JP2018170297A - All-solid-state battery - Google Patents

All-solid-state battery Download PDF

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JP2018170297A
JP2018170297A JP2018149946A JP2018149946A JP2018170297A JP 2018170297 A JP2018170297 A JP 2018170297A JP 2018149946 A JP2018149946 A JP 2018149946A JP 2018149946 A JP2018149946 A JP 2018149946A JP 2018170297 A JP2018170297 A JP 2018170297A
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glass
solid
layer
battery
battery element
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和仁 小笠
Kazuhito Ogasa
和仁 小笠
巧 西之園
Takumi NISHINOSONO
巧 西之園
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Ohara Inc
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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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

PROBLEM TO BE SOLVED: To provide an all-solid-state battery, capable of preventing a battery from being deteriorated by preventing moisture (water vapor) from entering from the outside and also capable of exhibiting original charge and discharge characteristics by suppressing the inhibition of expansion/contraction of an all-solid-state battery electrode and suppressing a reaction between a glass layer and a battery element.SOLUTION: In an all-solid-state battery, a buffer layer is provided so as to cover a battery element including a positive electrode, a negative electrode and a solid electrolyte, and a glass layer is provided around the buffer layer covering a periphery of the battery element. By the configuration of the glass layer, an electrode can be expanded and contracted, and by suppressing a reaction between the glass layer and the battery element, the battery element can maintain long-term charge/discharge performance.SELECTED DRAWING: Figure 1

Description

本発明は、全固体電池に関する。   The present invention relates to an all solid state battery.

無機固体電解質を用い、電極にも有機物を用いない全固体電池は、有機電解液の漏液や有機電解液からのガス発生の心配がないため、安全な電池として期待されている。また、全固体電池は、液系の電池と比較して電池反応以外の副反応が生じることが少ないため、液系の電池に比べて長寿命化が期待できる。   An all-solid battery that uses an inorganic solid electrolyte and does not use organic substances as an electrode is expected as a safe battery because there is no concern about leakage of the organic electrolyte or gas generation from the organic electrolyte. In addition, the all-solid-state battery is less likely to cause side reactions other than the battery reaction as compared with the liquid battery, so that it can be expected to have a longer life than the liquid battery.

このような全固体電池において、電池反応以外の副反応をより生じさせず、電池の劣化防止を図るため、外部からの水分（水蒸気）侵入を防ぐ必要がある。アルミラミネートパッケージングもコインカシメもいずれも接合部分に樹脂部分があるため、水分の侵入を完全には防げない。また、いずれもケーシングのための電池要素以外の体積が大きくなる。そのため、この体積が大きくなることを防ぎ、かつ確実に水分侵入を防ぐパッケージングが求められている。   In such an all-solid-state battery, it is necessary to prevent moisture (water vapor) from entering from the outside in order to prevent side reactions other than the battery reaction and prevent the battery from deteriorating. Since both aluminum laminate packaging and coin caulking have a resin part at the joint, moisture penetration cannot be completely prevented. In addition, in all cases, the volume other than the battery element for the casing is increased. Therefore, there is a need for packaging that prevents this volume from increasing and reliably prevents moisture intrusion.

例えば特許文献１の図６には、全固体電池の保存特性を向上させるために、正極活物質を含む正極と、負極活物質を含む負極と、正極と負極とに介在する固体電解質とで構成される電池要素を含み、電解質の周りにガラスフリットからなる封止部を有する、全固体電池が記載されている。   For example, FIG. 6 of Patent Document 1 includes a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and a solid electrolyte interposed between the positive electrode and the negative electrode in order to improve storage characteristics of an all-solid battery. An all-solid battery is described that includes a battery element that has a sealing portion made of glass frit around an electrolyte.

特開２００７‐８０８１２号公報JP 2007-80812 A

しかしながら、本発明者は、特許文献１のような全固体電池では、封止に用いるガラスによって、電極の膨張収縮が阻害され、またガラス層と電池要素との分解反応（電池要素中に含まれる正極層、負極層、固体電解質層の分解反応）により、電池の充放電特性を発揮できないおそれがある、という新たな技術課題を見出した。   However, in the all-solid-state battery as disclosed in Patent Document 1, the present inventor inhibits the expansion and contraction of the electrode by the glass used for sealing, and the decomposition reaction between the glass layer and the battery element (included in the battery element). A new technical problem has been found that there is a possibility that the charge / discharge characteristics of the battery may not be exhibited by the decomposition reaction of the positive electrode layer, the negative electrode layer, and the solid electrolyte layer.

本発明は、この課題に鑑みてなされたものであって、その目的とするところは、外部からの水分（水蒸気）侵入を防いで電池の劣化防止が可能で、かつ全固体電池の電極の膨張収縮の阻害を抑制することやガラス層と電池要素との分解反応を抑制することにより、本来の充放電特性を発揮することが可能な、全固体電池を提供することにある。   The present invention has been made in view of this problem. The object of the present invention is to prevent the deterioration of the battery by preventing the entry of moisture (water vapor) from the outside, and the expansion of the electrode of the all-solid-state battery. An object of the present invention is to provide an all-solid-state battery capable of exhibiting original charge / discharge characteristics by suppressing the inhibition of shrinkage and suppressing the decomposition reaction between the glass layer and the battery element.

そこで、本発明者は、正極と負極と固体電解質とを含む電池要素を覆うように、所定の緩衝層を設けることにより、封止に用いるガラス層を設けても、電極の膨張収縮を可能にし、またガラス層と電池要素との分解反応を抑制することにより、長期間充放電性能を維持できることを見出した。
具体的には、本発明は以下のようなものを提供する。 Therefore, the present inventor has provided a predetermined buffer layer so as to cover the battery element including the positive electrode, the negative electrode, and the solid electrolyte, thereby enabling expansion and contraction of the electrode even if a glass layer used for sealing is provided. Moreover, it discovered that charging / discharging performance could be maintained for a long time by suppressing the decomposition reaction of a glass layer and a battery element.
Specifically, the present invention provides the following.

（１） 全固体電池であって、
電池要素と第一の緩衝層とガラス層と導電板を含み、
該電池要素は、正極層と負極層と固体電解質層とを含み、
第一の緩衝層は、該電池要素の周面上の少なくとも一部を被覆し、
該ガラス層は、該電池要素と該第一の緩衝層とが全固体電池外に露出しないように、少なくとも該第一の緩衝層の周面上に設けられ、
該導電板は、該電池要素の両主面上に配置される、
該全固体電池。
（２）該電池要素と該導電板の間に、該電池要素の少なくとも一部を被覆するように、第二の緩衝層を設ける、（１）に記載の全固体電池。
（３）該第一の緩衝層はセラミックスを含む、（１）又は（２）に記載の全固体電池。
（４）該ガラス層のガラスは、ガラス転移点（Ｔｇ）が５００℃以下である、（１）〜（３）のいずれかに記載の全固体電池。
（５）該ガラス層のガラスは、Ｂ２Ｏ３、ＴｅＯ２、Ａ２Ｏ３（式中、Ａは、Ａｌ、Ｂｉ、Ｌａからなる群より選択される１種以上）及びＲｎ２Ｏ（式中、ＲｎはＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓからなる群より選択される１種以上）成分を含有するガラスである、である、（１）〜（４）のいずれかに記載の全固体電池。
（６）該ガラス層のガラスは、Ａ２Ｏ３（式中、Ａは、Ａｌ、Ｂｉ、Ｌａからなる群より選択される１種以上）、Ｒｎ２Ｏ（式中、ＲｎはＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓからなる群より選択される１種以上）及びＤ２Ｏ５（式中、ＤはＰ、Ｖからなる群より選択される１種以上）成分を含有するガラスである、（１）〜（４）のいずれかに記載の全固体電池。
（７）該導電板は、ステンレス鋼又はＣｏ基合金からなる、（１）〜（６）のいずれかに記載の全固体電池。
（８）該第二の緩衝層の材質が、気孔率が３０％以上の、炭素、ステンレス鋼、ニッケル、ニッケル合金又はアルミニウムである、である、（１）〜（７）のいずれかに記載の全固体電池。 (1) An all-solid battery,
Including a battery element, a first buffer layer, a glass layer, and a conductive plate;
The battery element includes a positive electrode layer, a negative electrode layer, and a solid electrolyte layer,
The first buffer layer covers at least part of the peripheral surface of the battery element;
The glass layer is provided on at least the peripheral surface of the first buffer layer so that the battery element and the first buffer layer are not exposed outside the all-solid-state battery,
The conductive plate is disposed on both main surfaces of the battery element.
The all solid state battery.
(2) The all-solid-state battery according to (1), wherein a second buffer layer is provided between the battery element and the conductive plate so as to cover at least a part of the battery element.
(3) The all-solid-state battery according to (1) or (2), wherein the first buffer layer includes ceramics.
(4) The all-solid-state battery according to any one of (1) to (3), wherein the glass of the glass layer has a glass transition point (Tg) of 500 ° C. or lower.
(5) The glass of the glass layer is B 2 O 3 , TeO 2 , A 2 O 3 (wherein A is one or more selected from the group consisting of Al, Bi, La) and Rn 2 O ( In the formula, Rn is a glass containing a component (one or more selected from the group consisting of Li, Na, K, Rb, and Cs). Solid battery.
(6) The glass of the glass layer is A 2 O 3 (wherein A is one or more selected from the group consisting of Al, Bi, La), Rn 2 O (where Rn is Li, Na) , One or more selected from the group consisting of K, Rb and Cs) and D 2 O 5 (wherein D is one or more selected from the group consisting of P and V). The all solid state battery according to any one of (1) to (4).
(7) The all-solid-state battery according to any one of (1) to (6), wherein the conductive plate is made of stainless steel or a Co-based alloy.
(8) The material of the second buffer layer is carbon, stainless steel, nickel, nickel alloy or aluminum having a porosity of 30% or more, and any one of (1) to (7) All-solid battery.

本発明によれば、外部からの水分（水蒸気）侵入を防ぐためにガラス層を設けても、電池要素の膨張収縮を可能にすることやガラス層と電池要素との分解反応を抑制することにより、充放電性能等の電池性能を長期間維持できる、劣化しにくい全固体電池を提供できる。
また、本発明によれば、電池要素が正極層や負極層や固体電解質層をそれぞれ複数積層した積層体であり電極の膨張収縮が大きくなるおそれがある場合でも、この緩衝層とガラス層の構成により、電池要素の膨張収縮の阻害を抑制して長時間充放電性能を維持できる、全固体電池を提供できる。 According to the present invention, even if a glass layer is provided to prevent moisture (water vapor) intrusion from the outside, by allowing expansion and contraction of the battery element and suppressing the decomposition reaction between the glass layer and the battery element, It is possible to provide an all solid state battery that can maintain battery performance such as charge / discharge performance for a long period of time and hardly deteriorates.
Further, according to the present invention, even if the battery element is a laminate in which a plurality of positive electrode layers, negative electrode layers, and solid electrolyte layers are laminated, and the expansion and contraction of the electrode may be increased, the configuration of the buffer layer and the glass layer. Thus, it is possible to provide an all-solid-state battery that can inhibit the expansion and contraction of the battery element and maintain long-time charge / discharge performance.

全固体電池の一例を示す断面図である。（ａ）は正面断面図であり、（ｂ）は（ａ）のＡ１−Ａ２部の平面断面図である。It is sectional drawing which shows an example of an all-solid-state battery. (A) is front sectional drawing, (b) is a plane sectional view of A1-A2 part of (a). 第一の緩衝層の配置を説明するための図（平面図）である。It is a figure (plan view) for demonstrating arrangement | positioning of a 1st buffer layer. 実施例で作製するシートＡ〜Ｇに形成される、開口部の模式図である。It is a schematic diagram of the opening part formed in sheet | seat AG produced in an Example.

以下、必要に応じて図１から図３を参照しながら、本発明の全固体電池及びその製造方法の実施形態について詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。なお、説明が重複する箇所については、適宜説明を省略する場合があるが、発明の趣旨を限定するものではない。   Hereinafter, embodiments of an all solid state battery and a method for manufacturing the same according to the present invention will be described in detail with reference to FIGS. 1 to 3 as necessary. However, the present invention is not limited to the following embodiments. Instead, it can be implemented with appropriate modifications within the scope of the object of the present invention. In addition, although description may be abbreviate | omitted suitably about the location where description overlaps, the meaning of invention is not limited.

（本発明の全固体電池の基本形態）
図１に示すように、本発明の全固体電池１は、電池要素５と第一の緩衝層４とガラス層３と導電板２とを含む。電池要素５は、正極層と負極層と固体電解質層とを含む。
電池要素５の周面上の少なくとも一部に第一の緩衝層４を被覆するが、電池要素５の周囲全面を被覆してもよい。
好ましくは、更に、電池要素５と導電板２の間に、電池要素５の主面の少なくとも一部を被覆するように、第二の緩衝層６を設ける。
ガラス層３は、電池要素５と第一の緩衝層４とが全固体電池１の外に露出しないように、少なくとも第一の緩衝層４の外側に設けられる。導電板５は、電池要素５の両主面上に配置される。
ここで、電池要素５の主面とは、電池要素の外側の面が、正極層のみの面側又は負極層のみの面側の面をいう。電池要素５の周面とは、電池要素５の主面以外の面をいう。
なお、図１や図２では、コイン型の（円筒状の）全固体電池を示しているが、本発明は、コイン型以外の形態（例えば四角柱のような多角形柱や楕円柱など）に変更して、実施することができる。 (Basic form of the all-solid-state battery of the present invention)
As shown in FIG. 1, the all solid state battery 1 of the present invention includes a battery element 5, a first buffer layer 4, a glass layer 3, and a conductive plate 2. Battery element 5 includes a positive electrode layer, a negative electrode layer, and a solid electrolyte layer.
The first buffer layer 4 is coated on at least a part of the peripheral surface of the battery element 5, but the entire periphery of the battery element 5 may be covered.
Preferably, a second buffer layer 6 is further provided between the battery element 5 and the conductive plate 2 so as to cover at least a part of the main surface of the battery element 5.
The glass layer 3 is provided at least outside the first buffer layer 4 so that the battery element 5 and the first buffer layer 4 are not exposed to the outside of the all-solid battery 1. The conductive plate 5 is disposed on both main surfaces of the battery element 5.
Here, the main surface of the battery element 5 refers to a surface on the surface side of only the positive electrode layer or the surface side of only the negative electrode layer on the outer surface of the battery element. The peripheral surface of the battery element 5 refers to a surface other than the main surface of the battery element 5.
1 and FIG. 2 show a coin-type (cylindrical) all-solid-state battery, but the present invention has a form other than a coin-type (for example, a polygonal column such as a square column or an elliptical column). Can be implemented.

（電池要素５について）
本発明の実施態様における電池要素５は、正極層と負極層と固体電解質層とを有し、電池反応に寄与する、電池の基本的な構成体である。固体電解質層は、正極層と負極層の間に配置されている。なお、本明細書では、正極層及び負極層を電極層と総称し、正極活物質及び負極活物質を電極活物質と総称して記載する。
電池要素５は、正極層と負極層と固体電解質層とが１層ずつ積層される形態でもよく、複数の正極層と複数の負極層と複数の固体電解質層とを積層する形態でもよい。
また、電池要素５の厚さは、体積効率（エネルギー密度の向上）の観点から、好ましくは外径の１／１０００、より好ましくは１／１００、さらに好ましくは１／１０を下限とし、強度の観点から、好ましくは外径の１／２倍、より好ましくは１倍、さらに好ましくは２倍を上限とする。 (About battery element 5)
The battery element 5 in the embodiment of the present invention is a basic battery structure that has a positive electrode layer, a negative electrode layer, and a solid electrolyte layer and contributes to a battery reaction. The solid electrolyte layer is disposed between the positive electrode layer and the negative electrode layer. In this specification, the positive electrode layer and the negative electrode layer are collectively referred to as an electrode layer, and the positive electrode active material and the negative electrode active material are collectively referred to as an electrode active material.
The battery element 5 may have a form in which a positive electrode layer, a negative electrode layer, and a solid electrolyte layer are stacked one by one, or may have a form in which a plurality of positive electrode layers, a plurality of negative electrode layers, and a plurality of solid electrolyte layers are stacked.
In addition, the thickness of the battery element 5 is preferably 1/1000 of the outer diameter, more preferably 1/100, and even more preferably 1/10 from the viewpoint of volume efficiency (improvement of energy density). From the viewpoint, the upper limit is preferably ½ times the outer diameter, more preferably 1 time, and even more preferably 2 times.

（正極層について）
本発明の実施態様における正極層は、下記正極活物質を含むが、下記固体電解質や、下記導電助剤を含んでいてもよい。正極層に接合される固体電解質層と正極層中の活物質とのイオン（例えばリチウムイオン）伝導パスを良好に形成する為に、正極層に、固体電解質や導電助剤が含まれるのが好ましい。 (About positive electrode layer)
The positive electrode layer in the embodiment of the present invention contains the following positive electrode active material, but may contain the following solid electrolyte or the following conductive auxiliary. In order to satisfactorily form an ion (for example, lithium ion) conduction path between the solid electrolyte layer bonded to the positive electrode layer and the active material in the positive electrode layer, the positive electrode layer preferably contains a solid electrolyte or a conductive aid. .

上記のものを含む正極層の作製は、例えば、電極活物質および導電助剤と共にイオン伝導性の固体電解質の粉末又は焼結後にイオン伝導性を発現する無機固体粉末を混合し、焼結や加圧成形などをすることにより行う。   The positive electrode layer including the above can be prepared, for example, by mixing an electrode active material and a conductive additive with an ion conductive solid electrolyte powder or an inorganic solid powder exhibiting ionic conductivity after sintering, and sintering or processing. This is done by pressure forming.

（負極層について）
本発明の実施態様における負極層は、下記負極活物質を含むが、下記固体電解質や導電助剤を含んでいてもよい。負極層に接合される固体電解質層と負極層中の活物質とのイオン（例えばリチウムイオン）伝導パスを良好に形成する為に、負極層に、イオン伝導助剤として、固体電解質が含まれるのが好ましい。 (About negative electrode layer)
The negative electrode layer in the embodiment of the present invention contains the following negative electrode active material, but may contain the following solid electrolyte and conductive aid. In order to satisfactorily form an ion (for example, lithium ion) conduction path between the solid electrolyte layer joined to the negative electrode layer and the active material in the negative electrode layer, the negative electrode layer contains a solid electrolyte as an ion conduction aid. Is preferred.

上記のものを含む負極層の作製は、例えば、電極活物質および導電助剤と共にイオン伝導性の固体電解質の粉末又は焼結後にイオン伝導性を発現する無機固体粉末を混合し、焼結や加圧成形などをすることにより行う。   The negative electrode layer including the above can be prepared, for example, by mixing an electrode active material and a conductive auxiliary agent with an ion conductive solid electrolyte powder or an inorganic solid powder exhibiting ionic conductivity after sintering, and sintering or processing. This is done by pressure forming.

（電極活物質）
電極活物質のうち正極活物質は、電池要素５の放電容量をより高めるために、イオン（例えばリチウムイオン）を吸蔵し易やすくすることができる物質であることが好ましい。例えば、ＬｉＦｅＰＯ４、ＬｉＣｏＰＯ４、ＬｉＣｏＯ２、ＬｉＭｎ２Ｏ４である。 (Electrode active material)
Of the electrode active materials, the positive electrode active material is preferably a material that can easily absorb ions (for example, lithium ions) in order to further increase the discharge capacity of the battery element 5. For example, LiFePO 4 , LiCoPO 4 , LiCoO 2 , LiMn 2 O 4 .

一方で、負極活物質は、電池要素５の放電容量をより高めるために、イオン（例えばリチウムイオン）を吸蔵し易やすくすることができる物質であることが好ましい。例えばＬｉ２Ｖ２（ＰＯ４）３、Ｌｉ２Ｆｅ２（ＰＯ４）３、ＬｉＦｅＰＯ４、Ｌｉ４Ｔｉ５Ｏ１２、ＳｉＯｘ（０．２５≦ｘ≦２）、Ｃｕ６Ｓｎ５である。 On the other hand, the negative electrode active material is preferably a substance that can easily store ions (for example, lithium ions) in order to further increase the discharge capacity of the battery element 5. For example, Li 2 V 2 (PO 4 ) 3 , Li 2 Fe 2 (PO 4 ) 3 , LiFePO 4 , Li 4 Ti 5 O 12 , SiOx (0.25 ≦ x ≦ 2), and Cu 6 Sn 5 .

（導電助剤）
本発明の実施態様では、電極層中に形成された狭い電子伝導経路を通じて伝導できる電流量を増大させ、電池要素５の充放電特性を高めるために、正極層を構成する正極材料中又は、負極層を構成する負極材料中に、導電助剤が含まれることが好ましい。
導電助剤として、炭素、並びにＮｉ、Ｆｅ、Ｍｎ、Ｃｏ、Ｍｏ、Ｃｒ、Ａｇ及びＣｕの少なくとも１種以上からなる金属及びこれらの合金を用いることできる。また、チタン、ステンレス、アルミニウム等の金属や、白金、銀、金、ロジウム等の貴金属を用いてもよい。また、ＷＯ３やＳｎＯ２のような金属酸化物を用いてもよい。 (Conductive aid)
In the embodiment of the present invention, in order to increase the amount of current that can be conducted through the narrow electron conduction path formed in the electrode layer and to improve the charge / discharge characteristics of the battery element 5, It is preferable that a conductive additive is contained in the negative electrode material constituting the layer.
As the conductive additive, carbon, a metal composed of at least one of Ni, Fe, Mn, Co, Mo, Cr, Ag, and Cu, and alloys thereof can be used. Alternatively, a metal such as titanium, stainless steel, or aluminum, or a noble metal such as platinum, silver, gold, or rhodium may be used. It may also be used metal oxides such as WO 3 or SnO 2.

（固体電解質層）
固体電解質層は、下記固体電解質を含む層であり、正極層及び負極層の間に介在する、イオン伝導性（例えばリチウムイオン伝導性）を有する層である。 (Solid electrolyte layer)
The solid electrolyte layer is a layer including the following solid electrolyte, and is a layer having ion conductivity (for example, lithium ion conductivity) interposed between the positive electrode layer and the negative electrode layer.

（固体電解質）
電極層や固体電解質層に含まれる固体電解質は、イオン伝導性（例えばリチウムイオン伝導性）を有する材料を用いることができる。例えばＮＡＳＩＣＯＮ型、β−Ｆｅ２（ＳＯ４）３型、及びペロブスカイト型から選ばれる酸化物の結晶や、Ｌｉ２Ｏ−Ｐ２Ｏ５系ガラスやＬｉ２Ｏ−Ｐ２Ｏ５−Ｍ’２Ｏ３系のガラス（ＰがＳｉに置換されたものも含む。Ｍ’はＡｌ、Ｂ、Ｙ、Ｓｃである。）などのリチウムイオン伝導性を有するガラス、を含有する材料が挙げられる。 (Solid electrolyte)
As the solid electrolyte contained in the electrode layer or the solid electrolyte layer, a material having ion conductivity (for example, lithium ion conductivity) can be used. For example, an oxide crystal selected from NASICON type, β-Fe 2 (SO 4 ) 3 type, and perovskite type, Li 2 O—P 2 O 5 glass, Li 2 O—P 2 O 5 —M ′ 2 Examples thereof include materials containing lithium ion conductive glass such as O 3 -based glass (including those in which P is replaced by Si, M ′ is Al, B, Y, Sc).

（電池要素５の作製）
原料組成物から、焼結や加圧成形等により、電極層前駆体、固体電解質層前駆体をそれぞれ作製する。これらの前駆体を積層し、焼成や加圧成形等で各層を接合することにより、電池要素５を作製する。 (Production of battery element 5)
From the raw material composition, an electrode layer precursor and a solid electrolyte layer precursor are respectively produced by sintering, pressure molding, or the like. The battery element 5 is produced by laminating these precursors and bonding the layers by firing or pressure molding.

なお、電極層上に集電体を積層する場合は、薄膜状の金属層を接合しても良く、前駆体から焼成により形成しても良い。電極層自体の電子伝導性が高ければ、集電体はなくても良い。   In addition, when laminating | stacking a collector on an electrode layer, a thin metal layer may be joined and you may form by baking from a precursor. If the electrode layer itself has high electron conductivity, the current collector may be omitted.

ここで、電池要素５に含まれる固体電解質、電極活物質及び導電助剤の含有量とこれらの組成は、電池要素５を構成する固体電解質層及び／又は電極層を削り出して、電界放出形透過電子顕微鏡（ＦＥ−ＴＥＭ）に搭載されたエネルギー損出分析装置若しくはＸ線分析装置、又は電界放出形走査顕微鏡（ＦＥ−ＳＥＭ）に搭載されたＸ線分析装置を用いて特定することが可能である。このような定量分析や点分析を用いることで、例えば固体電解質の存在の有無やその組成比がわかる。Ｘ線分析装置を用いた場合、Ｌｉ２Ｏは直接分析できないため、他の構成成分から電荷を算出することで、Ｌｉ２Ｏ含有量を推定する。 Here, the content of the solid electrolyte, the electrode active material and the conductive additive contained in the battery element 5 and the composition thereof are obtained by cutting out the solid electrolyte layer and / or the electrode layer constituting the battery element 5 to obtain a field emission type. It is possible to specify using an energy loss analyzer or X-ray analyzer mounted on a transmission electron microscope (FE-TEM), or an X-ray analyzer mounted on a field emission scanning microscope (FE-SEM) It is. By using such quantitative analysis or point analysis, for example, the presence or absence of a solid electrolyte and its composition ratio can be known. When an X-ray analyzer is used, Li 2 O cannot be analyzed directly, so the Li 2 O content is estimated by calculating the charge from other components.

（第一の緩衝層４について）
本発明の実施態様における第一の緩衝層４は、電池要素５の周面上の少なくとも一部を又は全部を被覆する層であり、電池要素５とガラス層３の間に設けられる層である。本発明の第一の緩衝層４には、所定の無機粒子を元とする材料（セラミックス等）を用いる。所定の無機粒子を元とする材料とは、電池要素５の膨張収縮を可能にし、電子絶縁性があり、電池要素５との反応性が低い、材料である。電池要素５の膨張収縮を可能にすることが求められるのは、サイクル特性の観点からである。電子絶縁性が求められるのは電気要素５の正極面や負極面に接触するため電極の短絡防止の観点からである。電池要素５との反応性が低いことが求められるのは、ガラス層３と電池要素５の反応（電池要素５中に含まれる正極層、負極層、固体電解質層の分解反応）を防ぐ観点からである。
また、耐水性を上げる上で吸湿性を有する材料や１０００℃まで加熱しても放熱あるいは吸熱反応を示さず重量の増減が１％以下である材料を用いるとより好ましい。例えば、ＺｒＯ２成分、ＳｉＯ２成分、ＭｇＯ成分、Ａｌ２Ｏ３成分やＣａＣＯ３成分を含む材料であり、ＺｒＯ２成分が９５質量％以上含有する材料、ＳｉＯ２成分を９５質量％以上含有する材料、Ａｌ２Ｏ３成分が９５質量％以上含有する材料、ＣａＣＯ３成分が９５質量％以上含有する材料、ＺｒＯ２成分が１００質量の材料、ＳｉＯ２成分を１００質量％以上の材料、Ａｌ２Ｏ３成分が１００質量％の材料、ＣａＣＯ３成分が１００質量％の材料も挙げられる。
第一の緩衝層４の材料の形状は、例えば球状、繊維状、中空状の形状であるが、膨張収縮時の体積変化を吸収し、形状の崩れが少ない、繊維状の形状が好ましい。例えば、このような形状の材料として、Ａｌ２Ｏ３成分及びＳｉＯ２成分を含有するセラミック繊維や、シリカ繊維、アルミナ繊維、グラスウールの材料が挙げられる。
また、第一の緩衝層４の厚さは、電池要素５の膨張収縮の影響を吸収する観点とガラス層３と電池要素５の反応を抑制する観点から、好ましくは電池要素外径の１／１０００、より好ましくは１／１００、さらに好ましくは１／５０を下限とし、エネルギー密度の観点から、好ましくは１／５、より好ましくは１／１０、さらに好ましくは１／２０を上限とする。 (About the first buffer layer 4)
The first buffer layer 4 in the embodiment of the present invention is a layer that covers at least a part or all of the peripheral surface of the battery element 5, and is a layer provided between the battery element 5 and the glass layer 3. . For the first buffer layer 4 of the present invention, a material (ceramics or the like) based on predetermined inorganic particles is used. The material based on the predetermined inorganic particles is a material that enables expansion and contraction of the battery element 5, is electronically insulating, and has low reactivity with the battery element 5. The battery element 5 is required to be able to expand and contract from the viewpoint of cycle characteristics. Electronic insulation is required from the viewpoint of preventing short-circuiting of the electrodes because they are in contact with the positive and negative electrode surfaces of the electric element 5. Low reactivity with the battery element 5 is required from the viewpoint of preventing the reaction between the glass layer 3 and the battery element 5 (the decomposition reaction of the positive electrode layer, the negative electrode layer, and the solid electrolyte layer contained in the battery element 5). It is.
Further, in order to increase water resistance, it is more preferable to use a material having hygroscopicity or a material that does not exhibit heat dissipation or endothermic reaction even when heated to 1000 ° C. and has a weight increase or decrease of 1% or less. For example, a material containing a ZrO 2 component, a SiO 2 component, a MgO component, an Al 2 O 3 component or a CaCO 3 component, a material containing a ZrO 2 component of 95% by mass or more, and a SiO 2 component containing 95% by mass or more. Material, material containing 95% or more of Al 2 O 3 component, material containing 95% or more of CaCO 3 component, material containing ZrO 2 component of 100%, material containing SiO 2 component of 100% or more, Al 2 A material in which the O 3 component is 100% by mass and a material in which the CaCO 3 component is 100% by mass are also included.
The shape of the material of the first buffer layer 4 is, for example, a spherical shape, a fibrous shape, or a hollow shape, but a fibrous shape that absorbs a volume change at the time of expansion and contraction and has little shape collapse is preferable. For example, examples of the material having such a shape include ceramic fibers containing an Al 2 O 3 component and an SiO 2 component, silica fibers, alumina fibers, and glass wool materials.
In addition, the thickness of the first buffer layer 4 is preferably 1/0 of the outer diameter of the battery element from the viewpoint of absorbing the influence of expansion and contraction of the battery element 5 and suppressing the reaction between the glass layer 3 and the battery element 5. 1000, more preferably 1/100, more preferably 1/50 is the lower limit, and from the viewpoint of energy density, the upper limit is preferably 1/5, more preferably 1/10, and even more preferably 1/20.

（第一の緩衝層４の作製法）
電池要素５に塗布するための、第一の緩衝層４に用いるスラリー状の材料を準備する。電池要素５の周面上に、このスラリー状の材料を塗布し、このスラリー状の材料を乾燥させることにより、第一の緩衝層４を作製する。 (Method for producing first buffer layer 4)
A slurry-like material used for the first buffer layer 4 to be applied to the battery element 5 is prepared. The slurry-like material is applied on the peripheral surface of the battery element 5, and the slurry-like material is dried to produce the first buffer layer 4.

（ガラス層３について）
本発明の実施態様におけるガラス層３は、全固体電池１への外部からの水分（水蒸気）侵入を防ぐために設けられる層である。ガラス層３に用いるガラスは、ガラスの熱的安定性や化学的安定性を有し、外部からの水分（水蒸気）侵入を防ぎ、かつ粉体状態又はペーストとして扱いやすくする観点から、ガラス転移点（Ｔｇ）が５００℃以下であるのが好ましく、４００℃以下であるのが好ましく、３５０℃以下であるのが更に好ましい。例えば、酸化物基準のモル％で、所定量のＢ２Ｏ３、ＴｅＯ２、Ａ２Ｏ３（式中、Ａは、Ａｌ、Ｂｉ、Ｌａからなる群より選択される１種以上）及びＲｎ２Ｏ（式中、ＲｎはＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓからなる群より選択される１種以上）成分を含有するガラスである（以下Ｔｅ系ガラスという）や、所定量のＡ２Ｏ３（式中、Ａは、Ａｌ、Ｂｉ、Ｌａからなる群より選択される１種以上）、Ｒｎ２Ｏ（式中、ＲｎはＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓからなる群より選択される１種以上）及びＤ２Ｏ５（式中、ＤはＰ、Ｖからなる群より選択される１種以上）成分を含有するガラス（以下リン酸系ガラスという）を用いることができる。なお、「酸化物基準」とは、ガラス構成成分の原料として使用される炭酸塩や硝酸塩等が溶融時に全て分解され酸化物へ変化すると仮定した場合に、該生成酸化物の総和を１００モル％として、ガラス中に含有される各成分を標記した組成である。
また、ガラス層３の厚さは、強度と水分透過性および耐久性の観点から、好ましくは０．０１ｍｍ、より好ましくは０．０２ｍｍ、さらに好ましくは０．０５ｍｍを下限とし、エネルギー密度の観点から、好ましくは０．５ｍｍ、より好ましくは０．３ｍｍ、さらに好ましくは０．２ｍｍを上限とする。 (About glass layer 3)
The glass layer 3 in the embodiment of the present invention is a layer provided in order to prevent moisture (water vapor) from entering the all solid state battery 1 from the outside. The glass used for the glass layer 3 has a glass transition point from the viewpoint of having the thermal stability and chemical stability of the glass, preventing moisture (water vapor) from entering from the outside, and facilitating handling as a powder or paste. (Tg) is preferably 500 ° C. or less, preferably 400 ° C. or less, and more preferably 350 ° C. or less. For example, a predetermined amount of B 2 O 3 , TeO 2 , A 2 O 3 (wherein A is one or more selected from the group consisting of Al, Bi, and La) and Rn in mol% based on oxide. 2 O (wherein Rn is one or more selected from the group consisting of Li, Na, K, Rb and Cs) or a glass containing a predetermined amount of A 2 O (hereinafter referred to as Te glass). 3 (wherein A is one or more selected from the group consisting of Al, Bi and La), Rn 2 O (wherein Rn is selected from the group consisting of Li, Na, K, Rb and Cs) One or more) and D 2 O 5 (wherein D is one or more selected from the group consisting of P and V) components (hereinafter referred to as phosphate glass) can be used. The “oxide standard” means that the total amount of the generated oxides is 100 mol% when it is assumed that carbonates and nitrates used as raw materials for glass constituents are all decomposed and changed to oxides when melted. As a composition in which each component contained in the glass is marked.
Further, the thickness of the glass layer 3 is preferably 0.01 mm, more preferably 0.02 mm, and still more preferably 0.05 mm from the viewpoint of strength, moisture permeability and durability, and from the viewpoint of energy density. The upper limit is preferably 0.5 mm, more preferably 0.3 mm, and still more preferably 0.2 mm.

以下、Ｔｅ系ガラスやリン酸塩系ガラスに含有される好ましい成分について説明する。なお、各成分はモル％にて表現する。モル％で表されるガラス組成は全て酸化物基準でのモル％で表されたものである。   Hereinafter, preferable components contained in the Te glass and the phosphate glass will be described. Each component is expressed in mol%. All glass compositions expressed in mol% are expressed in mol% on an oxide basis.

まず、Ｔｅ系ガラスに含有される成分について記載する。   First, the components contained in the Te glass will be described.

ＴｅＯ２成分はガラス形成酸化物の役割を果たし、ガラスの安定性の向上に寄与し、５００℃以下の低いガラス転移点（Ｔｇ）とするのにも寄与する成分である。このような観点から、ＴｅＯ２成分の含有量の上限は９０％とするのが好ましく、７０％とするのがより好ましく、６５％とするのが最も好ましく、またＴｅＯ２成分の含有量の下限は５％とするのが好ましく、１５％とするのがより好ましく、２０％とするのが最も好ましい。 The TeO 2 component is a component that plays the role of a glass-forming oxide, contributes to the improvement of the stability of the glass, and contributes to a low glass transition point (Tg) of 500 ° C. or lower. From such a viewpoint, the upper limit of the TeO 2 component content is preferably 90%, more preferably 70%, most preferably 65%, and the lower limit of the TeO 2 component content. Is preferably 5%, more preferably 15%, and most preferably 20%.

Ｂ２Ｏ３はガラスの形成酸化物であり、ガラスの安定性の向上に寄与する成分である。５００℃以下の低いガラス転移点（Ｔｇ）とするのには、Ｂ２Ｏ３の含有量の上限は８０％とすることが好ましく、６０％とすることがより好ましく、５０％とすることが最も好ましく、Ｂ２Ｏ３の含有量の下限は５％以上とするのが好ましく、８％以上とするのがより好ましく、１２％以上とするのが最も好ましい。 B 2 O 3 is a glass-forming oxide and is a component that contributes to improving the stability of the glass. In order to obtain a low glass transition point (Tg) of 500 ° C. or lower, the upper limit of the content of B 2 O 3 is preferably 80%, more preferably 60%, and more preferably 50%. Most preferably, the lower limit of the content of B 2 O 3 is preferably 5% or more, more preferably 8% or more, and most preferably 12% or more.

Ａｌ２Ｏ３はガラス安定性の向上に効果があり、特に熱処理においてガラスの安定性を維持するのに寄与する成分である。ガラスの安定性を保つために、Ａｌ２Ｏ３の含有量の下限は０．１％とするのが好ましく、４％とするのがより好ましく、８％とするのが最も好ましい。しかし、Ａｌ２Ｏ３の含有量が過剰に多い場合、ガラス転移点（Ｔｇ）が高くなると共に結晶化しやすくため、これらを防ぐために、Ａｌ２Ｏ３の含有量の上限は４０％とするのが好ましく、３０％とするのがより好ましく、２２％とするのが最も好ましい。 Al 2 O 3 is effective in improving the glass stability, and is a component that contributes to maintaining the stability of the glass particularly during heat treatment. In order to maintain the stability of the glass, the lower limit of the content of Al 2 O 3 is preferably 0.1%, more preferably 4%, and most preferably 8%. However, when the content of Al 2 O 3 is excessively large, the glass transition point (Tg) is increased and crystallization is facilitated. In order to prevent these, the upper limit of the content of Al 2 O 3 is 40%. Is preferable, 30% is more preferable, and 22% is most preferable.

ガラスを粉体状態やペースト状態にした後、被覆作業を行うとガラスが結晶化し、被覆作業（ガラス封止層を設ける作業）がしにくい。粉体状態／ペースト状態でも、安定なガラスを維持するためには、酸化物基準のモル％で表されたＡｌ２Ｏ３／ＴｅＯ２比は０．１以上が好ましく、０．１５以上がより好ましく、０．２以上が最も好ましい。しかし、Ａｌ２Ｏ３／ＴｅＯ２比が大きすぎるとガラス転移点（Ｔｇ）が高くなりすぎると共に結晶化しやすくなるため、その上限は１．５以下が好ましく、１．０以下がより好ましく、０．７以上が最も好ましい。 When the coating operation is performed after the glass is in a powder state or a paste state, the glass is crystallized, and the coating operation (operation for providing a glass sealing layer) is difficult. In order to maintain a stable glass even in the powder state / paste state, the Al 2 O 3 / TeO 2 ratio expressed in mol% based on the oxide is preferably 0.1 or more, more preferably 0.15 or more. Preferably, 0.2 or more is the most preferable. However, if the Al 2 O 3 / TeO 2 ratio is too large, the glass transition point (Tg) becomes too high and crystallization tends to occur, so the upper limit is preferably 1.5 or less, more preferably 1.0 or less, and 0 .7 or more is most preferable.

Ｂｉ２Ｏ３成分はガラス形成酸化物の役割を果たし、特に熱処理においてガラスの安定性を維持することと、低Ｔｇ化（ガラスの低温処理化）に寄与する成分である。しかし、含有量が多すぎるとガラス安定性が損なわれ、ガラス化しづらくなるとともに化学的耐久性が悪化するおそれがある。よって、Ｂｉ２Ｏ３量は上限を４０％とするのが好ましく、１５％とするのがより好ましく、５％とするのが最も好ましい。 The Bi 2 O 3 component plays the role of a glass-forming oxide, and is a component that contributes to maintaining the stability of the glass during heat treatment and lowering the Tg (lowering the glass temperature). However, when there is too much content, glass stability will be impaired, and it will become difficult to vitrify, and there exists a possibility that chemical durability may deteriorate. Therefore, the upper limit of Bi 2 O 3 content is preferably 40%, more preferably 15%, and most preferably 5%.

Ｌａ２Ｏ３成分は化学的耐久性の向上に寄与するが、含有量が多すぎるとガラス転移点（Ｔｇ）も上昇おそれがある。従って、Ｌａ２Ｏ３成分は、上限を３０％とするのが好ましく、２０％とするのがより好ましく、１０％とするのが最も好ましい。また、特に前記効果を充分に得たい場合は下限を０．１％とするのが好ましく、０．２％とするのがより好ましく、０．３％とするのが最も好ましい。 The La 2 O 3 component contributes to the improvement of chemical durability, but if the content is too large, the glass transition point (Tg) may also increase. Therefore, the upper limit of the La 2 O 3 component is preferably 30%, more preferably 20%, and most preferably 10%. In particular, when it is desired to sufficiently obtain the above effect, the lower limit is preferably 0.1%, more preferably 0.2%, and most preferably 0.3%.

Ｒｎ２Ｏ（Ｒ＝Ｌｉ，Ｎａ，Ｋ，Ｃｓ）成分はガラス溶解の際にバッチの発泡性を抑え、ガラスの溶融性と安定性の向上、ガラス転移点（Ｔｇ）の低減及び４００ｎｍでの透過率向上に効果が大きい有用な成分であるが、多く入るとガラスの化学耐久性が悪くなりやすいので、上限を５０％とするのが好ましく、４５％とするのがさらに好ましい。 Rn 2 O (R = Li, Na, K, Cs) component suppresses the foamability of the batch during glass melting, improves the meltability and stability of the glass, reduces the glass transition point (Tg) and at 400 nm. Although it is a useful component having a large effect in improving the transmittance, the chemical durability of the glass tends to deteriorate when added in a large amount, so the upper limit is preferably 50%, and more preferably 45%.

次に、リン酸系ガラスに含有される成分について記載する。なお、Ａ２Ｏ３（Ａ＝Ａｌ、Ｂｉ、Ｌａ）成分やＲｎ２Ｏ（Ｒ＝Ｌｉ、Ｎａ、Ｋ、Ｃｓ）成分については、上述の通りである。 Next, it describes about the component contained in phosphate glass. The A 2 O 3 (A = Al, Bi, La) component and the Rn 2 O (R = Li, Na, K, Cs) component are as described above.

Ｐ２Ｏ５成分はガラス骨格を形成する成分であり、ガラスの安定化に寄与する成分である。 P 2 O 5 component is a component for forming a glass network, which is a component that contributes to the stabilization of the glass.

Ｖ２Ｏ５成分は低Ｔｇ化（ガラスの低温処理化）に寄与する成分である。 V 2 O 5 component is a component that contributes to low Tg (low temperature treatment of glass).

ＺｒＯ２成分は化学的耐久性の向上に寄与する成分である。任意に添加し得る成分であるが、含有量が多すぎるとガラスの溶融性と安定性も低下すると共にガラス転移点（Ｔｇ）も大幅に上昇する。従って、ＺｒＯ２成分の含有量の上限を１５％とするのが好ましく、１０％とするのがより好ましく、５％とするのが最も好ましい。 The ZrO 2 component is a component that contributes to improvement of chemical durability. Although it is a component that can be optionally added, if the content is too large, the meltability and stability of the glass are lowered and the glass transition point (Tg) is also significantly increased. Therefore, the upper limit of the content of the ZrO 2 component is preferably 15%, more preferably 10%, and most preferably 5%.

ガラスのＴｇは、ＪＯＧＩＳ（日本光学硝子工業会規格）８−２００３に則り、熱膨張曲線の低温側と高温側の２つの直線部分を外挿して得られる交点から求める。   The Tg of the glass is determined from the intersection obtained by extrapolating two linear portions of the low temperature side and the high temperature side of the thermal expansion curve according to JOGIS (Japan Optical Glass Industry Association Standard) 8-2003.

なお、ガラス層３に用いられる材料（ガラス粉末）は、十分な耐候性をもち低温で封止処理できる材料であればよい。上述のＴｅ系ガラスやリン酸塩系ガラス以外でも、ガラス層３に用いられる材料として、市販の電子部品気密封止・接着用などに適したガラス粉末を用いることもできる。具体的には、日立化成株式会社製環境適合バナジウム系低融点ガラス「バニーテクト」ＶＰ―１１７５（標準封止条件３７０℃ １０分）、ＶＰ―１１７６（標準封止条件３８０℃ １０分）、ＶＰ―１１７７（標準封止条件３９０℃ １０分）、ＶＰ―１１７９（標準封止条件４００℃ １０分）や、旭硝子製低温シール用無鉛フリット ＫＰ３１２ＡＳ（（標準封止条件４３０℃ １０分）、旭硝子製ガラスフリットＴ０１５を用いても良い。   In addition, the material (glass powder) used for the glass layer 3 should just be a material which has sufficient weather resistance and can be sealed at low temperature. In addition to the Te glass and phosphate glass described above, as a material used for the glass layer 3, a commercially available glass powder suitable for hermetic sealing / adhesion of electronic components can also be used. Specifically, environmentally-friendly vanadium-based low melting glass “Bunny Tect” VP-1175 (standard sealing condition 370 ° C. 10 minutes), VP-1176 (standard sealing condition 380 ° C. 10 minutes), VP- 1177 (standard sealing condition 390 ° C. 10 minutes), VP-1179 (standard sealing condition 400 ° C. 10 minutes), Asahi Glass lead-free frit KP312AS (standard sealing condition 430 ° C. 10 minutes), Asahi Glass glass Frit T015 may be used.

（ガラス層３の作製法）
第一の緩衝層４に塗布するための、ガラス層３に用いるスラリー状の材料を準備する。スラリーに用いるバインダーは、脱脂温度の点で、アクリルバインダーが最も好ましい。電池要素５と第一の緩衝層４とが全固体電池１外に露出しないように、少なくとも第一の緩衝層４の周面上に、このスラリー状の材料を塗布し、このスラリー状の材料を乾燥後に脱脂・焼成させることにより、ガラス層３を作製する。 (Production method of glass layer 3)
A slurry-like material used for the glass layer 3 to be applied to the first buffer layer 4 is prepared. The binder used for the slurry is most preferably an acrylic binder in terms of the degreasing temperature. The slurry-like material is applied on at least the peripheral surface of the first buffer layer 4 so that the battery element 5 and the first buffer layer 4 are not exposed to the outside of the all-solid battery 1. The glass layer 3 is produced by degreasing and baking after drying.

（導電板２について）
本発明の実施態様における導電板２は、集電体としての機能を有し、かつ外部からの水分（水蒸気）の侵入を防ぐためのものである。導電板２は、上述の電池要素５の両主面上に配置される。導電板２に用いられる材料としては、導電性と耐水性および耐熱性の観点から、耐熱性を有する例えばマルテンサイト系ステンレス鋼（ＳＵＳ４１０）やＣｏ基合金などの導電性を有した材料、又はグラッシーカーボンや、ガラスにカーボンを高分散させた導電性ガラスや、導電性セラミックスを用いることができる。
導電板２の厚さは、エネルギー密度の観点から重量が軽く薄い方が好ましく、好ましくは０．５ｍｍ、より好ましくは０．４ｍｍ、さらに好ましくは０．２ｍｍを上限とする。また、強度の観点から、ある程度の厚みがある方が好ましく、導電板２の厚さは、好ましくは０．０１ｍｍ、より好ましくは０．０２ｍｍ、さらに好ましくは０．０５ｍｍを下限とする。 (About conductive plate 2)
The conductive plate 2 in the embodiment of the present invention has a function as a current collector and prevents moisture (water vapor) from entering from the outside. The conductive plate 2 is disposed on both main surfaces of the battery element 5 described above. As the material used for the conductive plate 2, from the viewpoint of conductivity, water resistance and heat resistance, heat-resistant materials such as martensitic stainless steel (SUS410) and Co-based alloys, or glassy are used. Carbon, conductive glass in which carbon is highly dispersed in glass, or conductive ceramics can be used.
The thickness of the conductive plate 2 is preferably light and thin from the viewpoint of energy density, preferably 0.5 mm, more preferably 0.4 mm, and still more preferably 0.2 mm. Further, from the viewpoint of strength, it is preferable that there is a certain thickness, and the thickness of the conductive plate 2 is preferably 0.01 mm, more preferably 0.02 mm, and still more preferably 0.05 mm.

（第二の緩衝層６について）
本発明の実施態様における第二の緩衝層６は、電池要素５の厚み方向の膨張収縮を可能にして充放電不良防止を図るための部材であり、電池要素５と導電板２の間に、電池要素５の少なくとも一部を被覆するように設ける。
第二の緩衝層６には、集電性の観点から、電子伝導性等を有し、電池要素５の膨張収縮を可能にするような柔軟性を有し、かつガラスを封止する際に変質しない耐熱性を有する材料を用いることができる。例えば、この材料は、気孔率が３０％以上の（好ましくは気孔率が４０％以上の、更に好ましくは気孔率が５０％の）、炭素、ステンレス鋼、ニッケル、ニッケル合金又はアルミニウムである。具体的には、カーボンフェルト、発泡金属（多孔質金属）又はアルミメッシュからなる材料である。
また、第二の緩衝層６の厚さは、電池要素５の膨張収縮による体積変化を吸収する観点から、好ましくは電池要素５の厚さの１／１００００、より好ましくは１／１０００、さらに好ましくは１／１００を下限とし、エネルギー密度の観点から、好ましくは外径の電池要素５の厚さの１／１０倍、より好ましくは、さらに好ましくは１／５を上限とする。
なお、電池要素５の周面方向への膨張収縮が少ない場合は、下記実施例２１のように第一の緩衝層４を含まず、電池要素５とガラス層３と導電板２と第二の緩衝層６とを含む全固体電池１を構成することも考えられる。 (About the second buffer layer 6)
The second buffer layer 6 in the embodiment of the present invention is a member that enables expansion and contraction in the thickness direction of the battery element 5 and prevents charge / discharge failure, and between the battery element 5 and the conductive plate 2, It is provided so as to cover at least a part of the battery element 5.
The second buffer layer 6 has electron conductivity and the like from the viewpoint of current collection, has flexibility to enable expansion and contraction of the battery element 5, and seals the glass. A heat-resistant material that does not change quality can be used. For example, the material is carbon, stainless steel, nickel, nickel alloy or aluminum having a porosity of 30% or more (preferably having a porosity of 40% or more, more preferably 50%). Specifically, it is a material made of carbon felt, foam metal (porous metal) or aluminum mesh.
Further, the thickness of the second buffer layer 6 is preferably 1 / 10,000, more preferably 1/1000, and still more preferably from the viewpoint of absorbing volume change due to expansion and contraction of the battery element 5. 1/100 is the lower limit, and from the viewpoint of energy density, the upper limit is preferably 1/10 times the thickness of the battery element 5 having an outer diameter, more preferably 1/5.
When the expansion and contraction in the circumferential direction of the battery element 5 is small, the first buffer layer 4 is not included as in Example 21 below, and the battery element 5, the glass layer 3, the conductive plate 2, and the second buffer layer 5 are not included. It is also conceivable to configure the all-solid battery 1 including the buffer layer 6.

（固体電解質の準備）
固体電解質として、セラミック電解質とガラス電解質を用いた。
負極スラリー用及び固体電解質ペースト用の固体電解質用セラミック電解質として、Ｌｉ１．３Ａｌ０．１Ｚｒ１．８Ｙ０．１Ｓｉ０．１Ｐ２．９Ｏ１２を作製した。原料としてＬｉ２ＣＯ３、ＺｒＯ２、Ａｌ２Ｏ３、Ｙ２Ｏ３及びＳｉＯ２の紛体と、Ｈ３ＰＯ４溶液とを量論比で混合した後、白金板上にて１４８０℃で１時間焼成した。焼成した原料の混合物をスタンプミルで２００μｍ以下に粉砕し、φ２ｍｍのＹＴＺボール、エタノールを加え、遊星ボールミルで粉砕した。得られた粉末を乾燥し、１．０μｍ（Ｄ５０）のセラミック電解質粉末を得た。
正極スラリー用の固体電解質用セラミック電解質として、Ｌｉ１．７Ａｌ０．４Ｚｒ１．８Ｙ０．１Ｓｉ０．２Ｐ２．８Ｏ１２を作製した。原料としてＬｉ２ＣＯ３、ＺｒＯ２、Ａｌ２Ｏ３、Ｙ２Ｏ３及びＳｉＯ２の紛体と、Ｈ３ＰＯ４溶液とを量論比で混合した後、白金板上にて１４８０℃で１時間焼成した。焼成した原料の混合物をスタンプミルで２００μｍ以下に粉砕し、φ２ｍｍのＹＴＺボール、エタノールを加え、遊星ボールミルで粉砕した。得られた粉末を乾燥し、１．０μｍ（Ｄ５０）のセラミック電解質粉末を得た。 (Preparation of solid electrolyte)
As the solid electrolyte, a ceramic electrolyte and a glass electrolyte were used.
Li 1.3 Al 0.1 Zr 1.8 Y 0.1 Si 0.1 P 2.9 O 12 was produced as a ceramic electrolyte for a solid electrolyte for a negative electrode slurry and a solid electrolyte paste. Li 2 CO 3 , ZrO 2 , Al 2 O 3 , Y 2 O 3, and SiO 2 powder and a H 3 PO 4 solution were mixed in a stoichiometric ratio as raw materials, and then mixed at 1480 ° C. on a platinum plate. Baked for hours. The fired mixture of raw materials was pulverized to 200 μm or less with a stamp mill, φ2 mm YTZ balls and ethanol were added, and pulverized with a planetary ball mill. The obtained powder was dried to obtain a 1.0 μm (D50) ceramic electrolyte powder.
Li 1.7 Al 0.4 Zr 1.8 Y 0.1 Si 0.2 P 2.8 O 12 was produced as the ceramic electrolyte for the solid electrolyte for the positive electrode slurry. Li 2 CO 3 , ZrO 2 , Al 2 O 3 , Y 2 O 3, and SiO 2 powder and a H 3 PO 4 solution were mixed in a stoichiometric ratio as raw materials, and then mixed at 1480 ° C. on a platinum plate. Baked for hours. The fired mixture of raw materials was pulverized to 200 μm or less with a stamp mill, φ2 mm YTZ balls and ethanol were added, and pulverized with a planetary ball mill. The obtained powder was dried to obtain a 1.0 μm (D50) ceramic electrolyte powder.

ガラス電解質として、Ｌｉ２Ｏ−Ａｌ２Ｏ３−Ｐ２Ｏ５系ガラスを作製した。酸化物基準組成で、５０ｍｏｌ％のＬｉ２Ｏと、６ｍｏｌ％のＡｌ２Ｏ３と、４４ｍｏｌ％のＰ２Ｏ５とを含有するように原料を秤量して均一に混合した後、坩堝に投入して１２５０℃で溶解した。熔解したガラスを水中にキャストすることで、ガラス電解質を作製した。この電解質を、スタンプミルと遊星ボールミルを用いて平均粒子径２μｍ（Ｄ５０）まで粉砕することで、ガラス電解質粉末を得た。 As the glass electrolyte, to prepare a Li 2 O-Al 2 O 3 -P 2 O 5 -based glass. The raw materials were weighed and mixed uniformly so as to contain 50 mol% Li 2 O, 6 mol% Al 2 O 3 , and 44 mol% P 2 O 5 with an oxide reference composition, and then charged into a crucible. And dissolved at 1250 ° C. A glass electrolyte was produced by casting the melted glass into water. The electrolyte was pulverized to an average particle size of 2 μm (D50) using a stamp mill and a planetary ball mill to obtain a glass electrolyte powder.

（正極スラリー・負極スラリー・固体電解質スラリーの作製）
正極スラリーは、正極活物質としてＬｉＦｅＰＯ４を用い、これに上述のセラミック電解質及びガラス電解質と、導電助剤であるアセチレンブラックを表１に示す量で混合し、これにバインダー、分散剤、湿潤材、可塑剤及び溶剤を表２に示す量で加えてボールミルで混合して作製した。
負極スラリーは、負極活物質としてＬｉ４Ｔｉ５Ｏ１２を用い、これに上述のセラミック電解質及びガラス電解質と、導電助剤であるアセチレンブラックを表１に示す量で混合し、これにバインダー、分散剤、湿潤材、可塑剤及び溶剤を表２に示す量で加えてボールミルで混合して作製した。
固体電解質スラリーは、上述のセラミック電解質及びガラス電解質を表１に示す量で混合し、これにバインダー、分散剤、湿潤材、可塑剤及び溶剤を表２に示す量で加えてボールミルで混合して作製した。
なお、表２記載のＤＯＳは、セバシン酸ジ−２−エチルヘキシルである。 (Preparation of positive electrode slurry, negative electrode slurry, solid electrolyte slurry)
The positive electrode slurry uses LiFePO 4 as a positive electrode active material, and the ceramic electrolyte and glass electrolyte described above and acetylene black, which is a conductive additive, are mixed in the amounts shown in Table 1, and a binder, a dispersant, a wetting material are mixed therewith. A plasticizer and a solvent were added in the amounts shown in Table 2 and mixed by a ball mill.
The negative electrode slurry uses Li 4 Ti 5 O 12 as a negative electrode active material, and the ceramic electrolyte and glass electrolyte described above and acetylene black, which is a conductive additive, are mixed in the amounts shown in Table 1, and a binder and dispersion are mixed therewith. An agent, a wetting material, a plasticizer and a solvent were added in the amounts shown in Table 2 and mixed by a ball mill.
The solid electrolyte slurry is prepared by mixing the above-mentioned ceramic electrolyte and glass electrolyte in the amounts shown in Table 1, adding a binder, a dispersant, a wetting material, a plasticizer and a solvent in the amounts shown in Table 2, and mixing them with a ball mill. Produced.
Note that DOS described in Table 2 is di-2-ethylhexyl sebacate.

Figure 2018170297
Figure 2018170297

Figure 2018170297
Figure 2018170297

表１と２に記載の正極スラリーを塗工機で塗布し、厚さ８０μｍ、幅１８ｃｍ、長さ５ｍのシートを作製し、そのシートを１２ｃｍ角に裁断することにより正極シートを作製した。
表１と２に記載の負極スラリーを塗工機で塗布し、厚さ８０μｍ、幅１８ｃｍ、長さ５ｍのシートを作製し、そのシートを１２ｃｍ角に裁断することにより負極シートを作製した。
表１と２に記載の固体電解質スラリーを塗工機で塗布し、厚さ３０μｍ、幅１８ｃｍ、長さ５ｍのシートを作製し、そのシートを１２ｃｍ角に裁断することにより固体電解質シートを作製した。 The positive electrode slurry described in Tables 1 and 2 was applied by a coating machine to prepare a sheet having a thickness of 80 μm, a width of 18 cm, and a length of 5 m, and the sheet was cut into a 12 cm square to prepare a positive electrode sheet.
The negative electrode slurry described in Tables 1 and 2 was applied by a coating machine to prepare a sheet having a thickness of 80 μm, a width of 18 cm, and a length of 5 m, and the sheet was cut into a 12 cm square to prepare a negative electrode sheet.
The solid electrolyte slurry described in Tables 1 and 2 was applied with a coating machine to produce a sheet having a thickness of 30 μm, a width of 18 cm, and a length of 5 m, and the sheet was cut into a 12 cm square to produce a solid electrolyte sheet. .

このうち、正極シート及び負極シートに、レーザ加工機（パナソニック電工ＳＵＮＸ社製、型番ＬＰＶ−１５Ｕ）を用いてレーザを照射し、直径１ｍｍの円形の開口を有する開口部を形成した。図３（ｃ）に示すように開口部を形成した正極シートをシートＣとして７枚準備し、図３（ａ）に示すように開口部を形成した負極シートをシートＡとして７枚準備した。このとき、正極シートと負極シートで、異なる位置に開口部を形成するようにした。また、図３（ｄ）に示すように開口部を形成しない正極シートをシートＤとして１枚準備し、図３（ｂ）に示すように開口部を形成しない負極シートをシートＢとして１枚準備した。
他方で、固体電解質シートにも、レーザ加工機を用いてレーザを照射し、正極シート及び負極シートのうち少なくとも一方の開口部の中心と重なる位置に、直径０．８ｍｍの円形の開口を有する開口部を形成した。このとき、図３（ｇ）に示すように正極シートの開口部の中心と重なる位置のみに開口部を形成した固体電解質シートをシートＧとして１枚準備し、図３（ｆ）に示すように負極シートの開口部の中心と重なる位置のみに開口部を形成した固体電解質シートをシートＦとして１枚準備し、図３（ｅ）に示すように両方の位置に開口部を形成した固体電解質シートをシートＥとして１３枚準備した。
シートＡ〜Ｇに形成する開口部の模式図を図３に示す。 Among these, the positive electrode sheet and the negative electrode sheet were irradiated with laser using a laser processing machine (manufactured by Panasonic Electric Works SUNX Co., Ltd., model number LPV-15U) to form an opening having a circular opening with a diameter of 1 mm. As shown in FIG. 3 (c), seven positive electrode sheets having openings formed thereon were prepared as sheets C, and seven negative electrode sheets having openings formed therein as sheets A were prepared as shown in FIG. At this time, the positive electrode sheet and the negative electrode sheet were formed with openings at different positions. Further, as shown in FIG. 3D, one sheet of positive electrode sheet not forming an opening is prepared as a sheet D, and one sheet of negative electrode sheet not forming an opening is prepared as a sheet B as shown in FIG. did.
On the other hand, the solid electrolyte sheet is irradiated with laser using a laser processing machine, and an opening having a circular opening with a diameter of 0.8 mm is provided at a position overlapping with the center of at least one opening of the positive electrode sheet and the negative electrode sheet. Part was formed. At this time, as shown in FIG. 3F, one sheet of solid electrolyte sheet having an opening formed only at a position overlapping with the center of the opening of the positive electrode sheet is prepared as a sheet G, and as shown in FIG. A solid electrolyte sheet in which an opening is formed only at a position overlapping with the center of the opening of the negative electrode sheet is prepared as a sheet F, and a solid electrolyte sheet in which openings are formed at both positions as shown in FIG. 13 sheets were prepared as sheet E.
The schematic diagram of the opening part formed in sheet | seat AG is shown in FIG.

次いで、枚葉式積層機（アルファーシステム株式会社製）を用いて、正極シート、正極シート、固体電解質シート、負極シート、固体電解質シート及び正極シートの順で交互に積層した。より具体的には、シートＤ、シートＦ、シートＡ、シートＥ、シートＣ及びシートＣを順に積層した後、シートＥ、シートＡ、シートＥ、シートＣ及びシートＣの順で６回繰り返して積層し、その後シートＧ及びシートＢを順に積層した。このとき、２枚の正極シートの共通する位置にある開口部と、その開口部に隣接する固体電解質シートにある開口部を重ね合せるとともに、負極シートの開口部とそれに隣接する固体電解質シートにある開口部を重ね合せた。
このとき、離形処理後のシート外寸は１５ｃｍ角になるようにし、各層を積層するごとに仮積層を行い、最後に本積層として２段階のプレスを行った。仮積層は常圧で行い、１００ｋＰａのプレス圧で行った。次いで、真空脱気を行い、シート中の気泡を取り除いた。その後に行われる本積層は２５０ｋＰａのプレス圧で行いシート積層体を得た。 Subsequently, the positive electrode sheet, the positive electrode sheet, the solid electrolyte sheet, the negative electrode sheet, the solid electrolyte sheet, and the positive electrode sheet were alternately stacked in this order using a single wafer type laminator (manufactured by Alpha System Co., Ltd.). More specifically, after the sheet D, the sheet F, the sheet A, the sheet E, the sheet C, and the sheet C are sequentially stacked, the sheet E, the sheet A, the sheet E, the sheet C, and the sheet C are repeated six times in this order. After that, the sheet G and the sheet B were sequentially laminated. At this time, the opening at the common position of the two positive electrode sheets and the opening at the solid electrolyte sheet adjacent to the opening are overlapped, and the opening of the negative electrode sheet and the solid electrolyte sheet adjacent thereto are present. The openings were overlapped.
At this time, the outer dimension of the sheet after the release treatment was set to 15 cm square, temporary lamination was performed every time each layer was laminated, and finally, two-stage pressing was performed as the main lamination. Temporary lamination was performed at normal pressure and a press pressure of 100 kPa. Next, vacuum deaeration was performed to remove bubbles in the sheet. Subsequent lamination was performed at a pressing pressure of 250 kPa to obtain a sheet laminate.

このシート積層体を直径１１ｍｍでくり抜き、窒素雰囲気中で３時間にわたり４００℃で脱脂した。その後、成形型に入れて上型を乗せ、油圧プレスで２０００ｋｇ／ｃｍ２の圧力を掛けながら６００℃まで２℃／ｓｅｃの昇温速度で加熱し、６００℃に到達した後に圧力を開放して室温まで放冷した。外周０．７５ｍｍを＃８００の砥石で研磨し、直径９．５ｍｍの電池要素５を得た。得られた電池要素５についての構成を表３と表４に示す。 This sheet laminate was cut out at a diameter of 11 mm and degreased at 400 ° C. for 3 hours in a nitrogen atmosphere. Thereafter, the upper mold is placed in a mold, heated to 600 ° C. at a rate of 2 ° C./sec while applying a pressure of 2000 kg / cm 2 with a hydraulic press, and after reaching 600 ° C., the pressure is released. Allowed to cool to room temperature. The outer periphery of 0.75 mm was polished with a # 800 grindstone to obtain a battery element 5 having a diameter of 9.5 mm. The configurations of the obtained battery element 5 are shown in Tables 3 and 4.

Figure 2018170297
Figure 2018170297

Figure 2018170297
Figure 2018170297

（第一の緩衝層４に用いるためのスラリー（スラリーＡ）の準備）
電池要素５の周面上に第一の緩衝層４を配置するため、第一の緩衝層４に用いるためのスラリーを、以下のように準備した。調合は３００ｃｃポリプロピレン容器で行った。下記表４に示した緩衝層材料（Ａｌ２Ｏ３ＴＯＭＢＯ（登録商標）、ＳｉＯ２又はＣａＣＯ３）６０ｇ、バインダー１０ｇ（互応化学工業株式会社製、ＫＦＡ−６１１）、溶剤（互応化学工業株式会社製、テキサノール）２０ｇ、分散剤１ｇ（ＢＹＫ製、ＤＩＳＰＥＲＢＹＫ１８０）を加え、可塑剤（互応化学工業製、ＤＯＡ）０．５ｇ、Φ１０ｍｍのＹＴＺボール１００ｇを入れて、泡とり錬太郎（ＴＨＩＮＫＹ社製、ＡＲＶ−２００）を用いて１０００ｒｐｍにて５分間混練を３セット実施後、ＹＴＺボールを分離し、１００Ｔｏｒｒ、１０００ｒｐｍにて５分間脱泡し、第一の緩衝層４に用いるためのスラリーを完成させた。なお、上述のＴＯＭＢＯは、ニチアス株式会社製ファインフレックス（登録商標）バルクファイバー（Ｎｏ．５２００−Ｚ（Ａｌ２Ｏ３３４質量％、ＳｉＯ２５０質量％及びＺｒＯ２１６質量％））である。 (Preparation of slurry (slurry A) for use in first buffer layer 4)
In order to arrange the first buffer layer 4 on the peripheral surface of the battery element 5, a slurry for use in the first buffer layer 4 was prepared as follows. Blending was performed in a 300 cc polypropylene container. 60 g of buffer layer material (Al 2 O 3 TOMBO (registered trademark), SiO 2 or CaCO 3 ) shown in Table 4 below, 10 g of binder (manufactured by Kyoyo Chemical Industry Co., Ltd., KFA-611), solvent (Kyoyo Chemical Industry Co., Ltd.) 20 g of texanol), 1 g of dispersant (manufactured by BYK, DISPERBYK180), 0.5 g of plasticizer (manufactured by Kyoyo Chemical Industry, DOA), and 100 g of YTZ balls having a diameter of 10 mm, After three sets of kneading for 5 minutes at 1000 rpm using ARV-200), the YTZ balls were separated and defoamed at 100 Torr and 1000 rpm for 5 minutes to complete the slurry for use in the first buffer layer 4. It was. In addition, the above-mentioned TOMBO is a fine flex (registered trademark) bulk fiber (No. 5200-Z (Al 2 O 3 34 mass%, SiO 2 50 mass% and ZrO 2 16 mass%)) manufactured by NICHIAS Corporation.

（導電板２の準備）
マルテンサイト系ステンレス鋼（ＳＵＳ３１６Ｌ）を準備した。大きさ（φ）は９．６ｍｍ、厚さは０．１５ｍｍである。 (Preparation of conductive plate 2)
Martensitic stainless steel (SUS316L) was prepared. The size (φ) is 9.6 mm, and the thickness is 0.15 mm.

（ガラス層３に用いるためのスラリー（スラリーＢ）の準備）
電池要素５や第一の緩衝層４の外周側面にガラス層３を配置するため、ガラス層３に用いるためのスラリーを、以下のように準備した。
下記表５に示す酸化物基準のモル％で表されたに示す組成比となるように、硼酸、メタリン酸アルミニウム、酸化アルミニウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、メタリン酸リチウム、リン酸リチウム、酸化ジルコニウム、二酸化テルルなどのガラス原料バッチを調合した。ガラス原料バッチはアルミナるつぼ、石英るつぼ、金るつぼ、又は白金坩堝へ充填し、電気炉により７５０℃〜１３００℃の温度で３０分から４時間加熱溶融した。溶融したガラスは板上に成形し、徐冷した。作製したガラスは、スタンプミルとアルミナ乳鉢を用いて平均粒子径で５０μｍまで粉砕した。 (Preparation of slurry (slurry B) for use in glass layer 3)
In order to arrange the glass layer 3 on the outer peripheral side surfaces of the battery element 5 and the first buffer layer 4, a slurry for use in the glass layer 3 was prepared as follows.
Boric acid, aluminum metaphosphate, aluminum oxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium metaphosphate, lithium phosphate, so as to have the composition ratio shown in mol% of oxide basis shown in Table 5 below. Glass raw material batches such as zirconium oxide and tellurium dioxide were prepared. The glass raw material batch was filled into an alumina crucible, a quartz crucible, a gold crucible, or a platinum crucible, and heated and melted at a temperature of 750 ° C. to 1300 ° C. for 30 minutes to 4 hours in an electric furnace. The molten glass was formed on a plate and slowly cooled. The produced glass was pulverized to an average particle size of 50 μm using a stamp mill and an alumina mortar.

Figure 2018170297
Figure 2018170297

調合は３００ｃｃポリプロピレン容器で行った。表３に示したガラス又は市販のガラス（旭硝子製のＫＰ３１２ＡＳ（Ｔｇが２８０℃）若しくはＴ０１５（Ｔｇが３２０℃））を６０ｇ、バインダー２０ｇ（互応化学製、ＫＦＡ−６１１）、溶剤２０ｇ（互応化学製、テキサノール）、分散剤１ｇ（ＢＹＫ製、ＤＩＳＰＥＲＢＹＫ１８０）、可塑剤（互応化学製、ＤＯＡ）を加え、Φ１０ｍｍのＹＴＺボール１００ｇを入れて、泡とり錬太郎（ＴＨＩＮＫＹ社製、ＡＲＶ−２００）を用いて１０００ｒｐｍにて５分間混練を３セット実施後、ＹＴＺボールを分離し、１００Ｔｏｒｒ、１０００ｒｐｍにて５分間脱泡してスラリーとした。   Blending was performed in a 300 cc polypropylene container. Glass shown in Table 3 or commercially available glass (KP312AS (Tg: 280 ° C.) or T015 (Tg: 320 ° C.) manufactured by Asahi Glass) 60 g, binder 20 g (Kohyo Chemical Co., KFA-611), solvent 20 g (Kohyo Chemical) Manufactured, Texanol), 1 g of dispersing agent (manufactured by BYK, DISPERBYK180), plasticizer (manufactured by Kyoyo Kagaku, DOA), put 100 g of YTZ balls of Φ10 mm, and add Awatori Rentaro (made by THINKY, ARV-200). After three sets of kneading at 1000 rpm for 5 minutes, YTZ balls were separated and defoamed at 100 Torr and 1000 rpm for 5 minutes to obtain a slurry.

（第二の緩衝層６に用いるための材料の準備）
カーボンフェルト、発泡金属（多孔質金属）又はアルミメッシュからなる材料を準備して、第二の緩衝層として準備した。大きさ（φ）は９．６ｍｍ、厚さは０．１５ｍｍである。 (Preparation of material for use in second buffer layer 6)
A material made of carbon felt, foam metal (porous metal) or aluminum mesh was prepared and prepared as a second buffer layer. The size (φ) is 9.6 mm, and the thickness is 0.15 mm.

（全固体電池１の作製）
表６に示す材質および配置、図２に示す配置にて、導電板２、第二の緩衝層６、電池要素５、第二の緩衝層６、導電板２の順で挟み、導電板２上の両面から５００ｇの加重をかけて固定した。
この固定後、電池要素５の周面上に、上述のスラリーＡを塗布し、スラリーの乾燥処理（１００℃、１０分間）を行い、第一の緩衝層４を設けた。
この乾燥処理後、該第一の緩衝層４や電池要素５の周面上に上述のスラリーＢを塗布し、スラリーの乾燥処理（１００℃、１０分間）を行い、ガラス層３を設けた。
この乾燥後、導電板上の上面から５００ｇの加重をかけ、窒素雰囲気で３５０℃まで昇温後、１時間保持し、露点０℃のドライエアーに切り替えて４時間脱脂した。
脱脂後、４３０℃まで昇温し、１０分間かけて、ガラス層３を軟化させた後、降温し、ケーシングし、全固体電池１を得た。
なお、以下表６記載の実施例２１として、第一の緩衝層４を設けない例を作製した。 (Preparation of all-solid battery 1)
With the materials and arrangements shown in Table 6 and the arrangement shown in FIG. 2, the conductive plate 2, the second buffer layer 6, the battery element 5, the second buffer layer 6, and the conductive plate 2 are sandwiched in this order on the conductive plate 2 It fixed by applying a weight of 500 g from both sides.
After the fixing, the above-described slurry A was applied on the peripheral surface of the battery element 5, and the slurry was subjected to a drying process (100 ° C., 10 minutes) to provide the first buffer layer 4.
After the drying treatment, the slurry B described above was applied on the peripheral surfaces of the first buffer layer 4 and the battery element 5, and the slurry was dried (100 ° C., 10 minutes) to provide the glass layer 3.
After this drying, a weight of 500 g was applied from the upper surface on the conductive plate, the temperature was raised to 350 ° C. in a nitrogen atmosphere, held for 1 hour, switched to dry air with a dew point of 0 ° C., and degreased for 4 hours.
After degreasing, the temperature was raised to 430 ° C. and the glass layer 3 was softened over 10 minutes, and then the temperature was lowered and casing was performed to obtain the all-solid battery 1.
In addition, the example which does not provide the 1st buffer layer 4 as Example 21 of Table 6 below was produced.

Figure 2018170297
Figure 2018170297

表６の標記について説明する。周面配置とは電池要素５の周面に第一の緩衝層４を設ける配置をいい、主面配置とは電池要素５の主面に第二の緩衝層６を設ける配置をいう。ここで、電池要素５の主面とは、電池要素の外側の面が、正極層のみの面側又は負極層のみの面側の面をいう。電池要素５の周面とは、電池要素５の主面以外の面をいう。
周面配置については、「全周」は第一の緩衝層を全周設けたことを示し、「１／２（ａ、ｂ）」は第一の緩衝層４を全周のうち図２に示すａとｂの位置に設けたことを示し、「１／２（ａ、ｃ）」は第一の緩衝層４を全周のうち図２に示すａとｃの位置に設けたことを示し、「なし」は第一の緩衝層４を設けていないことを示す。主面の配置については、「両面」は第二の緩衝層６を両主面に設けた例を示し、「上面」は第二の緩衝層６を上面のみ設けた例を示す。「上面」とは、主面であって電池要素５の開口部を形成しない正極シートが設けられた側の面をいう。 The titles in Table 6 will be described. The peripheral surface arrangement refers to an arrangement in which the first buffer layer 4 is provided on the peripheral surface of the battery element 5, and the main surface arrangement refers to an arrangement in which the second buffer layer 6 is provided on the main surface of the battery element 5. Here, the main surface of the battery element 5 refers to a surface on the surface side of only the positive electrode layer or the surface side of only the negative electrode layer on the outer surface of the battery element. The peripheral surface of the battery element 5 refers to a surface other than the main surface of the battery element 5.
Regarding the circumferential arrangement, “all circumference” indicates that the first buffer layer is provided all around, and “½ (a, b)” indicates that the first buffer layer 4 is provided in FIG. “1/2 (a, c)” indicates that the first buffer layer 4 is provided at the positions a and c shown in FIG. 2 in the entire circumference. "None" indicates that the first buffer layer 4 is not provided. Regarding the arrangement of the main surfaces, “both surfaces” indicates an example in which the second buffer layer 6 is provided on both main surfaces, and “upper surface” indicates an example in which the second buffer layer 6 is provided only on the upper surface. The “upper surface” refers to a surface on the side where the positive electrode sheet that is the main surface and does not form the opening of the battery element 5 is provided.

（全固体電池の評価）
実施例について、コイン電池評価治具（アスカ電子製）を用い、下側に正極、上側に負極を配置して、電池性能の評価をした。セットしたコイン評価治具は、加速試験のため恒温恒湿槽内に入れ、６０℃、湿度８０％下にて、交流テスターであるＬＣＲメータ（日置電機、３５２２−５０）による抵抗測定と充放電試験を行った。充放電レートは１／１０Ｃ（１０時間で電極活物質を全て使う充放電電流）と定電流充電、定電流放電とし、充電時カットオフ電圧は２．８Ｖ、放電時カットオフ電圧は０．３Ｖとした。評価結果（充放電試験、サイクル試験結果）を以下表７に示す。 (Evaluation of all-solid-state battery)
About the Example, the coin battery evaluation jig | tool (made by Asuka Electronics) was used, the positive electrode was arrange | positioned at the lower side, the negative electrode was arrange | positioned at the upper side, and battery performance was evaluated. The set coin evaluation jig is placed in a constant temperature and humidity chamber for an acceleration test, resistance measurement and charge / discharge with an LCR meter (Hioki Electric, 3522-50) as an AC tester at 60 ° C. and a humidity of 80%. A test was conducted. Charge / discharge rate is 1 / 10C (charge / discharge current using all electrode active material in 10 hours), constant current charge, constant current discharge, cut-off voltage at charge is 2.8V, cut-off voltage at discharge is 0.3V It was. The evaluation results (charge / discharge test and cycle test results) are shown in Table 7 below.

（比較例１）
比較例１として、電池要素５のみの例を作製した。この電池要素５の構成は、上述の実施例と同じである。電池要素５を、１００℃真空乾燥１時間乾燥後、コイン電池評価治具（アスカ電子製）を用い、下側に正極面、上側に負極面を配置して集電を取った。セットしたコイン評価治具は、加速試験のため恒温恒湿槽内に入れ、６０℃、湿度８０％下にてＬＣＲメータによる抵抗測定と充放電試験を行った。充放電レートは１／１０Ｃと定電流充電、定電流放電とし、充電時カットオフ電圧は２．８Ｖ、放電時カットオフ電圧は０．３Ｖとした。評価結果（充放電試験、サイクル試験結果）を以下表７に示す。 (Comparative Example 1)
As Comparative Example 1, an example of only the battery element 5 was produced. The configuration of the battery element 5 is the same as that in the above-described embodiment. After the battery element 5 was vacuum-dried at 100 ° C. for 1 hour, a coin battery evaluation jig (manufactured by Asuka Electronics Co., Ltd.) was used to collect current by arranging a positive electrode surface on the lower side and a negative electrode surface on the upper side. The set coin evaluation jig was placed in a constant temperature and humidity chamber for an acceleration test, and resistance measurement and a charge / discharge test were performed using an LCR meter at 60 ° C. and a humidity of 80%. The charging / discharging rate was 1/10 C, constant current charging and constant current discharging, the charging cutoff voltage was 2.8 V, and the discharging cutoff voltage was 0.3 V. The evaluation results (charge / discharge test and cycle test results) are shown in Table 7 below.

（比較例２）
比較例２として、電池要素５にアルミラミネートパッケージをした例を作製した。電池要素５を１００℃真空乾燥１時間乾燥させた。パッケージングは露点−５０℃のドライルームにて実施した。タブフィルムとアルミラミネートフィルム、銅箔、アルミ箔で作製したセルホルダーを用いて、セルを真空状態でパッケージングした。なお、負極側を銅箔（集電体）、正極側をアルミ箔（集電体）とした。クリップで止め、加速試験のため恒温恒湿槽内に入れ、６０℃、湿度８０％下にてＬＣＲメータによる抵抗測定と充放電試験を行った。充放電レートは１／１０Ｃと定電流充電、定電流放電とし、充電時カットオフ電圧は２．８Ｖ、放電時カットオフ電圧は０．３Ｖとした。評価結果（充放電試験、サイクル試験結果）を以下表７に示す。 (Comparative Example 2)
As Comparative Example 2, an example in which an aluminum laminate package was used for the battery element 5 was produced. The battery element 5 was dried at 100 ° C. under vacuum for 1 hour. Packaging was performed in a dry room having a dew point of -50 ° C. The cell was packaged in a vacuum state using a cell holder made of a tab film, an aluminum laminate film, copper foil, and aluminum foil. The negative electrode side was a copper foil (current collector), and the positive electrode side was an aluminum foil (current collector). The sample was stopped with a clip, placed in a constant temperature and humidity chamber for an acceleration test, and subjected to resistance measurement and charge / discharge test using an LCR meter at 60 ° C. and a humidity of 80%. The charging / discharging rate was 1/10 C, constant current charging and constant current discharging, the charging cutoff voltage was 2.8 V, and the discharging cutoff voltage was 0.3 V. The evaluation results (charge / discharge test and cycle test results) are shown in Table 7 below.

（比較例３）
比較例３として、電池要素５にコインカシメを施した例を作製した。電池要素５を１００℃真空乾燥１時間乾燥させた。パッケージングは露点−５０℃のドライルームにて実施した。正極側と負極側にそれぞれカーボンペーパーの緩衝層を設けた上で、カシメ型のΦ１５ｍｍの金属製コインケース（ＳＵＳ３１０製）に入れてカシメにて密封した。コイン評価治具を用いてコインケースの集電をとった。セットしたコイン評価治具は、加速試験のため恒温恒湿槽内に入れ、６０℃、湿度８０％下にてＬＣＲメータによる抵抗測定と充放電試験を行った。評価結果（充放電試験、サイクル試験結果）を以下表７に示す。 (Comparative Example 3)
As Comparative Example 3, an example in which the battery element 5 was subjected to coin caulking was produced. The battery element 5 was dried at 100 ° C. under vacuum for 1 hour. Packaging was performed in a dry room having a dew point of -50 ° C. After providing a buffer layer of carbon paper on each of the positive electrode side and the negative electrode side, it was placed in a caulking type Φ15 mm metal coin case (made of SUS310) and sealed with caulking. The coin case was collected using a coin evaluation jig. The set coin evaluation jig was placed in a constant temperature and humidity chamber for an acceleration test, and resistance measurement and a charge / discharge test were performed using an LCR meter at 60 ° C. and a humidity of 80%. The evaluation results (charge / discharge test and cycle test results) are shown in Table 7 below.

Figure 2018170297
Figure 2018170297

（評価結果の考察）
実施例２１を除いたいずれの実施例も１００サイクル容量維持率は高くなった。比較例１では、ケースが無いため、重量が軽く高いエネルギー密度を示したが、サイクル劣化が激しく１００サイクルで３％となった。比較例１については、露点５０℃以下のドライルーム内で実施した充放電試験でのサイクル維持率は１００％であったため、この劣化は、湿度の影響であると考えられる。一方、実施例では、湿度の影響による劣化を抑制できていることを示している。
また、緩衝層の材質に吸湿能力のあるＣａＣＯ３を用いた実施例９のサイクル劣化が最も低い。このことからも、全固体電池においても湿度の影響が強いことがわかる。本評価でも、微量水分が混入しているため、電池形成後にも水分を除去、又は形成中に水分混入できる吸湿能力のある材料が、第一の緩衝層４の材質として、より有効であることが確認できた。
放電容量は比較例３と実施例７が最も高かった。実施例７については、側面緩衝層に反応性の低いＺｒＯ２が添加されている材料を用いたことと、緩衝効果が高い繊維状構造を用いたことにより、シールによる放電容量低下が抑制できるものと考えられる。抵抗については、比較例３とアルミメッシュを用いた実施例１７が最も低かった、集電が良くとれているためと考えられる。電池のエネルギー密度、サイクル特性などを総合すると、実施例１３が最も高い性能を示した。 (Consideration of evaluation results)
In all the examples except Example 21, the 100 cycle capacity retention rate was high. In Comparative Example 1, since there was no case, the weight was light and the energy density was high, but the cycle deterioration was severe and became 3% in 100 cycles. About Comparative Example 1, since the cycle maintenance rate in the charge / discharge test conducted in a dry room having a dew point of 50 ° C. or less was 100%, this deterioration is considered to be an influence of humidity. On the other hand, in the Example, it has shown that the deterioration by the influence of humidity can be suppressed.
Further, the cycle deterioration of Example 9 using CaCO 3 having a moisture absorption capability as the material of the buffer layer is the lowest. This also shows that the influence of humidity is strong even in all solid state batteries. Even in this evaluation, since a very small amount of water is mixed, a material capable of removing moisture even after the battery is formed or having water absorption ability that can be mixed during the formation is more effective as the material of the first buffer layer 4. Was confirmed.
The discharge capacity was the highest in Comparative Example 3 and Example 7. Regarding Example 7, the use of a material in which low-reactivity ZrO 2 is added to the side buffer layer and the use of a fibrous structure having a high buffer effect can suppress a decrease in discharge capacity due to the seal. it is conceivable that. Regarding the resistance, it is considered that Comparative Example 3 and Example 17 using the aluminum mesh were the lowest, and the current collection was good. When the energy density, cycle characteristics, etc. of the battery were combined, Example 13 showed the highest performance.

１ 全固体電池
２ 導電板
３ ガラス層
４ 第一の緩衝層
５ 電池要素
６ 第二の緩衝層 DESCRIPTION OF SYMBOLS 1 All-solid-state battery 2 Conductive plate 3 Glass layer 4 First buffer layer 5 Battery element 6 Second buffer layer

Claims (8)

全固体電池であって、
電池要素と第一の緩衝層とガラス層と導電板を含み、
該電池要素は、正極層と負極層と固体電解質層とを含み、
第一の緩衝層は、該電池要素の周面上の少なくとも一部を被覆し、
該ガラス層は、該電池要素と該第一の緩衝層とが全固体電池外に露出しないように、少なくとも該第一の緩衝層の周面上に設けられ、
該導電板は、該電池要素の両主面上に配置される。
ことを特徴とする、該全固体電池。 An all-solid battery,
Including a battery element, a first buffer layer, a glass layer, and a conductive plate;
The battery element includes a positive electrode layer, a negative electrode layer, and a solid electrolyte layer,
The first buffer layer covers at least part of the peripheral surface of the battery element;
The glass layer is provided on at least the peripheral surface of the first buffer layer so that the battery element and the first buffer layer are not exposed outside the all-solid-state battery,
The conductive plate is disposed on both main surfaces of the battery element.
The all-solid-state battery characterized by the above-mentioned. 該電池要素と該導電板の間に、該電池要素の少なくとも一部を被覆するように、第二の緩衝層を設ける、請求項１記載の全固体電池。   The all-solid-state battery according to claim 1, wherein a second buffer layer is provided between the battery element and the conductive plate so as to cover at least a part of the battery element. 該第一の緩衝層はセラミックスを含む、請求項１又は２に記載の全固体電池。   The all-solid-state battery according to claim 1, wherein the first buffer layer includes ceramics. 該ガラス層のガラスは、ガラス転移点（Ｔｇ）が５００℃以下である、請求項１〜３のいずれかに記載の全固体電池。   The glass of this glass layer is an all-solid-state battery in any one of Claims 1-3 whose glass transition point (Tg) is 500 degrees C or less. 該ガラス層のガラスは、Ｂ２Ｏ３、ＴｅＯ２、Ａ２Ｏ３（式中、Ａは、Ａｌ、Ｂｉ、Ｌａからなる群より選択される１種以上）及びＲｎ２Ｏ（式中、ＲｎはＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓからなる群より選択される１種以上）成分を含有するガラスである、請求項１〜４のいずれかに記載の全固体電池。 The glass of the glass layer includes B 2 O 3 , TeO 2 , A 2 O 3 (wherein A is one or more selected from the group consisting of Al, Bi, La) and Rn 2 O (wherein 5. The all-solid-state battery according to claim 1, wherein Rn is a glass containing one or more components selected from the group consisting of Li, Na, K, Rb, and Cs. 該ガラス層のガラスは、Ａ２Ｏ３（式中、Ａは、Ａｌ、Ｂｉ、Ｌａからなる群より選択される１種以上）、Ｒｎ２Ｏ（ＲｎはＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓからなる群より選択される１種以上）及びＤ２Ｏ５（式中、ＤはＰ、Ｖからなる群より選択される１種以上）成分を含有するガラスである、請求項１〜４のいずれかに記載の全固体電池。 The glass of the glass layer is A 2 O 3 (wherein A is one or more selected from the group consisting of Al, Bi, La), Rn 2 O (Rn is Li, Na, K, Rb, Cs). 1 or more selected from the group consisting of) and D 2 O 5 (wherein D is one or more selected from the group consisting of P and V), which is a glass containing components. The all-solid-state battery in any one. 該導電板は、ステンレス鋼又はＣｏ基合金からなる、請求項１〜６のいずれかに記載の全固体電池。   The all-solid-state battery according to claim 1, wherein the conductive plate is made of stainless steel or a Co-based alloy. 該第二の緩衝層が、気孔率が３０％以上の、炭素、ステンレス鋼、ニッケル、ニッケル合金又はアルミニウムである、請求項１〜７のいずれかに記載の全固体電池。   The all-solid-state battery according to any one of claims 1 to 7, wherein the second buffer layer is carbon, stainless steel, nickel, a nickel alloy, or aluminum having a porosity of 30% or more.
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