JP7017484B2 - Manufacturing method of all-solid-state battery - Google Patents

Manufacturing method of all-solid-state battery Download PDF

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JP7017484B2
JP7017484B2 JP2018151890A JP2018151890A JP7017484B2 JP 7017484 B2 JP7017484 B2 JP 7017484B2 JP 2018151890 A JP2018151890 A JP 2018151890A JP 2018151890 A JP2018151890 A JP 2018151890A JP 7017484 B2 JP7017484 B2 JP 7017484B2
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layer
battery
negative electrode
current collector
active material
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JP2020027742A (en
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哲也 早稲田
耕作 益田
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Toyota Motor Corp
I Pex Inc
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Dai Ichi Seiko Co Ltd
Toyota Motor Corp
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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

Description

本開示は、全固体電池に関する。特に、本開示は、電池積層体及び電池積層体を被覆している樹脂層を有する全固体電池に関する。 The present disclosure relates to an all-solid-state battery. In particular, the present disclosure relates to a battery laminate and an all-solid-state battery having a resin layer covering the battery laminate.

近年、樹脂を用いて電池を封止する技術が種々開示されている。 In recent years, various techniques for sealing a battery using a resin have been disclosed.

例えば、特許文献１では、全固体電池素子を熱硬化性樹脂又は熱可塑性樹脂から構成する外装体で被覆する技術が開示されている。 For example, Patent Document 1 discloses a technique of coating an all-solid-state battery element with an exterior body made of a thermosetting resin or a thermoplastic resin.

また、特許文献２では、バイポーラ型の積層電池を複数個有し、複数の積層電池の全体をモールド樹脂によって封止された全固体電池が開示されている。 Further, Patent Document 2 discloses an all-solid-state battery having a plurality of bipolar type laminated batteries and having the entire plurality of laminated batteries sealed with a mold resin.

一般的に、全固体電池は、単位電池を１以上含む電池積層体を有し、この単位電池は、正極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層を、この順で積層してなる。また、電池積層体では、一般的に、正極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層のうちの少なくとも１層が、他の層よりも外方に延出している延出部を有し、電池積層体の側面においては、延出部間に隙間が形成されている。 Generally, an all-solid-state battery has a battery laminate containing one or more unit batteries, and the unit battery has a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode collection. The electric body layers are laminated in this order. Further, in the battery laminate, in general, at least one of the positive electrode current collector layer, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector layer is larger than the other layers. It has an extending portion extending outward, and a gap is formed between the extending portions on the side surface of the battery laminate.

側面にこのような隙間を有する電池積層体の側面を樹脂層で被覆する際に、樹脂をその隙間まで確実に埋め込むために、様々な技術が開発されている。 When the side surface of the battery laminate having such a gap on the side surface is covered with the resin layer, various techniques have been developed in order to surely embed the resin up to the gap.

例えば特許文献３では、延出部間に隙間が形成されている電池積層体の側面に対して、隙間に液状の樹脂を供給し、そして樹脂を硬化させることによって、樹脂層で被覆されている全固体電池を製造する方法が開示されている。 For example, in Patent Document 3, a liquid resin is supplied to the side surface of the battery laminate in which a gap is formed between the extending portions, and the resin is cured to cover the side surface with the resin layer. A method for manufacturing an all-solid-state battery is disclosed.

特開２０００－１０６１５４号公報Japanese Unexamined Patent Publication No. 2000-106154 特開２０１４－１１６１５６号公報Japanese Unexamined Patent Publication No. 2014-116156 特開２０１７－２２０４４７号公報Japanese Unexamined Patent Publication No. 2017-20447

通常、電池積層体の側面を樹脂層で被覆する全固体電池の製造方法は、樹脂を供給する工程及び樹脂を硬化させる工程を含んでいる。このため、電池積層体の側面に樹脂層を形成するために、時間が掛かって生産コストが高くなる可能性がある。 Usually, a method for manufacturing an all-solid-state battery in which the side surface of a battery laminate is coated with a resin layer includes a step of supplying a resin and a step of curing the resin. Therefore, since the resin layer is formed on the side surface of the battery laminate, it takes time and the production cost may increase.

したがって、本開示は、上記事情を鑑みてなされたものであり、短時間で電池積層体の側面に樹脂層を形成できる全固体電池の製造方法を提供することを目的とする。 Therefore, the present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a method for manufacturing an all-solid-state battery capable of forming a resin layer on a side surface of a battery laminate in a short time.

本開示の本発明者は、下記の工程を含む全固体電池の製造方法により、上記課題を解決できることを見出した：
（ａ）２以上の単位電池を含む電池積層体を準備すること、ここで、前記単位電池は、正極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層をこの順に積層することによって構成されており、前記正極集電体層、前記正極活物質層、前記固体電解質層、前記負極活物質層、及び前記負極集電体層のうちの少なくとも１層が、前記電池積層体の側面において、他の層よりも外方に延出している延出部を有し、かつ前記延出部間に隙間が形成されており；並びに
（ｂ）前記電池積層体を収容しており、かつ加熱されている金型に、熱硬化性樹脂を注入することによって、前記電池積層体の側面に樹脂層を形成すること、ここで、前記熱硬化性樹脂の粘度が、５Ｐａ・ｓ以上１０Ｐａ・ｓ以下であり、前記熱硬化性樹脂の注入圧が１ＭＰａ以上３ＭＰａ以下である。 The present inventor of the present disclosure has found that the above problems can be solved by a method for manufacturing an all-solid-state battery including the following steps:
(A) Preparing a battery laminate containing two or more unit batteries, wherein the unit battery includes a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector. The body layers are laminated in this order, and at least one of the positive electrode current collector layer, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector layer. The layer has an extension portion extending outward from the other layers on the side surface of the battery laminate, and a gap is formed between the extension portions; and (b) the battery. By injecting a thermosetting resin into a mold that houses and is heated, a resin layer is formed on the side surface of the battery laminate, wherein the thermocurable resin is used. The viscosity is 5 Pa · s or more and 10 Pa · s or less, and the injection pressure of the thermosetting resin is 1 MPa or more and 3 MPa or less.

本開示の全固体電池の製造方法によれば、短時間で電池積層体の側面に樹脂層を形成することができる。 According to the method for manufacturing an all-solid-state battery of the present disclosure, a resin layer can be formed on a side surface of a battery laminate in a short time.

図１は、本開示にかかる工程（ａ）の一態様を示す概略断面図である。FIG. 1 is a schematic cross-sectional view showing an aspect of step (a) according to the present disclosure. 図２は、本開示にかかる工程（ｂ）の一態様を示す概略断面図である。FIG. 2 is a schematic cross-sectional view showing an aspect of step (b) according to the present disclosure. 図３は、本開示の全固体電池の一例を示す概略断面図である。FIG. 3 is a schematic cross-sectional view showing an example of the all-solid-state battery of the present disclosure. 図４は、実施例４、比較例３及び比較例７の製造された全固体電池の断面写真である。FIG. 4 is a cross-sectional photograph of the manufactured all-solid-state batteries of Example 4, Comparative Example 3, and Comparative Example 7.

以下、図面を参照しながら、本開示を実施するための形態について、詳細に説明する。なお、説明の便宜上、各図において、同一又は相当する部分には同一の参照符号を付し、重複説明は省略する。実施の形態の各構成要素は、全てが必須のものであるとは限らず、一部の構成要素を省略可能な場合もある。ただし、以下の図に示される形態は本開示の例示であり、本開示を限定するものではない。 Hereinafter, embodiments for carrying out the present disclosure will be described in detail with reference to the drawings. For convenience of explanation, the same reference numerals are given to the same or corresponding parts in each figure, and duplicate explanations will be omitted. Not all of the components of the embodiment are essential, and some components may be omitted. However, the form shown in the figure below is an example of the present disclosure and does not limit the present disclosure.

《全固体電池の製造方法》
本開示の全固体電池の製造方法は、下記の工程を含む：
（ａ）２以上の単位電池を含む電池積層体を準備すること、ここで、単位電池は、正極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層をこの順に積層することによって構成されており、正極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層のうちの少なくとも１層が、電池積層体の側面において、他の層よりも外方に延出している延出部を有し、かつ延出部間に隙間が形成されており；並びに
（ｂ）電池積層体を収容しており、かつ加熱されている金型に、熱硬化性樹脂を注入することによって、電池積層体の側面に樹脂層を形成すること、ここで、熱硬化性樹脂の粘度が５Ｐａ・ｓ以上１０Ｐａ・ｓ以下であり、熱硬化性樹脂の注入圧が１ＭＰａ以上３ＭＰａ以下である。 << Manufacturing method of all-solid-state battery >>
The method for manufacturing an all-solid-state battery of the present disclosure includes the following steps:
(A) Preparing a battery laminate containing two or more unit batteries, wherein the unit battery includes a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector. The layers are laminated in this order, and at least one of the positive electrode current collector layer, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector layer is a battery laminate. On the side of, it has an extension that extends outward from the other layers, and a gap is formed between the extensions; and (b) it houses the battery laminate and By injecting a thermosetting resin into a heated mold, a resin layer is formed on the side surface of the battery laminate, where the viscosity of the thermosetting resin is 5 Pa · s or more and 10 Pa · s or less. Yes, the injection pressure of the thermosetting resin is 1 MPa or more and 3 MPa or less.

〈工程（ａ）〉
工程（ａ）では、２以上の単位電池を含む電池積層体を準備する。 <Step (a)>
In step (a), a battery laminate containing two or more unit batteries is prepared.

ここで、単位電池は、正極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層をこの順に積層することによって構成されており、正極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層のうちの少なくとも１層が、電池積層体の側面において、他の層よりも外方に延出している延出部を有し、かつ延出部間に隙間が形成されている。 Here, the unit battery is configured by laminating a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer in this order, and is composed of a positive electrode current collector layer. , At least one of the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector layer extends outward from the other layers on the side surface of the battery laminate. It has a portion and a gap is formed between the extending portions.

図１は、本開示にかかる工程（ａ）の一態様を示す概略断面図である。より具体的には、図１では、単位電池６ａ～６ｌを１１個含む電池積層体２０を準備した態様が示されている。 FIG. 1 is a schematic cross-sectional view showing an aspect of step (a) according to the present disclosure. More specifically, FIG. 1 shows an embodiment in which a battery laminate 20 including 11 unit batteries 6a to 6l is prepared.

これらの単位電池６ａ～６ｌは、いずれも正極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層を、この順に積層することによって構成されており、また、電池積層体２０の側面において、固体電解質層、負極活物質層、及び負極集電体層が、正極集電体層及び正極活物質層よりも外方に延出している延出部を有し、かつ延出部間に隙間Ｘ１～Ｘ５が形成されている。 Each of these unit batteries 6a to 6l is configured by laminating a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer in this order. Further, on the side surface of the battery laminate 20, an extension portion in which the solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector layer extend outward from the positive electrode current collector layer and the positive electrode active material layer is provided. It has, and gaps X1 to X5 are formed between the extending portions.

〈工程（ｂ）〉
工程（ｂ）では、電池積層体を収容しており、かつ加熱されている金型に、熱硬化性樹脂を注入することによって、電池積層体の側面に樹脂層を形成する。なお、この注入は、予め電池積層体を収容しており、かつ加熱されている金型を、減圧しておいて行うこともできる。 <Step (b)>
In the step (b), the resin layer is formed on the side surface of the battery laminate by injecting the thermosetting resin into the mold accommodating the battery laminate and being heated. It should be noted that this injection can also be performed by reducing the pressure of the mold in which the battery laminate is housed and heated in advance.

図２は、本開示にかかる工程（ｂ）の一態様を示す概略断面図である。より具体的には、図２（ａ）は、図１で準備した電池積層体２０が金型５０に収容されている態様を示している。なお、金型５０は、加熱されている。 FIG. 2 is a schematic cross-sectional view showing an aspect of step (b) according to the present disclosure. More specifically, FIG. 2A shows an embodiment in which the battery laminate 20 prepared in FIG. 1 is housed in the mold 50. The mold 50 is heated.

本開示において、電池積層体を金型に入れてから、金型を加熱してもよく、電池積層体を加熱されている金型に入れてもよい。また、金型の加熱温度は、特に限定されず、用いる熱硬化性樹脂の硬化できる温度範囲において適宜設定できる。 In the present disclosure, the battery laminate may be placed in a mold and then the mold may be heated, or the battery laminate may be placed in a heated mold. Further, the heating temperature of the mold is not particularly limited and can be appropriately set within a temperature range in which the thermosetting resin to be used can be cured.

図２（ｂ）は、電池積層体２０を収容しており、かつ加熱されている金型５０に、熱硬化性樹脂を注入することによって、電池積層体２０の側面に樹脂層２１が形成されている態様を示している。 FIG. 2B shows that the resin layer 21 is formed on the side surface of the battery laminate 20 by injecting the thermosetting resin into the mold 50 that houses the battery laminate 20 and is heated. It shows the aspect.

従来、熱硬化性樹脂の注入と加熱による硬化とは別の工程として広く行われていた。しかしながら、本開示の本発明者は、熱硬化性樹脂を加熱してもすぐには硬化せずに、むしろ場合によっては粘度が低下し、その後で硬化することに基づいて、特定範囲の粘度と注入圧を用いることによって、側面に隙間を有する電池積層体の側面を樹脂層で確実に被覆できることを見出して、本開示に想到した。 Conventionally, injection of a thermosetting resin and curing by heating have been widely performed as separate steps. However, the inventor of the present disclosure has a specific range of viscosities based on the fact that the thermosetting resin does not cure immediately when heated, but rather decreases in viscosity in some cases and then cures. We have come up with the present disclosure by finding that the side surface of the battery laminate having a gap on the side surface can be reliably covered with the resin layer by using the injection pressure.

本開示において、用いる熱硬化性樹脂は、特に限定されず、例えば電池積層体に損傷を与えない程度の温度で硬化できる樹脂材料から適宜選択できる。 In the present disclosure, the thermosetting resin used is not particularly limited, and can be appropriately selected from, for example, a resin material that can be cured at a temperature that does not damage the battery laminate.

熱硬化性樹脂としては、ポリウレタン、天然ゴム、合成ゴム、エポキシ樹脂、フェノール樹脂、ポリエステル、ポリアミド、シリコーン、シアネート樹脂及び／又はそれを原料としたプレポリマー、ビスマレイミド－トリアジン樹脂、メラミン樹脂、熱硬化性ポリイミド等、並びにこれらの熱硬化性樹脂の１種以上を含む混合物が挙げられる。なお、熱硬化性樹脂としては、加熱によって硬化が促進される限り、常温硬化型の樹脂も含まれるものとする。 Examples of the thermosetting resin include polyurethane, natural rubber, synthetic rubber, epoxy resin, phenol resin, polyester, polyamide, silicone, cyanate resin and / or a prepolymer made from the same, bismaleimide-triazine resin, melamine resin, and heat. Examples thereof include curable polyimides and the like, as well as mixtures containing one or more of these thermosetting resins. The thermosetting resin also includes a room temperature curable resin as long as the curing is promoted by heating.

熱硬化性樹脂の粘度が５Ｐａ・ｓ未満であると、電池積層体の側面の延出部間の隙間に注入された熱硬化性樹脂が流出してしまう可能性があり、よって延出部間の隙間に樹脂層を確実に形成できないおそれがある。また、熱硬化性樹脂の粘度が１０Ｐａ・ｓを超えると、電池積層体の側面の延出部が変形してしまうおそれがある。したがって、本開示において、熱硬化性樹脂の粘度は５Ｐａ・ｓ以上１０Ｐａ・ｓ以下であると規定している。なお、熱硬化性樹脂の粘度は、６Ｐａ・ｓ以上、７Ｐａ・ｓ以上、８Ｐａ・ｓ以上、又は９Ｐａ・ｓ以上であってもよく、また９Ｐａ・ｓ以下、８Ｐａ・ｓ以下、７Ｐａ・ｓ以下、又は６Ｐａ・ｓ以下であってもよい。 If the viscosity of the thermosetting resin is less than 5 Pa · s, the thermosetting resin injected into the gap between the extending portions on the side surface of the battery laminate may flow out, and therefore, between the extending portions. There is a possibility that the resin layer cannot be reliably formed in the gaps between the two. Further, if the viscosity of the thermosetting resin exceeds 10 Pa · s, the extended portion on the side surface of the battery laminate may be deformed. Therefore, the present disclosure stipulates that the viscosity of the thermosetting resin is 5 Pa · s or more and 10 Pa · s or less. The viscosity of the thermosetting resin may be 6 Pa · s or more, 7 Pa · s or more, 8 Pa · s or more, or 9 Pa · s or more, and 9 Pa · s or less, 8 Pa · s or less, 7 Pa · s. It may be less than or equal to 6 Pa · s or less.

なお、本開示において、熱硬化性樹脂の粘度は、加熱時における粘度とする。 In the present disclosure, the viscosity of the thermosetting resin is the viscosity at the time of heating.

また、熱硬化性樹脂の注入圧が１ＭＰａ未満であると、電池積層体の側面の延出部間の隙間に樹脂が入らずボイドが発生してしまう恐れがある。また、熱硬化性樹脂の注入圧が５ＭＰａ以上であると、電池積層体の側面の延出部が変形してしまうおそれがある。したがって、本開示において、熱硬化性樹脂の注入圧は、１ＭＰａ以上３ＭＰａ以下であると規定している。なお、熱硬化性樹脂の注入圧は、１．５ＭＰａ以上、１．８ＭＰａ以上、２．０ＭＰａ以上、２．５ＭＰａ以上、又は２．８ＭＰａ以上であってもよく、また２．８ＭＰａ以下、２．５８ＭＰａ以下、２．０ＭＰａ以下、１．８ＭＰａ以下、又は１．５ＭＰａ以下であってもよい。 Further, if the injection pressure of the thermosetting resin is less than 1 MPa, the resin may not enter the gap between the extending portions on the side surface of the battery laminate and voids may be generated. Further, if the injection pressure of the thermosetting resin is 5 MPa or more, the extended portion on the side surface of the battery laminate may be deformed. Therefore, the present disclosure stipulates that the injection pressure of the thermosetting resin is 1 MPa or more and 3 MPa or less. The injection pressure of the thermosetting resin may be 1.5 MPa or more, 1.8 MPa or more, 2.0 MPa or more, 2.5 MPa or more, or 2.8 MPa or more, and 2.8 MPa or less, 2. It may be 58 MPa or less, 2.0 MPa or less, 1.8 MPa or less, or 1.5 MPa or less.

このように、本開示の方法によって、側面の延出部間に隙間が形成されている電池積層体の側面に樹脂層を形成することができる。 As described above, according to the method of the present disclosure, the resin layer can be formed on the side surface of the battery laminate in which a gap is formed between the extending portions on the side surface.

電池積層体の積層方向の上側及び下側の端面を樹脂層で被覆しないことが好ましい場合、例えば工程（ｂ）の前に、電池積層体の積層方向の上側及び下側の端面を挟み込むようにして保持するジグによって、電池積層体の積層方向の上側及び下側の端面を保護することができる。あるいは、この場合、電池積層体の積層方向の上側及び下側の端面にマスキングテープを貼り付けることもできる。 When it is preferable not to cover the upper and lower end faces of the battery laminate in the stacking direction with the resin layer, for example, before the step (b), the upper and lower end faces of the battery laminate in the stacking direction are sandwiched. It is possible to protect the upper and lower end faces of the battery laminate in the stacking direction by the jig held by the jig. Alternatively, in this case, masking tape can be attached to the upper and lower end faces of the battery laminate in the stacking direction.

《全固体電池》
上述した方法によって製造される本開示の全固体電池は、２以上の単位電池を含む電池積層体、及び電池積層体の側面に樹脂層を有する。 << All-solid-state battery >>
The all-solid-state battery of the present disclosure manufactured by the above-mentioned method has a battery laminate including two or more unit batteries, and a resin layer on the side surface of the battery laminate.

ここで、単位電池は、正極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層をこの順に積層することによって構成されており、正極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層のうちの少なくとも１層が、電池積層体の側面において、他の層よりも外方に延出している延出部を有し、かつ延出部間に隙間が形成されている。 Here, the unit battery is configured by laminating a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer in this order, and is composed of a positive electrode current collector layer. , At least one of the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector layer extends outward from the other layers on the side surface of the battery laminate. It has a portion and a gap is formed between the extending portions.

なお、電池積層体の側面とは、電池積層体に含まれる単位電池の各層の外縁によって構成されている面である。 The side surface of the battery laminate is a surface formed by the outer edges of each layer of the unit battery included in the battery laminate.

例えば、図３は、本開示の全固体電池の一例を示す概略断面図である。本開示の全固体電池１００では、固体電解質層３ａ～３ｄ、負極活物質層４ａ～４ｄ、及び負極集電体層５ａ～５ｄはそれぞれ、電池積層体１０の側面において、他の層、具体的には正極活物質層２ａ～２ｄ、及び正極集電体層１ａ～１ｄよりも外方に延出している延出部３０ｂ及び３０ｃを有し、かつ延出部３０ｂ及び３０ｃの間に隙間が形成されている。なお、この隙間も樹脂層１１で被覆されている。 For example, FIG. 3 is a schematic cross-sectional view showing an example of the all-solid-state battery of the present disclosure. In the all-solid-state battery 100 of the present disclosure, the solid electrolyte layers 3a to 3d, the negative electrode active material layers 4a to 4d, and the negative electrode current collector layers 5a to 5d are each another layer, specifically, on the side surface of the battery laminate 10. Has the positive electrode active material layers 2a to 2d and the extending portions 30b and 30c extending outward from the positive electrode current collector layers 1a to 1d, and there is a gap between the extending portions 30b and 30c. It is formed. This gap is also covered with the resin layer 11.

〈電池積層体〉
本開示において、電池積層体は、正極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層を、この順で積層してなる単位電池を２以上含む。すなわち、本開示において、電池積層体に含まれる単位電池の個数は、２以上であればよく、目的・用途に合わせて、随意に単位電池の個数を設定することができる。 <Battery laminate>
In the present disclosure, the battery laminate includes two or more unit batteries in which a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer are laminated in this order. .. That is, in the present disclosure, the number of unit batteries included in the battery laminate may be 2 or more, and the number of unit batteries can be arbitrarily set according to the purpose and application.

例えば、図３に示されている電池積層体１０は、４つの単位電池６ａ、６ｂ、６ｃ及び６ｄを有している。また、単位電池６ａは、正極集電体層１ａ、正極活物質層２ａ、固体電解質層３ａ、負極活物質層４ａ、及び負極集電体層５ａ（５ｂ）をこの順に積層することによって構成されている。単位電池６ｂは、負極集電体層５ａ（５ｂ）、負極活物質層４ｂ、固体電解質層３ｂ、正極活物質層２ｂ、及び正極集電体層１ｂ（１ｃ）をこの順に積層することによって構成されている。単位電池６ｃは、正極集電体層１ｂ（１ｃ）、正極活物質層２ｃ、固体電解質層３ｃ、負極活物質層４ｃ、及び負極集電体層５ｃ（５ｄ）をこの順に積層することによって構成されている。単位電池６は、負極集電体層５ｃ（５ｄ）、負極活物質層４ｄ、固体電解質層３ｄ、正極活物質層２ｄ、正極集電体層１ｄをこの順に積層することによって構成されている。 For example, the battery laminate 10 shown in FIG. 3 has four unit batteries 6a, 6b, 6c and 6d. Further, the unit battery 6a is configured by laminating a positive electrode current collector layer 1a, a positive electrode active material layer 2a, a solid electrolyte layer 3a, a negative electrode active material layer 4a, and a negative electrode current collector layer 5a (5b) in this order. ing. The unit battery 6b is configured by laminating a negative electrode current collector layer 5a (5b), a negative electrode active material layer 4b, a solid electrolyte layer 3b, a positive electrode active material layer 2b, and a positive electrode current collector layer 1b (1c) in this order. Has been done. The unit battery 6c is configured by laminating a positive electrode current collector layer 1b (1c), a positive electrode active material layer 2c, a solid electrolyte layer 3c, a negative electrode active material layer 4c, and a negative electrode current collector layer 5c (5d) in this order. Has been done. The unit battery 6 is configured by laminating a negative electrode current collector layer 5c (5d), a negative electrode active material layer 4d, a solid electrolyte layer 3d, a positive electrode active material layer 2d, and a positive electrode current collector layer 1d in this order.

また、図１に示されている電池積層体２０は、１１個の単位電池６ａ～６ｌを有する態様である。なお、各単位電池の構成の詳細は、上述した電池積層体１０における単位電池の説明を参照されたい。 Further, the battery laminate 20 shown in FIG. 1 is an embodiment having 11 unit batteries 6a to 6l. For details of the configuration of each unit battery, refer to the description of the unit battery in the battery laminate 10 described above.

本開示において、電池積層体は、モノポーラ型の電池積層体であってもよく、バイポーラ型の電池積層体であってもよい。 In the present disclosure, the battery laminate may be a monopolar type battery laminate or a bipolar type battery laminate.

モノポーラ型の電池積層体である場合、積層方向に隣接する２つの単位電池は、正極集電体層又は負極集電体層を共有するモノポーラ型の構成であってよい。例えば、図３に示されているように、隣接する単位電池６ａ及び６ｂは、負極集電体層５ａ（５ｂ）を共有しており、隣接する単位電池６ｂ及び６ｃは、正極集電体層１ｂ（１ｃ）を共有しており、また隣接する単位電池６ｃ及び６ｄは、負極集電体層５ｃ（５ｄ）を共有しており、これらの単位電池６ａ、６ｂ、６ｃ及び６ｄを合わせてモノポーラ型の電池積層体１０を構成している。 In the case of a monopolar type battery laminate, the two unit batteries adjacent to each other in the stacking direction may have a monopolar type configuration sharing a positive electrode current collector layer or a negative electrode current collector layer. For example, as shown in FIG. 3, adjacent unit batteries 6a and 6b share a negative electrode current collector layer 5a (5b), and adjacent unit batteries 6b and 6c share a positive electrode current collector layer. 1b (1c) is shared, and adjacent unit batteries 6c and 6d share a negative electrode current collector layer 5c (5d), and these unit batteries 6a, 6b, 6c and 6d are combined into a monopolar. It constitutes a type of battery laminate 10.

バイポーラ型の電池積層体である場合、積層方向に隣接する２つの単位電池は、正極及び負極集電体層の両方として用いられる正極／負極集電体層を共有するバイポーラ型の構成であってよい。したがって、例えば電池積層体は、正極及び負極集電体層の両方として用いられる正極／負極集電体層を共有する３つの単位電池の積層体であってよく、具体的には、正極集電体層、正極活物質層、固体電解質層、負極活物質層、正極／負極集電体層、正極活物質層、固体電解質層、負極活物質層、正極／負極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層を、この順で有することができる（図示せず）。また、この場合において、「正極／負極集電体層」は、正極及び負極集電体層の両方として用いられるため、本開示でいう「正極集電体層」又は「負極集電体層」のいずれにも当てはまる。 In the case of a bipolar type battery laminate, the two unit batteries adjacent to each other in the stacking direction have a bipolar type configuration sharing a positive electrode / negative electrode current collector layer used as both a positive electrode and a negative electrode current collector layer. good. Therefore, for example, the battery laminate may be a laminate of three unit batteries sharing a positive electrode / negative electrode current collector layer used as both a positive electrode and a negative electrode current collector layer, and specifically, a positive electrode current collector. Body layer, positive electrode active material layer, solid electrolyte layer, negative electrode active material layer, positive electrode / negative electrode current collector layer, positive electrode active material layer, solid electrolyte layer, negative electrode active material layer, positive electrode / negative electrode current collector layer, positive electrode active material A layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer can be provided in this order (not shown). Further, in this case, since the "positive electrode / negative electrode current collector layer" is used as both the positive electrode and the negative electrode current collector layer, the "positive electrode current collector layer" or the "negative electrode current collector layer" referred to in the present disclosure. It applies to any of the above.

本開示において、正極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層のうちの少なくとも１層が、電池積層体の側面において、他の層よりも外方に延出している延出部を有し、かつ延出部間に隙間が形成されていれば、延出部を有する層は、正極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層のうちのどの層に限定されるものではない。 In the present disclosure, at least one of the positive electrode collector layer, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector layer is more than the other layers on the side surface of the battery laminate. If there is an extending portion extending outward and a gap is formed between the extending portions, the layer having the extending portion is a positive electrode current collector layer, a positive electrode active material layer, and a solid electrolyte layer. , The negative electrode active material layer, and the negative electrode current collector layer are not limited to any of the layers.

なお、リチウムイオン電池に代表される積層型の全固体電池では、充電時に正極活物質層から放出されたリチウムイオンを負極活物質層に確実かつスムーズに移動させるために、負極活物質層及び負極集電体層が正極活物質層及び正極集電体層よりも大面積で形成することが好ましい。したがって、負極活物質層、負極集電体層、及び固体電解質層が延出部を有することが好ましい。 In a laminated all-solid-state battery represented by a lithium ion battery, a negative electrode active material layer and a negative electrode are used in order to reliably and smoothly move the lithium ions released from the positive electrode active material layer to the negative electrode active material layer during charging. It is preferable that the current collector layer is formed in a larger area than the positive electrode active material layer and the positive electrode current collector layer. Therefore, it is preferable that the negative electrode active material layer, the negative electrode current collector layer, and the solid electrolyte layer have an extending portion.

延出部の延出距離（長さ）は、特に限定されず、目的とする全固体電池の目的・用途に合わせて、随意に設定することができる。例えば延出部の延出距離（長さ）は、０．５ｍｍ以上、１ｍｍ以上、１．５ｍｍ以上、２ｍｍ以上、２．５ｍｍ以上、又は３ｍｍ以上であってもよく、また１０ｍｍ以下、８ｍｍ以下、５ｍｍ以下、４．５ｍｍ以下、又は３ｍｍ以下であってもよい。 The extension distance (length) of the extension portion is not particularly limited, and can be arbitrarily set according to the purpose and application of the target all-solid-state battery. For example, the extension distance (length) of the extension portion may be 0.5 mm or more, 1 mm or more, 1.5 mm or more, 2 mm or more, 2.5 mm or more, or 3 mm or more, and 10 mm or less, 8 mm or less. It may be 5 mm or less, 4.5 mm or less, or 3 mm or less.

延出部間の距離（すなわち、延出部間の隙間の高さ）は、特に限定されず、目的とする全固体電池の目的・用途に合わせて、随意に設定することができる。例えば延出部の延出距離（長さ）は、３０μｍ以上、４０μｍ以上、５０μｍ以上、６０μｍ以上、７０μｍ以上、８０μｍ以上、９０μｍ以上、１００μｍ以上、又は１２０μｍ以上であってもよく、また２００μｍ以下、１８０μｍ以下、１６０μｍ以下、１４０μｍ以下、又は１２０μｍ以下であってもよい。 The distance between the extension portions (that is, the height of the gap between the extension portions) is not particularly limited, and can be arbitrarily set according to the purpose and application of the target all-solid-state battery. For example, the extension distance (length) of the extension portion may be 30 μm or more, 40 μm or more, 50 μm or more, 60 μm or more, 70 μm or more, 80 μm or more, 90 μm or more, 100 μm or more, or 120 μm or more, and 200 μm or less. , 180 μm or less, 160 μm or less, 140 μm or less, or 120 μm or less.

また、本開示の全固体電池は、正極集電体層に電気的に接続されている正極集電タブを有し、負極集電体層に電気的に接続されている負極集電タブを有していてもよい。この場合、これらの集電タブが樹脂層から突出していてよい。この構成によれば、集電タブを介して、電池積層体で発生した電力を外部に取り出すことができる。 Further, the all-solid-state battery of the present disclosure has a positive electrode current collector tab electrically connected to the positive electrode current collector layer and a negative electrode current collector tab electrically connected to the negative electrode current collector layer. You may be doing it. In this case, these current collecting tabs may protrude from the resin layer. According to this configuration, the electric power generated in the battery laminate can be taken out to the outside through the current collector tab.

また、正極集電体層は、面方向に突出する正極集電体突出部を有していてよく、この正極集電体突出部には、正極集電タブが電気的に接続されていてよい。同様に、負極集電体層は、負極集電体突出部を有していてよく、この負極集電体突出部には、負極集電タブが電気的に接続されていてよい。 Further, the positive electrode current collector layer may have a positive electrode current collector protruding portion protruding in the plane direction, and a positive electrode current collecting tab may be electrically connected to the positive electrode current collector protruding portion. .. Similarly, the negative electrode current collector layer may have a negative electrode current collector protruding portion, and a negative electrode current collector tab may be electrically connected to the negative electrode current collector protruding portion.

本開示の全固体電池では、電池積層体が、積層方向に拘束されていることができる。これによって、充放電の際に、全固体電池積層体の各層の内部及び各層の間における、イオン及び電子の伝導性を改良して、電池反応をより促進することができる。 In the all-solid-state battery of the present disclosure, the battery laminate can be constrained in the stacking direction. Thereby, during charging / discharging, the conductivity of ions and electrons can be improved inside each layer of the all-solid-state battery laminate and between each layer, and the battery reaction can be further promoted.

以下では、電池積層体にかかる各部材について詳細に説明する。なお、本開示を容易に理解するために、全固体リチウムイオン二次電池の電池積層体にかかる各部材を例として説明するが、本開示の全固体電池は、リチウムイオン二次電池に限定されず、幅広く適用できる。 Hereinafter, each member of the battery laminate will be described in detail. In order to easily understand the present disclosure, each member of the battery laminate of the all-solid-state lithium-ion secondary battery will be described as an example, but the all-solid-state battery of the present disclosure is limited to the lithium-ion secondary battery. It can be widely applied.

（正極集電体層）
正極集電体層に用いられる導電性材料は、特に限定されず、全固体電池に使用できるものを適宜採用されうる。例えば、正極集電体層に用いられる導電性材料は、ＳＵＳ、アルミニウム、銅、ニッケル、鉄、チタン、又はカーボン等であってよいが、これらに限定されない。 (Positive current collector layer)
The conductive material used for the positive electrode current collector layer is not particularly limited, and any material that can be used for an all-solid-state battery can be appropriately adopted. For example, the conductive material used for the positive electrode current collector layer may be, but is not limited to, SUS, aluminum, copper, nickel, iron, titanium, carbon, or the like.

正極集電体層の形状として、特に限定されず、例えば、箔状、板状、メッシュ状等を挙げることができる。これらの中で、箔状が好ましい。 The shape of the positive electrode current collector layer is not particularly limited, and examples thereof include a foil shape, a plate shape, and a mesh shape. Of these, foil-like is preferable.

（正極活物質層）
正極活物質層は、少なくとも正極活物質を含み、好ましくは後述する固体電解質をさらに含む。そのほか、使用用途や使用目的等に合わせて、例えば、導電助剤又はバインダー等の全固体電池の正極活物質層に用いられる添加剤を含むことができる。 (Positive electrode active material layer)
The positive electrode active material layer contains at least a positive electrode active material, and preferably further contains a solid electrolyte described later. In addition, an additive used for the positive electrode active material layer of an all-solid-state battery, such as a conductive auxiliary agent or a binder, can be included according to the intended use and purpose of use.

正極活物質の材料として、特に限定されない。例えば、正極活物質は、コバルト酸リチウム（ＬｉＣｏＯ２）、ニッケル酸リチウム（ＬｉＮｉＯ２）、マンガン酸リチウム（ＬｉＭｎ２Ｏ４）、ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２、Ｌｉ１＋ｘＭｎ２－ｘ－ｙＭｙＯ４（Ｍは、Ａｌ、Ｍｇ、Ｃｏ、Ｆｅ、Ｎｉ、及びＺｎから選ばれる１種以上の金属元素）で表される組成の異種元素置換Ｌｉ－Ｍｎスピネル等であってよいが、これらに限定されない。 The material of the positive electrode active material is not particularly limited. For example, the positive electrode active material is lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMn 2 O 4 ), LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , Li 1 + x. Different element substitution Li-Mn spinel having a composition represented by Mn 2- xy My O 4 (M is one or more metal elements selected from Al, Mg, Co, Fe, Ni, and Zn) and the like. However, it is not limited to these.

導電助剤としては、特に限定されない。例えば、導電助剤は、ＶＧＣＦ（気相成長法炭素繊維、Ｖａｐｏｒ Ｇｒｏｗｎ Ｃａｒｂｏｎ Ｆｉｂｅｒ）及びカーボンナノ繊維等の炭素材並びに金属材等であってよいが、これらに限定されない。 The conductive auxiliary agent is not particularly limited. For example, the conductive auxiliary agent may be, but is not limited to, a carbon material such as VGCF (vapor grown carbon fiber) and carbon nanofibers, and a metal material.

バインダーとしては、特に限定されない。例えば、バインダーは、ポリフッ化ビニリデン（ＰＶｄＦ）、カルボキシメチルセルロース（ＣＭＣ）、ブタジエンゴム（ＢＲ）若しくはスチレンブタジエンゴム（ＳＢＲ）等の材料、又はこれらの組合せであってよいが、これらに限定されない。 The binder is not particularly limited. For example, the binder may be, but is not limited to, a material such as polyvinylidene fluoride (PVdF), carboxymethyl cellulose (CMC), butadiene rubber (BR) or styrene butadiene rubber (SBR), or a combination thereof.

（固体電解質層）
固体電解質層は、少なくとも固体電解質を含む。固体電解質として、特に限定されず、全固体電池の固体電解質として利用可能な材料を用いることができる。例えば、固体電解質は、硫化物固体電解質、酸化物固体電解質、又はポリマー電解質等であってよいが、これらに限定されない。 (Solid electrolyte layer)
The solid electrolyte layer contains at least a solid electrolyte. The solid electrolyte is not particularly limited, and a material that can be used as a solid electrolyte for an all-solid-state battery can be used. For example, the solid electrolyte may be, but is not limited to, a sulfide solid electrolyte, an oxide solid electrolyte, a polymer electrolyte, or the like.

硫化物固体電解質の例として、硫化物系非晶質固体電解質、硫化物系結晶質固体電解質、又はアルジロダイト型固体電解質等が挙げられるが、これらに限定されない。具体的な硫化物固体電解質の例として、Ｌｉ２Ｓ－Ｐ２Ｓ５系（Ｌｉ７Ｐ３Ｓ１１、Ｌｉ３ＰＳ４、Ｌｉ８Ｐ２Ｓ９等）、Ｌｉ２Ｓ－ＳｉＳ２、ＬｉＩ－Ｌｉ２Ｓ－ＳｉＳ２、ＬｉＩ－Ｌｉ２Ｓ－Ｐ２Ｓ５、ＬｉＩ－ＬｉＢｒ－Ｌｉ２Ｓ－Ｐ２Ｓ５、Ｌｉ２Ｓ－Ｐ２Ｓ５－ＧｅＳ２（Ｌｉ１３ＧｅＰ３Ｓ１６、Ｌｉ１０ＧｅＰ２Ｓ１２等）、ＬｉＩ－Ｌｉ２Ｓ－Ｐ２Ｏ５、ＬｉＩ－Ｌｉ３ＰＯ４－Ｐ２Ｓ５、Ｌｉ７－ｘＰＳ６－ｘＣｌｘ等；又はこれらの組み合わせを挙げることができるが、これらに限定されない。 Examples of the sulfide solid electrolyte include, but are not limited to, a sulfide-based amorphous solid electrolyte, a sulfide-based crystalline solid electrolyte, and an argylodite-type solid electrolyte. As specific examples of sulfide solid electrolytes, Li 2 SP 2 S 5 series (Li 7 P 3 S 11 , Li 3 PS 4 , Li 8 P 2 S 9 , etc.), Li 2 S-SiS 2 , Li I -Li 2 S-SiS 2 , LiI-Li 2 SP 2 S 5 , LiI-LiBr-Li 2 SP 2 S 5 , Li 2 SP 2 S 5 -GeS 2 (Li 13 GeP 3 S 16 ) , Li 10 GeP 2 S 12 , etc.), LiI-Li 2 SP 2 O 5 , LiI-Li 3 PO 4 -P 2 S 5 , Li 7-x PS 6-x Cl x , etc .; or a combination thereof. It can be mentioned, but is not limited to these.

酸化物固体電解質の例として、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２、Ｌｉ７－ｘＬａ３Ｚｒ１－ｘＮｂｘＯ１２、Ｌｉ７－３ｘＬａ３Ｚｒ２ＡｌｘＯ１２、Ｌｉ３ｘＬａ２／３－ｘＴｉＯ３、Ｌｉ１＋ｘＡｌｘＴｉ２－ｘ（ＰＯ４）３、Ｌｉ１＋ｘＡｌｘＧｅ２－ｘ（ＰＯ４）３、Ｌｉ３ＰＯ４、又はＬｉ３＋ｘＰＯ４－ｘＮｘ（ＬｉＰＯＮ）等が挙げられるが、これらに限定されない。 Examples of solid oxide electrolytes are Li 7 La 3 Zr 2 O 12, Li 7-x La 3 Zr 1-x Nb x O 12, Li 7-3 x La 3 Zr 2 Al x O 12 , Li 3 x La 2 / 3-x TiO 3 , Li 1 + x Al x Ti 2-x (PO 4 ) 3 , Li 1 + x Al x Ge 2-x (PO 4 ) 3 , Li 3 PO 4 or Li 3 + x PO 4-x N x (LiPON ), Etc., but are not limited to these.

（ポリマー電解質）
ポリマー電解質としては、ポリエチレンオキシド（ＰＥＯ）、ポリプロピレンオキシド（ＰＰＯ）、及びこれらの共重合体等が挙げられるが、これらに限定されない。 (Polymer electrolyte)
Examples of the polymer electrolyte include, but are not limited to, polyethylene oxide (PEO), polypropylene oxide (PPO), and copolymers thereof.

固体電解質は、ガラスであっても、結晶化ガラス(ガラスセラミック)であってもよい。また、固体電解質層は、上述した固体電解質以外に、必要に応じてバインダー等を含んでもよい。具体例として、上述の「正極活物質層」で列挙された「バインダー」と同様であり、ここでは説明を省略する。 The solid electrolyte may be glass or crystallized glass (glass ceramic). Further, the solid electrolyte layer may contain a binder or the like, if necessary, in addition to the above-mentioned solid electrolyte. As a specific example, it is the same as the "binder" listed in the above-mentioned "positive electrode active material layer", and the description thereof is omitted here.

（負極活物質層）
負極活物質層は、少なくとも負極活物質を含み、好ましくは上述した固体電解質をさらに含む。そのほか、使用用途や使用目的等に合わせて、例えば、導電助剤又はバインダー等の全固体電池の負極活物質層に用いられる添加剤を含むことができる。 (Negative electrode active material layer)
The negative electrode active material layer contains at least the negative electrode active material, and preferably further contains the above-mentioned solid electrolyte. In addition, an additive used for the negative electrode active material layer of an all-solid-state battery such as a conductive auxiliary agent or a binder can be included according to the intended use and purpose of use.

負極活物質の材料として、特に限定されず、リチウムイオン等の金属イオンを吸蔵及び放出可能であることが好ましい。例えば、負極活物質は、合金系負極活物質又は炭素材料等であってよいが、これらに限定されない。 The material of the negative electrode active material is not particularly limited, and it is preferable that metal ions such as lithium ions can be occluded and released. For example, the negative electrode active material may be an alloy-based negative electrode active material, a carbon material, or the like, but is not limited thereto.

合金系負極活物質として、特に限定されず、例えば、Ｓｉ合金系負極活物質、又はＳｎ合金系負極活物質等が挙げられる。Ｓｉ合金系負極活物質には、ケイ素、ケイ素酸化物、ケイ素炭化物、ケイ素窒化物、又はこれらの固溶体等がある。また、Ｓｉ合金系負極活物質には、ケイ素以外の元素、例えば、Ｆｅ、Ｃｏ、Ｓｂ、Ｂｉ、Ｐｂ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇｅ、Ｉｎ、Ｓｎ、Ｔｉ等を含むことができる。Ｓｎ合金系負極活物質には、スズ、スズ酸化物、スズ窒化物、又はこれらの固溶体等がある。また、Ｓｎ合金系負極活物質には、スズ以外の元素、例えば、Ｆｅ、Ｃｏ、Ｓｂ、Ｂｉ、Ｐｂ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇｅ、Ｉｎ、Ｔｉ、Ｓｉ等を含むことができる。これらの中で、Ｓｉ合金系負極活物質が好ましい。 The alloy-based negative electrode active material is not particularly limited, and examples thereof include a Si alloy-based negative electrode active material and a Sn alloy-based negative electrode active material. Examples of the Si alloy-based negative electrode active material include silicon, silicon oxide, silicon carbide, silicon nitride, and a solid solution thereof. Further, the Si alloy-based negative electrode active material may contain elements other than silicon, for example, Fe, Co, Sb, Bi, Pb, Ni, Cu, Zn, Ge, In, Sn, Ti and the like. Sn alloy-based negative electrode active materials include tin, tin oxide, tin nitride, and solid solutions thereof. Further, the Sn alloy-based negative electrode active material can contain elements other than tin, for example, Fe, Co, Sb, Bi, Pb, Ni, Cu, Zn, Ge, In, Ti, Si and the like. Among these, a Si alloy-based negative electrode active material is preferable.

炭素材料として、特に限定されず、例えば、ハードカーボン、ソフトカーボン、又はグラファイト等が挙げられる。 The carbon material is not particularly limited, and examples thereof include hard carbon, soft carbon, graphite, and the like.

負極活物質層に用いられる固体電解質、導電助剤、バインダー等その他の添加剤については、上述した「正極活物質層」及び「固体電解質層」の項目で説明したものを適宜採用することができる。 As the solid electrolyte, the conductive auxiliary agent, the binder and other additives used for the negative electrode active material layer, those described in the above-mentioned "Positive electrode active material layer" and "Solid electrolyte layer" can be appropriately adopted. ..

（負極集電体層）
負極集電体層に用いられる導電性材料は、特に限定されず、全固体電池に使用できるものを適宜採用されうる。例えば、負極集電体層に用いられる導電性材料は、ＳＵＳ、アルミニウム、銅、ニッケル、鉄、チタン、又はカーボン等であってよいが、これらに限定されない。 (Negative electrode current collector layer)
The conductive material used for the negative electrode current collector layer is not particularly limited, and any material that can be used for an all-solid-state battery can be appropriately adopted. For example, the conductive material used for the negative electrode current collector layer may be, but is not limited to, SUS, aluminum, copper, nickel, iron, titanium, carbon, or the like.

負極集電体層の形状として、特に限定されず、例えば、箔状、板状、メッシュ状等を挙げることができる。これらの中で、箔状が好ましい。 The shape of the negative electrode current collector layer is not particularly limited, and examples thereof include a foil shape, a plate shape, and a mesh shape. Of these, foil-like is preferable.

本開示において、樹脂層は、全固体電池積層体の側面を被覆している。これによって、本開示の全固体電池の外側に、ラミネートフィルムや金属缶等の外装体を有さなくてもよい。したがって、本開示の全固体電池は、外装体を必要とする従来の全固体電池よりもコンパクトであり、これは、電池のエネルギー密度向上にも繋がる。ただし、本開示の１つの態様では、これらの外装体をさらに有していてもよい。 In the present disclosure, the resin layer covers the side surface of the all-solid-state battery laminate. As a result, it is not necessary to have an exterior body such as a laminated film or a metal can on the outside of the all-solid-state battery of the present disclosure. Therefore, the all-solid-state battery of the present disclosure is more compact than the conventional all-solid-state battery that requires an exterior body, which also leads to an improvement in the energy density of the battery. However, in one aspect of the present disclosure, these exterior bodies may be further provided.

また、本開示の全固体電池は、電池積層体の積層方向の上側の端面及び下側の端面が、フィルム等によって被覆されており、かつ少なくとも全固体電池積層体の側面が樹脂層によって被覆されている全固体電池であってもよい。また、本開示の全固体電池は、全固体電池積層体の積層方向の上側の端面及び／又は下側の端面も樹脂層によって被覆されている全固体電池であってもよい。 Further, in the all-solid-state battery of the present disclosure, the upper end face and the lower end face of the battery laminate in the stacking direction are covered with a film or the like, and at least the side surface of the all-solid-state battery laminate is covered with a resin layer. It may be an all-solid-state battery. Further, the all-solid-state battery of the present disclosure may be an all-solid-state battery in which the upper end face and / or the lower end face in the stacking direction of the all-solid-state battery laminate is also covered with a resin layer.

〈全固体電池の種類〉
本開示において、全固体電池の種類としては、全固体リチウムイオン電池、全固体ナトリウムイオン電池、全固体マグネシウムイオン電池及び全固体カルシウムイオン電池等を挙げることができる。中でも、全固体リチウムイオン電池及び全固体ナトリウムイオン電池が好ましく、特に、全固体リチウムイオン電池が好ましい。 <Types of all-solid-state batteries>
In the present disclosure, examples of the all-solid-state battery include an all-solid-state lithium ion battery, an all-solid-state sodium ion battery, an all-solid-state magnesium ion battery, and an all-solid-state calcium ion battery. Of these, an all-solid-state lithium-ion battery and an all-solid-state sodium-ion battery are preferable, and an all-solid-state lithium-ion battery is particularly preferable.

また、本開示の全固体電池は、一次電池であってもよく、二次電池であってもよいが、中でも、二次電池であることが好ましい。二次電池は、繰り返し充放電でき、例えば、車載用電池として有用だからである。よって、本開示の全固体電池が、全固体リチウムイオン二次電池であることが好ましい。 Further, the all-solid-state battery of the present disclosure may be a primary battery or a secondary battery, but among them, a secondary battery is preferable. This is because the secondary battery can be repeatedly charged and discharged, and is useful as, for example, an in-vehicle battery. Therefore, it is preferable that the all-solid-state battery of the present disclosure is an all-solid-state lithium-ion secondary battery.

以下に示す実施例を参照して本開示を更に詳しく説明するが、本開示の範囲は、実施例によって限定されるものではない。 The present disclosure will be described in more detail with reference to the examples shown below, but the scope of the present disclosure is not limited to the examples.

〈実施例及び比較例〉
図３に示す積層構造を有する電池積層体１０を準備した。なお、電池積層体１０の側面において、延出部３０ｂ及び３０ｃの長さは２ｍｍであり、延出部３０ｂ及び３０ｃの間の距離が１００μｍであった。 <Examples and comparative examples>
A battery laminate 10 having a laminated structure shown in FIG. 3 was prepared. On the side surface of the battery laminate 10, the lengths of the extending portions 30b and 30c were 2 mm, and the distance between the extending portions 30b and 30c was 100 μm.

そして、電池積層体１０を収容しており、かつ使用するエポキシ系の熱硬化性樹脂（硬化温度：１３０℃）の硬化温度を考慮して、１３０℃に加熱されている金型に、表１に示している熱硬化性樹脂の粘度及び注入圧の範囲に合わせて樹脂を注入して、電池積層体１０の側面に樹脂層を形成して、各実施例及び比較例の全固体電池を製造した。その結果は、表１に示す。また、実施例４、比較例３及び比較例７の製造された全固体電池の断面写真は、図４に示す。 Then, in consideration of the curing temperature of the epoxy-based thermosetting resin (curing temperature: 130 ° C.) that houses the battery laminate 10 and is used, the mold heated to 130 ° C. is placed in Table 1 The resin is injected according to the range of the viscosity and the injection pressure of the thermosetting resin shown in the above to form a resin layer on the side surface of the battery laminate 10 to manufacture all-solid-state batteries of Examples and Comparative Examples. did. The results are shown in Table 1. Further, a cross-sectional photograph of the manufactured all-solid-state battery of Example 4, Comparative Example 3 and Comparative Example 7 is shown in FIG.

Figure 0007017484000001
Figure 0007017484000001

表１及び図４の結果から明らかであるように、注入する際の熱硬化性樹脂の粘度が５Ｐａ・ｓ以上１０Ｐａ・ｓ以下であり、かつ注入圧が１ＭＰａ以上３ＭＰａ以下である実施例１～４では、問題なく、かつ短時間で電池積層体の側面に樹脂層を有する全固体電池を製造できた。一方、注入する際の熱硬化性樹脂の粘度が１５Ｐａ・ｓ以上であった比較例１～４、７及び８、並びに注入圧が５ＭＰａであった比較例５及び６のいずれにおいても、電池積層体の延出部の変形が起こったり、又は内部短絡が生じたりする問題があった。 As is clear from the results of Table 1 and FIG. 4, the viscosity of the thermosetting resin at the time of injection is 5 Pa · s or more and 10 Pa · s or less, and the injection pressure is 1 MPa or more and 3 MPa or less. In No. 4, an all-solid-state battery having a resin layer on the side surface of the battery laminate could be manufactured without any problem and in a short time. On the other hand, in all of Comparative Examples 1 to 4, 7 and 8 in which the viscosity of the thermosetting resin at the time of injection was 15 Pa · s or more, and Comparative Examples 5 and 6 in which the injection pressure was 5 MPa, the battery was laminated. There was a problem that the extension part of the body was deformed or an internal short circuit occurred.

１ａ、１ｂ、１ｃ、１ｄ 正極集電体層
２ａ、２ｂ、２ｃ、２ｄ 正極活物質層
３ａ、３ｂ、３ｃ、３ｄ、 固体電解質層
４ａ、４ｂ、４ｃ、４ｄ 負極活物質層
５ａ、５ｂ、５ｃ、５ｄ 負極集電体層
６ａ、６ｂ、６ｃ、６ｄ、６ｅ、６ｆ、６ｇ、６ｈ、６ｊ、６ｋ、６ｌ 単位電池
１０、２０ 電池積層体
１１、２１ 樹脂層
３０ｂ 延出部
３０ｃ 延出部
５０ 金型
１００ 全固体電池 1a, 1b, 1c, 1d Positive electrode current collector layer 2a, 2b, 2c, 2d Positive electrode active material layer 3a, 3b, 3c, 3d, solid electrolyte layer 4a, 4b, 4c, 4d Negative electrode active material layer 5a, 5b, 5c 5d Negative electrode current collector layer 6a, 6b, 6c, 6d, 6e, 6f, 6g, 6h, 6j, 6k, 6l Unit battery 10,20 Battery laminate 11,21 Resin layer 30b Extension part 30c Extension part 50 Mold 100 all-solid-state battery

Claims (1)

下記の工程を含む全固体電池の製造方法：
（ａ）２以上の単位電池を含む電池積層体を準備すること、ここで、前記単位電池は、正極集電体層、正極活物質層、固体電解質層、負極活物質層、及び負極集電体層をこの順に積層することによって構成されており、前記正極集電体層、前記正極活物質層、前記固体電解質層、前記負極活物質層、及び前記負極集電体層のうちの少なくとも１層が、前記電池積層体の側面において、他の層よりも外方に延出している延出部を有し、かつ前記延出部間に隙間が形成されており；並びに
（ｂ）前記電池積層体を収容しており、かつ加熱されている金型に、熱硬化性樹脂を注入することによって、前記電池積層体の側面に樹脂層を形成すること、ここで、前記熱硬化性樹脂の粘度が５Ｐａ・ｓ以上１０Ｐａ・ｓ以下であり、前記熱硬化性樹脂の注入圧が１ＭＰａ以上３ＭＰａ以下である。 Manufacturing method of all-solid-state battery including the following steps:
(A) Preparing a battery laminate containing two or more unit batteries, wherein the unit battery includes a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector. The body layers are laminated in this order, and at least one of the positive electrode current collector layer, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector layer. The layer has an extension portion extending outward from the other layers on the side surface of the battery laminate, and a gap is formed between the extension portions; and (b) the battery. By injecting a thermosetting resin into a mold that houses and is heated, a resin layer is formed on the side surface of the battery laminate, wherein the thermocurable resin is used. The viscosity is 5 Pa · s or more and 10 Pa · s or less, and the injection pressure of the thermosetting resin is 1 MPa or more and 3 MPa or less.
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JP2000106154A (en) 1998-09-28 2000-04-11 Matsushita Electric Ind Co Ltd Whole solid battery and its manufacture
WO2010150491A1 (en) 2009-06-22 2010-12-29 パナソニック株式会社 Surface mounting electronic component and manufacturing method therefor
JP2013089782A (en) 2011-10-18 2013-05-13 Nippon Chemicon Corp Manufacturing method of solid electrolytic capacitor
JP2016207582A (en) 2015-04-27 2016-12-08 トヨタ自動車株式会社 Manufacturing method for all-solid battery
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