチウム又ははリチウム合金を蒸着法で供給する。   Subsequently, as shown in FIG. 12B, a metal mask 27 having an opening 27 a is disposed above the substrate 1. Then, while swinging the metal mask 27 in the lateral direction D of the substrate 1, lithium or a lithium alloy is supplied as an electrode material 5w of the negative electrode film 5 onto the solid electrolyte film 4 through the opening 27a by a vapor deposition method.

これにより、第１実施形態の図５（ｂ）の工程と同様に、端５ｚに向かって膜厚T2が連続的に薄くなる周縁部５ｙを負極膜５に形成できると共に、周縁部５ｙよりも膜厚T1が厚い中央部５ｘを形成することができる。その中央部T1の膜厚は、例えば１０μm程度である。   As a result, as in the step of FIG. 5B of the first embodiment, the peripheral edge portion 5y whose film thickness T2 continuously decreases toward the end 5z can be formed in the negative electrode film 5, and more than the peripheral edge portion 5y. A central portion 5x having a thick film thickness T1 can be formed. The film thickness of the central portion T1 is, for example, about 10 μm.

また、周縁部５ｙの幅Wは、メタルマスク２７の振幅と略同一であり、この例では１００μm〜１０mm程度である。   Further, the width W of the peripheral portion 5y is substantially the same as the amplitude of the metal mask 27, and is about 100 μm to 10 mm in this example.

その後、図１３に示すように、第１実施形態の図６（ｂ）と同じ工程を行うことにより、封止膜６で負極膜５を覆う。   Thereafter, as shown in FIG. 13, the negative electrode film 5 is covered with the sealing film 6 by performing the same process as in FIG. 6B of the first embodiment.

以上により、本実施形態に係る全固体二次電池４０の基本構造が完成する。   As described above, the basic structure of the all-solid-state secondary battery 40 according to this embodiment is completed.

上記した本実施形態によれば、図１２（ｂ）のようにメタルマスク２７を揺動させることで膜厚T2が連続的に減少する負極膜５の周縁部５ｙを形成でき、これにより封止膜６に亀裂が生じるのを抑制することができる。   According to the present embodiment described above, the peripheral portion 5y of the negative electrode film 5 in which the film thickness T2 continuously decreases can be formed by swinging the metal mask 27 as shown in FIG. Generation of cracks in the film 6 can be suppressed.

（第４実施形態）
第３実施形態では、図１０に示したように、負極膜５の周縁部５ｙの膜厚T2を端５ｚに向けて連続的に薄くした。これに対し、本実施形態では負極膜５の膜厚を段階的に薄くする。 (Fourth embodiment)
In the third embodiment, as shown in FIG. 10, the film thickness T2 of the peripheral edge portion 5y of the negative electrode film 5 is continuously reduced toward the end 5z. On the other hand, in the present embodiment, the thickness of the negative electrode film 5 is reduced stepwise.

図１４は、本実施形態に係る全固体二次電池の断面図である。なお、図１４において第１〜３実施形態で説明したのと同じ要素にはこれらと同じ符号を付し、以下ではその説明を省略する。   FIG. 14 is a cross-sectional view of the all solid state secondary battery according to the present embodiment. In FIG. 14, the same elements as those described in the first to third embodiments are denoted by the same reference numerals, and description thereof is omitted below.

図１４に示すように、この全固体二次電池５０においては負極膜５が下側層５ａと上側層５ｂとを有する。その上側層５ｂの側面を下側層５ａの側面よりも後退させることで、この例では負極膜５の中央部５ｘから周縁部５ｙにかけて階段形状を付与し、負極膜５の膜厚をその端５ｚに向けて段階的に減少させる。   As shown in FIG. 14, in this all solid state secondary battery 50, the negative electrode film 5 has a lower layer 5a and an upper layer 5b. By retreating the side surface of the upper layer 5b from the side surface of the lower layer 5a, in this example, a staircase shape is given from the central portion 5x to the peripheral portion 5y of the negative electrode film 5, and the film thickness of the negative electrode film 5 is changed to its end Decrease in steps toward 5z.

なお、負極膜５の膜厚は特に限定されないが、この例では中央部５ｘの膜厚T1を２μm程度とし、周縁部５ｙの膜厚T2を１μm程度とする。   The film thickness of the negative electrode film 5 is not particularly limited, but in this example, the film thickness T1 of the central portion 5x is about 2 μm, and the film thickness T2 of the peripheral portion 5y is about 1 μm.

また、そして、下側層５ａの側面からの上側層５ｂの側面の後退量Lは、例えば１００μm〜１０mm程度とする。   Further, the retraction amount L of the side surface of the upper layer 5b from the side surface of the lower layer 5a is, for example, about 100 μm to 10 mm.

これによれば、第３実施形態と同様に放電時に負極膜５から正極膜３に移動するリチウムイオンの量を周縁部５ｙにおいて低減でき、リチウムイオンが原因の負極膜５の体積の減少量を中央部５ｘから周縁部５ｙに向けて減らすことができる。これにより、負極膜５の体積減少に封止膜６が容易に追従できるようになり、封止膜６に生じる亀裂を抑制できる。   According to this, similarly to the third embodiment, the amount of lithium ions moving from the negative electrode film 5 to the positive electrode film 3 during discharge can be reduced at the peripheral portion 5y, and the amount of decrease in the volume of the negative electrode film 5 caused by lithium ions can be reduced. It can reduce toward the peripheral part 5y from the center part 5x. Thereby, the sealing film 6 can easily follow the volume reduction of the negative electrode film 5, and cracks generated in the sealing film 6 can be suppressed.

次に、本実施形態に係る全固体二次電池の製造方法について説明する。   Next, a manufacturing method of the all solid state secondary battery according to the present embodiment will be described.

図１５〜図１６は、本実施形態に係る全固体二次電池の製造途中の断面図である。   15-16 is sectional drawing in the middle of manufacture of the all-solid-state secondary battery which concerns on this embodiment.

まず、第３実施形態の図１２（ａ）の工程を行うことで、図１５（ａ）のように基板１の上に集電体２、正極膜３、及び固体電解質膜４が順に形成された構造を作製する。   First, the current collector 2, the positive electrode film 3, and the solid electrolyte film 4 are sequentially formed on the substrate 1 as shown in FIG. 15A by performing the process of FIG. 12A of the third embodiment. The structure is made.

次いで、図１５（ｂ）に示すように、固体電解質膜４の上面と略同じ大きさの第１の開口２８ａを備えた第１のメタルマスク２８を基板１の上方に配する。そして、その第１の開口２８ａを通じて固体電解質膜４の上に負極膜５の電極材料５ｗとしてリチウムを蒸着法で供給することにより、負極膜５の下側層５ａを１μm程度の厚さに形成する。   Next, as shown in FIG. 15B, a first metal mask 28 having a first opening 28 a having the same size as the upper surface of the solid electrolyte membrane 4 is disposed above the substrate 1. Then, by supplying lithium as an electrode material 5w of the negative electrode film 5 onto the solid electrolyte film 4 through the first opening 28a by vapor deposition, the lower layer 5a of the negative electrode film 5 is formed to a thickness of about 1 μm. To do.

次に、図１６（ａ）に示すように、下側層５ａよりも小さい第２の開口２９ａを備えた第２のメタルマスク２９を基板１の上方に配する。その後、第２の開口２９ａを通じて下側層５ａの上に電極材料５ｗとしてリチウムマンガンオキサイドをスパッタ法で供給し、下側層５ａの側面から後退した上側層５ｂを１μm程度の厚さに形成する。   Next, as shown in FIG. 16A, a second metal mask 29 having a second opening 29 a smaller than the lower layer 5 a is disposed above the substrate 1. Thereafter, lithium manganese oxide is supplied as the electrode material 5w onto the lower layer 5a through the second opening 29a by sputtering, and the upper layer 5b receding from the side surface of the lower layer 5a is formed to a thickness of about 1 μm. .

ここまでの工程により、下側層５ａと上側層５ｂとを順に形成してなる負極膜５が得られる。   Through the steps so far, the negative electrode film 5 formed by sequentially forming the lower layer 5a and the upper layer 5b is obtained.

その後、図１６（ｂ）に示すように、第１実施形態の図６（ｂ）と同じ工程を行うことにより、封止膜６で負極膜５を覆う。   Thereafter, as shown in FIG. 16B, the negative electrode film 5 is covered with the sealing film 6 by performing the same process as in FIG. 6B of the first embodiment.

以上により、本実施形態に係る全固体二次電池５０の基本構造が完成する。   As described above, the basic structure of the all-solid-state secondary battery 50 according to this embodiment is completed.

その全固体二次電池５０においては、上記のように上側層５ｂの側面を下側層５ａから後退させることで負極膜５の断面形状が階段状となり、前述のように封止膜６に亀裂が生じるのを抑制することができる。   In the all-solid-state secondary battery 50, the side surface of the upper layer 5b is retreated from the lower layer 5a as described above, whereby the cross-sectional shape of the negative electrode film 5 becomes stepped, and the sealing film 6 is cracked as described above. Can be suppressed.

（第５実施形態）
本実施形態では、第１〜第４実施形態で説明した全固体二次電池を利用した電子機器について説明する。 (Fifth embodiment)
In this embodiment, an electronic apparatus using the all solid state secondary battery described in the first to fourth embodiments will be described.

図１７は、本実施形態に係る電子機器の断面図である。   FIG. 17 is a cross-sectional view of the electronic apparatus according to the present embodiment.

この電子機器６０は、例えばエネルギハーベスト技術において使用されるものであり、第１実施形態で説明した全固体二次電池２０と、この全固体二次電池２０の電力により駆動する回路６１とを有する。   The electronic device 60 is used in, for example, energy harvesting technology, and includes the all solid state secondary battery 20 described in the first embodiment and a circuit 61 that is driven by the power of the all solid state secondary battery 20. .

なお、全固体二次電池２０に代えて、第２〜第４実施形態で説明した全固体二次電池３０、４０、５０を用いてもよい。   Instead of the all solid state secondary battery 20, all the solid state secondary batteries 30, 40, 50 described in the second to fourth embodiments may be used.

回路６１は、基板１の上に設けられており、基板１の表面の不図示の配線により全固体二次電池２０の正極膜３と電気的に接続される。   The circuit 61 is provided on the substrate 1 and is electrically connected to the positive electrode film 3 of the all-solid-state secondary battery 20 by wiring (not shown) on the surface of the substrate 1.

また、全固体二次電池２０の負極膜５は、銅等を材料とする配線６２により回路６１と電気的に接続される。なお、この配線６２は、全固体二次電池２０の製造時に負極膜５の上に直接形成され、配線６２の一部が封止膜６により覆われる。   Further, the negative electrode film 5 of the all-solid-state secondary battery 20 is electrically connected to the circuit 61 by a wiring 62 made of copper or the like. The wiring 62 is formed directly on the negative electrode film 5 when the all solid state secondary battery 20 is manufactured, and a part of the wiring 62 is covered with the sealing film 6.

回路６１の機能は特に限定されないが、エネルギハーベスト技術において環境中の温度をモニタするための温度センサや、その温度センサの計測値を無線送信する機能を回路６１に設けるのが好ましい。また、人体の脈拍を計測するための脈拍センサとして回路６１を設けてもよい。   The function of the circuit 61 is not particularly limited, but it is preferable to provide the circuit 61 with a temperature sensor for monitoring the temperature in the environment in the energy harvesting technology and a function for wirelessly transmitting the measured value of the temperature sensor. Further, the circuit 61 may be provided as a pulse sensor for measuring the pulse of the human body.

このような電子機器６０においては、第１実施形態で説明したように封止膜６に亀裂が入りにくい全固体二次電池２０を使用しているため、長期間にわたって環境中の温度等を安定して測定することができる。   In such an electronic device 60, as described in the first embodiment, since the all-solid-state secondary battery 20 that does not easily crack in the sealing film 6 is used, the temperature in the environment and the like can be stabilized over a long period of time. Can be measured.

以上説明した各実施形態に関し、更に以下の付記を開示する。   The following additional notes are disclosed for each embodiment described above.

（付記１） 基板と、
前記基板の上に形成された第１の電極膜と、
前記第１の電極膜の上に形成された固体電解質膜と、
前記固体電解質膜の上に形成された第２の電極膜と、
前記第２の電極膜を覆う封止膜とを有し、
前記第１の電極膜と前記第２の電極膜の少なくとも一方が、第１の膜厚の中央部と、前記第１の膜厚よりも薄い第２の膜厚の周縁部とを有することを特徴とする全固体二次電池。 (Appendix 1) a substrate,
A first electrode film formed on the substrate;
A solid electrolyte membrane formed on the first electrode membrane;
A second electrode film formed on the solid electrolyte film;
A sealing film covering the second electrode film,
At least one of the first electrode film and the second electrode film has a central part having a first film thickness and a peripheral part having a second film thickness smaller than the first film thickness. All-solid-state secondary battery characterized.

（付記２） 前記第２の膜厚は、前記周縁部の端に向かって連続的に減少することを特徴とする付記１に記載の全固体二次電池。   (Supplementary note 2) The all-solid-state secondary battery according to Supplementary note 1, wherein the second film thickness continuously decreases toward an end of the peripheral edge.

（付記３） 前記第２の膜厚は、前記周縁部の端に向かって段階的に減少することを特徴とする付記１に記載の全固体二次電池。   (Additional remark 3) The said 2nd film thickness decreases in steps toward the edge of the said peripheral part, The all-solid-state secondary battery of Additional remark 1 characterized by the above-mentioned.

（付記４） 前記第１の電極膜は正極膜であり、
前記第２の電極膜は、リチウム又はリチウム合金を材料とする負極膜であり、
前記中央部と前記周縁部とが前記正極膜に設けられたことを特徴とする付記１乃至付記３のいずれかに記載の全固体二次電池。 (Supplementary Note 4) The first electrode film is a positive electrode film,
The second electrode film is a negative electrode film made of lithium or a lithium alloy,
The all-solid-state secondary battery according to any one of appendix 1 to appendix 3, wherein the central portion and the peripheral portion are provided on the positive electrode film.

（付記５） 前記第１の電極膜は、マンガン酸リチウムを材料とする正極膜であり、
前記第２の電極膜は、リチウム又はリチウム合金を材料とする負極膜であり、
前記中央部と前記周縁部とが前記負極膜に設けられたことを特徴とする付記１乃至付記３のいずれかに記載の全固体二次電池。 (Appendix 5) The first electrode film is a positive electrode film made of lithium manganate,
The second electrode film is a negative electrode film made of lithium or a lithium alloy,
The all-solid-state secondary battery according to any one of appendix 1 to appendix 3, wherein the central portion and the peripheral portion are provided on the negative electrode film.

（付記６） 基板の上に第１の電極膜を形成する工程と、
前記第１の電極膜の上に固体電解質膜を形成する工程と、
前記固体電解質膜の上に第２の電極膜を形成する工程と、
前記第２の電極膜を覆う封止膜を形成する工程とを有し、
前記第１の電極膜と前記第２の電極膜の少なくとも一方が、第１の膜厚の中央部と、前記第１の膜厚よりも薄い第２の膜厚の周縁部とを有することを特徴とする全固体二次電池の製造方法。 (Appendix 6) A step of forming a first electrode film on a substrate;
Forming a solid electrolyte membrane on the first electrode membrane;
Forming a second electrode film on the solid electrolyte film;
Forming a sealing film covering the second electrode film,
At least one of the first electrode film and the second electrode film has a central part having a first film thickness and a peripheral part having a second film thickness smaller than the first film thickness. A method for producing an all-solid secondary battery.

（付記７） 前記第１の電極膜を形成する工程において、
開口を備えたマスクを前記基板の上方に配し、前記基板に対して横方向に前記マスクを揺動させながら、前記開口を通じて前記基板の上に電極材料を供給することにより、前記第１の電極膜の端に向かって前記第２の膜厚が連続的に薄くなる前記周縁部を形成することを特徴とする付記６に記載の全固体二次電池の製造方法。 (Supplementary Note 7) In the step of forming the first electrode film,
A mask having an opening is disposed above the substrate, and an electrode material is supplied onto the substrate through the opening while swinging the mask laterally with respect to the substrate. The manufacturing method of an all-solid-state secondary battery according to appendix 6, wherein the peripheral portion where the second film thickness continuously decreases toward an end of the electrode film is formed.

（付記８） 前記第２の電極膜を形成する工程において、
開口を備えたマスクを前記基板の上方に配し、前記基板に対して横方向に前記マスクを揺動させながら、前記開口を通じて前記固体電解質膜の上に電極材料を供給することにより、前記第２の電極膜の端に向かって前記第２の膜厚が連続的に薄くなる前記周縁部を形成することを特徴とする付記６に記載の全固体二次電池の製造方法。 (Supplementary Note 8) In the step of forming the second electrode film,
A mask having an opening is disposed above the substrate, and an electrode material is supplied onto the solid electrolyte membrane through the opening while swinging the mask laterally with respect to the substrate. The manufacturing method of an all-solid-state secondary battery according to appendix 6, wherein the peripheral portion where the second film thickness continuously decreases toward the end of the second electrode film is formed.

（付記９） 全固体二次電池と、
全固体二次電池の電力により駆動する回路とを有し、
前記全固体二次電池が、
基板と、
前記基板の上に形成された第１の電極膜と、
前記第１の電極膜の上に形成された固体電解質膜と、
前記固体電解質膜の上に形成された第２の電極膜と、
前記第２の電極膜を覆う封止膜とを備え、
前記第１の電極膜と前記第２の電極膜の少なくとも一方が、第１の膜厚の中央部と、前記第１の膜厚よりも薄い第２の膜厚の周縁部とを備えたことを特徴とする電子機器。 (Supplementary note 9) an all-solid-state secondary battery;
A circuit driven by the power of the all-solid-state secondary battery,
The all solid state secondary battery is
A substrate,
A first electrode film formed on the substrate;
A solid electrolyte membrane formed on the first electrode membrane;
A second electrode film formed on the solid electrolyte film;
A sealing film covering the second electrode film,
At least one of the first electrode film and the second electrode film includes a central part having a first film thickness and a peripheral part having a second film thickness smaller than the first film thickness. Electronic equipment characterized by

１…基板、２…集電体、３…正極膜、３ａ…下側層、３ｂ…上側層、３ｘ…中央部、３ｙ…周縁部、３ｗ…電極材料、４…固体電解質膜、５…負極膜、５ａ…下側層、５ｂ…上側層、５ｗ…電極材料、６…封止膜、６ａ…無機酸化膜、６ｂ…樹脂膜、６ｘ…亀裂、７…リチウムイオン、８…金属リチウム、１０、２０、３０、４０、５０…全固体二次電池、２２、２７…メタルマスク、２２ａ、２７ａ…開口、２４、２８…第１のメタルマスク、２４ａ、２８ａ…第１の開口、２５、２９…第２のメタルマスク、２５ａ、２９ａ…第２の開口、６０…電子機器、６１…回路、６２…配線。 DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Current collector, 3 ... Positive electrode film, 3a ... Lower layer, 3b ... Upper layer, 3x ... Center part, 3y ... Peripheral part, 3w ... Electrode material, 4 ... Solid electrolyte membrane, 5 ... Negative electrode Membrane, 5a ... lower layer, 5b ... upper layer, 5w ... electrode material, 6 ... sealing film, 6a ... inorganic oxide film, 6b ... resin film, 6x ... crack, 7 ... lithium ion, 8 ... metallic lithium, 10 20, 30, 40, 50 ... all solid state secondary battery, 22, 27 ... metal mask, 22 a, 27 a ... opening, 24, 28 ... first metal mask, 24 a, 28 a ... first opening, 25, 29 ... second metal mask, 25a, 29a ... second opening, 60 ... electronic device, 61 ... circuit, 62 ... wiring.

Claims (5)

基板と、
前記基板の上に形成された第１の電極膜と、
前記第１の電極膜の上に形成された固体電解質膜と、
前記固体電解質膜の上に形成された第２の電極膜と、
前記第２の電極膜を覆う封止膜とを有し、
前記第１の電極膜と前記第２の電極膜の少なくとも一方が、第１の膜厚の中央部と、前記第１の膜厚よりも薄い第２の膜厚の周縁部とを有することを特徴とする全固体二次電池。 A substrate,
A first electrode film formed on the substrate;
A solid electrolyte membrane formed on the first electrode membrane;
A second electrode film formed on the solid electrolyte film;
A sealing film covering the second electrode film,
At least one of the first electrode film and the second electrode film has a central part having a first film thickness and a peripheral part having a second film thickness smaller than the first film thickness. All-solid-state secondary battery characterized. 前記第２の膜厚は、前記周縁部の端に向かって連続的に減少することを特徴とする請求項１に記載の全固体二次電池。   2. The all-solid-state secondary battery according to claim 1, wherein the second film thickness continuously decreases toward an end of the peripheral edge. 前記第２の膜厚は、前記周縁部の端に向かって段階的に減少することを特徴とする請求項１に記載の全固体二次電池。   2. The all-solid-state secondary battery according to claim 1, wherein the second film thickness decreases stepwise toward an end of the peripheral edge. 基板の上に第１の電極膜を形成する工程と、
前記第１の電極膜の上に固体電解質膜を形成する工程と、
前記固体電解質膜の上に第２の電極膜を形成する工程と、
前記第２の電極膜を覆う封止膜を形成する工程とを有し、
前記第１の電極膜と前記第２の電極膜の少なくとも一方が、第１の膜厚の中央部と、前記第１の膜厚よりも薄い第２の膜厚の周縁部とを有することを特徴とする全固体二次電池の製造方法。 Forming a first electrode film on the substrate;
Forming a solid electrolyte membrane on the first electrode membrane;
Forming a second electrode film on the solid electrolyte film;
Forming a sealing film covering the second electrode film,
At least one of the first electrode film and the second electrode film has a central part having a first film thickness and a peripheral part having a second film thickness smaller than the first film thickness. A method for producing an all-solid secondary battery. 全固体二次電池と、
全固体二次電池の電力により駆動する回路とを有し、
前記全固体二次電池が、
基板と、
前記基板の上に形成された第１の電極膜と、
前記第１の電極膜の上に形成された固体電解質膜と、
前記固体電解質膜の上に形成された第２の電極膜と、
前記第２の電極膜を覆う封止膜とを備え、
前記第１の電極膜と前記第２の電極膜の少なくとも一方が、第１の膜厚の中央部と、前記第１の膜厚よりも薄い第２の膜厚の周縁部とを備えたことを特徴とする電子機器。 An all-solid-state secondary battery;
A circuit driven by the power of the all-solid-state secondary battery,
The all solid state secondary battery is
A substrate,
A first electrode film formed on the substrate;
A solid electrolyte membrane formed on the first electrode membrane;
A second electrode film formed on the solid electrolyte film;
A sealing film covering the second electrode film,
At least one of the first electrode film and the second electrode film includes a central part having a first film thickness and a peripheral part having a second film thickness smaller than the first film thickness. Electronic equipment characterized by
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