JP2018181527A - All-solid battery - Google Patents
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- JP2018181527A JP2018181527A JP2017077003A JP2017077003A JP2018181527A JP 2018181527 A JP2018181527 A JP 2018181527A JP 2017077003 A JP2017077003 A JP 2017077003A JP 2017077003 A JP2017077003 A JP 2017077003A JP 2018181527 A JP2018181527 A JP 2018181527A
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- 229910052744 lithium Inorganic materials 0.000 description 6
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Classifications
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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
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- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Connection Of Batteries Or Terminals (AREA)
Abstract
Description
本願は発電要素を複数積層した全固体電池を開示する。 The present application discloses an all-solid-state battery in which a plurality of power generation elements are stacked.
特許文献１には、積層電極群の外側に、絶縁体を介して２枚の金属板を配置してなる短絡形成兼放熱促進ユニットを備えた、積層型ポリマー電解質電池が開示されている。特許文献１に開示された電池によれば、電池の釘刺し試験時等において電極同士が短絡した場合に、短絡形成兼放熱促進ユニットに短絡電流を流すことで発電要素の電圧を低減することができ、且つ、当該ユニット等にて発生した熱を外部へとスムーズに放熱することができるものと考えられる。特許文献２、３にも、釘刺し等の電池の内部短絡による熱の発生を抑制するための種々の技術が開示されている。 Patent Document 1 discloses a laminate type polymer electrolyte battery provided with a short circuit formation and heat radiation promotion unit in which two metal plates are disposed outside the laminate electrode group via an insulator. According to the battery disclosed in Patent Document 1, when the electrodes are short-circuited at the time of a nail penetration test of the battery or the like, the voltage of the power generation element can be reduced by flowing the short circuit current to the short circuit formation and heat radiation promotion unit. It is considered that the heat generated by the unit or the like can be dissipated to the outside smoothly. Patent Literatures 2 and 3 also disclose various techniques for suppressing the generation of heat due to an internal short circuit of a battery such as a nail stick.
発電要素を複数積層しつつ電気的に並列に接続した全固体電池においては、釘刺し試験によって発電要素を短絡させると、一部の発電要素から他の発電要素へと電子が流れ込み（以下、これを「回り込み電流」という場合がある。）、一部の発電要素の温度が局所的に上昇してしまうという課題が生じる。このような課題に対し、発電要素とは別に短絡電流分散体を設け、釘刺し試験において一部の発電要素とともに短絡電流分散体も短絡させ、他の発電要素からの回り込み電流を、一部の発電要素だけでなく、短絡抵抗が小さい短絡電流分散体へと分散させることで、一部の発電要素の温度のみが局所的に上昇することを防止できるものと考えられる（図７）。 In an all-solid-state battery in which a plurality of power generation elements are connected in parallel and electrically connected in parallel, when the power generation elements are short-circuited by a nail penetration test, electrons flow from some of the power generation elements into the other power generation elements Is sometimes referred to as “loop current”), there is a problem that the temperature of some of the power generation elements rises locally. To solve this problem, a short circuit current dispersion is provided separately from the power generation element, and in the nail penetration test, the short circuit current dispersion is also shorted together with some of the power generation elements. It is thought that local temperature increase of only some of the power generation elements can be prevented by dispersing the power generation elements not only to the power generation elements but also to the short circuit current dispersion having a small short circuit resistance (FIG. 7).
短絡電流分散体は、釘刺しによって適切に短絡させる観点から、発電要素に近接して設けられる。さらに、電池のエネルギー密度を向上させる観点等から、発電要素に隣接して設けられる。例えば、特許文献１に開示されているように、積層電極群（複数の発電要素）の外側に短絡電流分散体を近接させるようにして積層する。しかしながら、短絡電流分散体を発電要素に近接させた場合、釘刺し等による短絡時、短絡電流分散体の温度が過度に上昇することで、近接する発電要素の温度も過度に上昇させてしまう虞がある。 The short circuit current dispersion is provided in close proximity to the power generation element from the viewpoint of appropriately shorting by nailing. Furthermore, from a viewpoint of improving the energy density of a battery etc., it is provided adjacent to a power generation element. For example, as disclosed in Patent Document 1, the short-circuit current dispersion is laminated in the vicinity of the outside of the laminated electrode group (a plurality of power generation elements). However, when the short-circuit current dispersion is brought close to the power generation element, the temperature of the short-circuit current dispersion may be excessively increased when the short-circuit current dispersion is excessively short at the time of short circuit by nailing or the like. There is.
本発明者らは、上記の課題を解決するために鋭意研究を進めたところ、以下の複数の知見を得た。
（１）発電要素を複数積層しつつ電気的に並列に接続した全固体電池において、電池への釘刺し時、釘貫通後よりも、釘を刺し込んでいる最中に、発電要素に印加される荷重が大きくなり、発電要素の短絡抵抗（正極集電体層と負極集電体層との直接接触による抵抗）が小さくなって、大きな回り込み電流が発生する。
（２）発電要素を複数積層しつつ電気的に並列に接続した全固体電池において、釘貫通後は、発電要素に印加される荷重が小さくなり、発電要素の短絡抵抗が大きくなって、回り込み電流が小さくなる。
（３）すなわち、電池への釘刺し時、釘を刺し込んでいる最中において、回り込み電流を短絡電流分散体へと分散させる一方、釘貫通後は、短絡電流分散体の温度上昇を抑制できるような機能を設けるとよい。
（４）短絡電流分散体において、釘を刺し込んでいる最中の高圧時（例えば、１００ＭＰａ）における第１の集電体層と第２の集電体層との接触抵抗を小さなものとし、且つ、釘貫通後の低圧時（例えば、５ＭＰａ）における第１の集電体層と第２の集電体層との接触抵抗を大きなものとすることで、電池への釘刺し時、釘を刺し込んでいる最中において、回り込み電流を短絡電流分散体へと多く分散させる一方、釘貫通後は、短絡電流分散体の抵抗が大きくなることで、短絡電流分散体に流れ込む回り込み電流量を少なくでき、短絡電流分散体の温度上昇を抑制できる。
The inventors of the present invention conducted earnest studies to solve the above problems, and obtained the following findings.
(1) In an all-solid battery in which a plurality of power generation elements are electrically connected in parallel while being stacked, a plurality of power generation elements are applied to the power generation elements during nailing of the battery than during nailing. Load increases, and the short circuit resistance of the power generation element (resistance due to direct contact between the positive electrode current collector layer and the negative electrode current collector layer) decreases, and a large wraparound current is generated.
(2) In an all solid battery in which a plurality of power generation elements are electrically connected in parallel while being stacked, after passing through the nail, the load applied to the power generation elements becomes small and the short circuit resistance of the power generation elements becomes large. Becomes smaller.
(3) In other words, when the battery is nailed into the battery or while the nail is being pierced, the sneak current is dispersed to the short circuit current dispersion, while after the nail is penetrated, the temperature rise of the short circuit current dispersion can be suppressed. It is good to provide such a function.
(4) In the short-circuit current dispersion, the contact resistance between the first current collector layer and the second current collector layer at a high pressure (for example, 100 MPa) in the process of piercing a nail is made small, In addition, by setting the contact resistance between the first current collector layer and the second current collector layer at a low pressure (for example, 5 MPa) after penetrating the nail, the nail is inserted when the battery is nailed. During penetration, a large amount of sneak current is dispersed into the short circuit current dispersion, while after penetration of the nail, the resistance of the short circuit current dispersion is increased, thereby reducing the amount of sneak current flowing into the short circuit current dispersion. Thus, the temperature rise of the short circuit current dispersion can be suppressed.
以上の知見に基づき、本願は上記課題を解決するための手段の一つとして、
少なくとも１つの短絡電流分散体と複数の発電要素とが積層された全固体電池であって、前記短絡電流分散体において、第１の集電体層と第２の集電体層と前記第１の集電体層及び前記第２の集電体層の間に設けられた絶縁層とが積層されており、前記発電要素において、正極集電体層と正極材層と固体電解質層と負極材層と負極集電体層とが積層されており、前記第１の集電体層が前記正極集電体層と電気的に接続されており、前記第２の集電体層が前記負極集電体層と電気的に接続されており、複数の前記発電要素同士が電気的に並列に接続されており、前記発電要素に近接する前記短絡電流分散体に備えられる前記第１の集電体層及び前記第２の集電体層の５ＭＰａにおける接触抵抗Ｒ１と１００ＭＰａにおける接触抵抗Ｒ２との比（Ｒ１／Ｒ２）が１．６以上である、全固体電池
を開示する。
Based on the above findings, the present application is one of means for solving the above-mentioned problems.
An all solid battery in which at least one short circuit current dispersion and a plurality of power generation elements are stacked, wherein the first current collector layer, the second current collector layer, and the first current collector in the short circuit current dispersion. And an insulating layer provided between the second current collector layer, the positive electrode current collector layer, the positive electrode material layer, the solid electrolyte layer, and the negative electrode material in the power generation element. Layer and a negative electrode current collector layer are laminated, the first current collector layer is electrically connected to the positive electrode current collector layer, and the second current collector layer is the negative electrode current collector layer. The first current collector electrically connected to the current collector layer, the plurality of power generation elements being electrically connected in parallel, and provided in the short circuit current dispersion in proximity to the power generation element the ratio of the contact resistance R 2 in the contact resistance R 1 and 100MPa at 5MPa layer and the second collector layer R 1 / R 2) is not less than 1.6, discloses an all-solid battery.
「近接」は「隣接」の意味も含むものとする。
「前記第１の集電体層及び前記第２の集電体層の５ＭＰａにおける接触抵抗」とは、集電体層同士を５ＭＰａの圧力で互いに押し付けた場合の集電体層間の抵抗をいう。
「前記第１の集電体層及び前記第２の集電体層の…１００ＭＰａにおける接触抵抗」とは、集電体層同士を１００ＭＰａの圧力で互いに押し付けた場合の集電体層間の抵抗をいう。
"Proximity" also includes the meaning of "adjacent".
The “contact resistance of the first current collector layer and the second current collector layer at 5 MPa” means the resistance between the current collector layers when the current collector layers are mutually pressed at a pressure of 5 MPa. .
“The contact resistance of the first current collector layer and the second current collector layer at 100 MPa” refers to the resistance between the current collector layers when the current collector layers are mutually pressed at a pressure of 100 MPa. Say.
本開示の全固体電池においては、短絡電流分散体を構成する第１の集電体層及び第２の集電体層の組み合わせとして、５ＭＰａといった低圧化における接触抵抗が、１００ＭＰａといった高圧下において接触抵抗よりも大きな値となる集電体層の組み合わせを採用している。これにより、釘刺し時の短絡電流分散体及び発電要素の短絡時、釘を刺している最中の高圧時において短絡電流分散体の短絡抵抗を小さなものとすることができ、釘貫通後の低圧時において短絡電流分散体の短絡抵抗を大きなものとすることができる。よって釘刺し時、釘を刺し込んでいる最中において、回り込み電流を短絡電流分散体へと多く分散させる一方、釘貫通後は、短絡電流分散体の抵抗が大きくなることで、短絡電流分散体に流れ込む回り込み電流量を少なくでき、短絡電流分散体の温度上昇を抑制できる。すなわち、短絡電流分散体が過度に温度上昇することを抑制でき、近接する発電要素の温度上昇も抑制できる。 In the all-solid-state battery of the present disclosure, as a combination of the first current collector layer and the second current collector layer constituting the short circuit current dispersion, the contact resistance at low pressure such as 5 MPa contacts under high pressure such as 100 MPa. The combination of the current collector layer which has a value larger than the resistance is adopted. This makes it possible to reduce the short-circuit resistance of the short-circuit current dispersion at the time of high-pressure during the nailing, at the time of short-circuiting of the short-circuit current dispersion and the power generating element at the time of nailing. In some cases, the short circuit resistance of the short circuit current dispersion can be made large. Therefore, at the time of piercing the nail, during the piercing of the nail, a large amount of sneak current is dispersed to the short circuit current dispersion, while after penetration of the nail, the resistance of the short circuit current dispersion becomes large. The amount of sneak current flowing into the short circuit current dispersion can be reduced, and the temperature rise of the short circuit current dispersion can be suppressed. That is, excessive temperature rise of the short circuit current dispersion can be suppressed, and temperature rise of the adjacent power generation element can also be suppressed.
１．全固体電池１００
図１に、全固体電池１００の層構成を概略的に示す。図１においては、説明の便宜上、集電体層同士（集電タブ同士）の接続部分や、電池ケース等を省略して示している。図２に、全固体電池１００を構成する短絡電流分散体１０の層構成を概略的に示す。図２（Ａ）が外観斜視図、図２（Ｂ）がＩＩＢ−ＩＩＢ断面図である。図３に、全固体電池１００を構成する発電要素２０の層構成を概略的に示す。図３（Ａ）が外観斜視図、図３（Ｂ）がＩＩＩＢ−ＩＩＩＢ断面図、である。
1. All solid battery 100
The layer configuration of the all-solid battery 100 is schematically shown in FIG. In FIG. 1, for convenience of description, connection portions between current collector layers (current collection tabs), a battery case, and the like are omitted. FIG. 2 schematically shows the layer configuration of the short circuit current dispersion 10 constituting the all solid state battery 100. 2A is an external perspective view, and FIG. 2B is a cross-sectional view taken along the line IIB-IIB. FIG. 3 schematically shows the layer configuration of the power generation element 20 constituting the all solid state battery 100. As shown in FIG. FIG. 3A is an external perspective view, and FIG. 3B is a cross-sectional view taken along the line IIIB-IIIB.
図１〜３に示すように、全固体電池１００は、少なくとも１つの短絡電流分散体１０と複数の発電要素２０、２０、…とが積層されてなる。短絡電流分散体１０において、第１の集電体層１１と第２の集電体層１２と第１の集電体層１１及び第２の集電体層１２の間に設けられた絶縁層１３とが積層されている。発電要素２０において、正極集電体層２１と正極材層２２と固体電解質層２３と負極材層２４と負極集電体層２５とが積層されている。全固体電池１００においては、第１の集電体層１１が正極集電体層２１と電気的に接続されており、第２の集電体層１２が負極集電体層２５と電気的に接続されており、複数の発電要素２０、２０、…同士が電気的に並列に接続されている。ここで、全固体電池１００においては、発電要素２０に近接する短絡電流分散体１０に備えられる第１の集電体層１１及び第２の集電体層１２の５ＭＰａにおける接触抵抗Ｒ１と１００ＭＰａにおける接触抵抗Ｒ２との比（Ｒ１／Ｒ２）が１．６以上である点に特徴を有する。 As shown in FIGS. 1 to 3, the all solid state battery 100 is formed by laminating at least one short circuit current dispersion 10 and a plurality of power generation elements 20, 20,. In the short-circuit current dispersion 10, an insulating layer provided between the first current collector layer 11, the second current collector layer 12, the first current collector layer 11, and the second current collector layer 12 13 and are stacked. In the power generation element 20, the positive electrode current collector layer 21, the positive electrode material layer 22, the solid electrolyte layer 23, the negative electrode material layer 24, and the negative electrode current collector layer 25 are stacked. In the all solid state battery 100, the first current collector layer 11 is electrically connected to the positive electrode current collector layer 21, and the second current collector layer 12 is electrically connected to the negative electrode current collector layer 25. The plurality of power generation elements 20, 20,... Are electrically connected in parallel. Here, in the all solid battery 100, the contact resistances R 1 and 100 MPa at 5 MPa of the first current collector layer 11 and the second current collector layer 12 provided in the short circuit current dispersion 10 close to the power generation element 20. Is characterized in that the ratio (R 1 / R 2 ) to the contact resistance R 2 in the above is 1.6 or more.
１．１．短絡電流分散体１０
短絡電流分散体１０は、第１の集電体層１１と、第２の集電体層１２と、第１の集電体層１１及び第２の集電体層１２の間に設けられる絶縁層１３と、を備える。このような構成を備えた短絡電流分散体１０は、電池の通常使用時において第１の集電体層１１と第２の集電体層１２とが絶縁層１３によって適切に絶縁される一方で、釘刺しによる短絡時には第１の集電体層１１と第２の集電体層１２とが接触して電気抵抗が小さくなる。
1.1. Short circuit current dispersion 10
The short circuit current dispersion 10 is an insulation provided between the first current collector layer 11, the second current collector layer 12, and the first current collector layer 11 and the second current collector layer 12. And a layer 13. In the short-circuit current dispersion 10 having such a configuration, while the first current collector layer 11 and the second current collector layer 12 are appropriately insulated by the insulating layer 13 during normal use of the battery, At the time of a short circuit due to a nail sticking, the first current collector layer 11 and the second current collector layer 12 come into contact with each other to reduce the electrical resistance.
１．１．１．第１の集電体層１１及び第２の集電体層１２
第１の集電体層１１及び第２の集電体層１２は、金属箔や金属メッシュ等により構成すればよい。特に金属箔が好ましい。集電体層１１、１２を構成する金属としては、Ｃｕ、Ｎｉ、Ａｌ、Ｆｅ、Ｔｉ、Ｚｎ、Ｃｏ、Ｃｒ、Ａｕ、Ｐｔ、ステンレス鋼等が挙げられる。集電体層１１や集電体層１２は、その表面に、接触抵抗を調整するための何らかのコート層を有していてもよい。例えば、導電材と樹脂とを含むコート層である。
1.1.1. First current collector layer 11 and second current collector layer 12
The first current collector layer 11 and the second current collector layer 12 may be made of metal foil, metal mesh or the like. In particular, metal foils are preferred. As a metal which comprises the collector layers 11 and 12, Cu, Ni, Al, Fe, Ti, Zn, Co, Cr, Au, Pt, stainless steel etc. are mentioned. The current collector layer 11 and the current collector layer 12 may have any coating layer for adjusting the contact resistance on their surfaces. For example, it is a coat layer containing a conductive material and a resin.
第１の集電体層１１及び第２の集電体層１２は、上記したような各種材料から、低圧時（５ＭＰａ）における接触抵抗Ｒ１と高圧時（１００ＭＰａ）における接触抵抗Ｒ２との比（Ｒ１／Ｒ２）が１．６以上となる組み合わせを採用すればよい。好ましくは、比（Ｒ１／Ｒ２）が５．１以上となる組み合わせを採用する。例えば、第１の集電体層としてステンレス鋼箔を、第２の集電体層として銅箔を用いた場合、上記の比（Ｒ１／Ｒ２）が５．１以上となり得る。後述の実施例において、種々の金属箔の組み合わせについて、低圧時の接触抵抗と高圧時の接触抵抗とについて具体的な数値を示す。 The first current collector layer 11 and the second current collector layer 12 are made of the above-mentioned various materials, and the contact resistance R 1 at low pressure (5 MPa) and the contact resistance R 2 at high pressure (100 MPa) A combination in which the ratio (R 1 / R 2 ) is 1.6 or more may be employed. Preferably, a combination in which the ratio (R 1 / R 2 ) is 5.1 or more is employed. For example, when stainless steel foil is used as the first current collector layer and copper foil is used as the second current collector layer, the above ratio (R 1 / R 2 ) can be 5.1 or more. In the following examples, specific combinations of various metal foils will be shown for the contact resistance at low pressure and the contact resistance at high pressure.
第１の集電体層１１及び第２の集電体層１２の厚みは特に限定されるものではない。例えば０．１μｍ以上１ｍｍ以下であることが好ましく、１μｍ以上１００μｍ以下であることがより好ましい。集電体層１１、１２の厚みをこのような範囲とした場合、釘刺し時、集電体層１１、１２を互いにより適切に接触させることができ、短絡電流分散体１０をより適切に短絡させることができる。 The thicknesses of the first current collector layer 11 and the second current collector layer 12 are not particularly limited. For example, the thickness is preferably 0.1 μm or more and 1 mm or less, and more preferably 1 μm or more and 100 μm or less. When the thickness of the current collector layers 11 and 12 is in such a range, the current collector layers 11 and 12 can be more appropriately brought into contact with each other at the time of nailing, and the short circuit current dispersion 10 is more appropriately shorted. It can be done.
図２に示すように、第１の集電体層１１は集電タブ１１ａを備えており、当該集電タブ１１ａを介して発電要素２０の正極集電体層２１に電気的に接続されていることが好ましい。一方、第２の集電体層１２は集電タブ１２ａを備えており、当該集電タブ１２ａを介して発電要素２０の負極集電体層２５に電気的に接続されていることが好ましい。集電タブ１１ａは第１の集電体層１１と同じ材質であってもよいし、異なる材質であってもよい。集電タブ１２ａは第２の集電体層１２と同じ材質であってもよいし、異なる材質であってもよい。尚、釘刺し等の短絡時、短絡電流分散体１０へとより多くの回り込み電流を流す観点から、集電タブ１１ａ及び集電タブ１２ａにおける電気抵抗は、後述の正極集電タブ２１ａ及び負極集電タブ２５ａにおける電気抵抗よりも小さいことが好ましい。 As shown in FIG. 2, the first current collector layer 11 includes a current collection tab 11a, and is electrically connected to the positive electrode current collector layer 21 of the power generation element 20 via the current collection tab 11a. Is preferred. On the other hand, it is preferable that the 2nd current collection layer 12 is provided with current collection tab 12a, and is electrically connected to the current collection layer 25 of electric power generation element 20 via the current collection tab 12a concerned. The current collection tab 11a may be the same material as the first current collector layer 11, or may be a different material. The current collection tab 12a may be the same material as the second current collector layer 12 or may be a different material. The electrical resistance of the current collecting tab 11a and the current collecting tab 12a is set to the positive electrode current collecting tab 21a and the negative electrode current collector, which will be described later, from the viewpoint of passing more sneak current to the short circuit current dispersion 10 at the time of short circuiting. Preferably, it is smaller than the electrical resistance of the electrical tab 25a.
１．１．２．絶縁層１３
全固体電池１００において、絶縁層１３は、電池の通常使用時において、第１の集電体層１１と第２の集電体層１２とを絶縁するものであればよい。絶縁層１３は、有機材料からなる絶縁層であっても、無機材料からなる絶縁層であっても、有機材料と無機材料とが混在する絶縁層であってもよい。特に、有機材料からなる絶縁層が好ましい。通常使用時に割れによる短絡発生確率が低いという観点から有利だからである。
1.1.2. Insulating layer 13
In the all-solid-state battery 100, the insulating layer 13 only needs to insulate the first current collector layer 11 and the second current collector layer 12 during normal use of the battery. The insulating layer 13 may be an insulating layer made of an organic material, an insulating layer made of an inorganic material, or an insulating layer in which an organic material and an inorganic material are mixed. In particular, an insulating layer made of an organic material is preferable. This is because it is advantageous from the viewpoint that the probability of occurrence of a short circuit due to cracking is low during normal use.
絶縁層１３を構成し得る有機材料としては各種樹脂が挙げられる。例えば、各種熱可塑性樹脂や各種熱硬化性樹脂である。特にポリイミド、ポリアミドイミド、ポリエーテルエーテルケトン、ポリフェニレンサルファイド等のスーパーエンジニアリングプラスチックが好ましい。通常、熱硬化性樹脂は、熱可塑性樹脂よりも熱安定性が高く、且つ、硬質で脆い。すなわち、熱硬化性樹脂により絶縁層１３を構成した場合において、短絡電流分散体１０の釘刺しを行った場合、絶縁層１３が容易に破断し、第１の集電体層１１や第２の集電体層１２の変形に対して絶縁層１３が追従することを抑制でき、第１の集電体層１１と第２の集電体層１２とをより容易に接触させることができる。また、絶縁層１３の温度が上昇したとしても熱分解を抑制できる。 As an organic material which can constitute insulating layer 13, various resin is mentioned. For example, various thermoplastic resins and various thermosetting resins. In particular, super engineering plastics such as polyimide, polyamideimide, polyetheretherketone and polyphenylene sulfide are preferable. In general, thermosetting resins have higher thermal stability than thermoplastic resins, and are hard and brittle. That is, in the case where the insulating layer 13 is formed of a thermosetting resin, when the short circuiting current dispersion 10 is nailed, the insulating layer 13 is easily broken, and the first current collector layer 11 or the second current collector layer 11 is formed. It can be suppressed that the insulating layer 13 follows the deformation of the current collector layer 12, and the first current collector layer 11 and the second current collector layer 12 can be more easily brought into contact with each other. Moreover, even if the temperature of the insulating layer 13 rises, thermal decomposition can be suppressed.
絶縁層１３を構成し得る無機材料としては各種セラミックが挙げられる。例えば、無機酸化物である。尚、表面に酸化物被膜を有する金属箔によって絶縁層１３を構成してもよい。例えば、アルマイト処理によって、アルミニウム箔の表面に陽極酸化皮膜を形成することで、表面に酸化アルミニウム被膜を有するアルミニウム箔が得られる。この場合、酸化皮膜の厚みは０．０１μｍ以上５μｍ以下であることが好ましい。下限がより好ましくは０．１μｍ以上であり、上限がより好ましくは１μｍ以下である。 As an inorganic material which can constitute insulating layer 13, various ceramics are mentioned. For example, it is an inorganic oxide. The insulating layer 13 may be formed of a metal foil having an oxide film on the surface. For example, by forming an anodic oxide film on the surface of aluminum foil by alumite treatment, an aluminum foil having an aluminum oxide film on the surface can be obtained. In this case, the thickness of the oxide film is preferably 0.01 μm to 5 μm. The lower limit is more preferably 0.1 μm or more, and the upper limit is more preferably 1 μm or less.
絶縁層１３の厚みは特に限定されるものではない。例えば０．１μｍ以上１ｍｍ以下であることが好ましく、１μｍ以上１００μｍ以下であることがより好ましい。絶縁層１３の厚みをこのような範囲とした場合、電池の通常使用時、第１の集電体層１１と第２の集電体層１２とをより適切に絶縁することができるとともに、釘刺し等の外部応力による変形によって第１の集電体層１１と第２の集電体層１２とをより適切に導通させて、内部短絡させることができる。 The thickness of the insulating layer 13 is not particularly limited. For example, the thickness is preferably 0.1 μm or more and 1 mm or less, and more preferably 1 μm or more and 100 μm or less. When the thickness of the insulating layer 13 is in such a range, the first current collector layer 11 and the second current collector layer 12 can be more appropriately insulated during normal use of the battery, and the nail The first current collector layer 11 and the second current collector layer 12 can be more properly conducted to cause an internal short circuit by deformation due to external stress such as piercing.
１．２．発電要素２０
発電要素２０は、正極集電体層２１と正極材層２２と固体電解質層２３と負極材層２４と負極集電体層２５とが積層されてなる。すなわち、発電要素２０は単電池として機能し得る。
1.2. Power generation element 20
The power generation element 20 is formed by laminating the positive electrode current collector layer 21, the positive electrode material layer 22, the solid electrolyte layer 23, the negative electrode material layer 24, and the negative electrode current collector layer 25. That is, the power generation element 20 can function as a single battery.
１．２．１．正極集電体層２１
正極集電体層２１は、金属箔や金属メッシュ等により構成すればよい。特に金属箔が好ましい。正極集電体層２１を構成する金属としては、Ｎｉ、Ｃｒ、Ａｕ、Ｐｔ、Ａｌ、Ｆｅ、Ｔｉ、Ｚｎ、ステンレス鋼等が挙げられる。正極集電体層２１は、その表面に、接触抵抗を調整するための何らかのコート層を有していてもよい。例えば、導電材と樹脂とを含むコート層等である。正極集電体層２１の厚みは特に限定されるものではない。例えば０．１μｍ以上１ｍｍ以下であることが好ましく、１μｍ以上１００μｍ以下であることがより好ましい。
1.2.1. Positive electrode current collector layer 21
The positive electrode current collector layer 21 may be made of metal foil, metal mesh or the like. In particular, metal foils are preferred. As a metal which comprises the positive electrode collector layer 21, Ni, Cr, Au, Pt, Al, Fe, Ti, Zn, stainless steel etc. are mentioned. The positive electrode current collector layer 21 may have on the surface thereof any coating layer for adjusting the contact resistance. For example, a coat layer or the like containing a conductive material and a resin. The thickness of the positive electrode current collector layer 21 is not particularly limited. For example, the thickness is preferably 0.1 μm or more and 1 mm or less, and more preferably 1 μm or more and 100 μm or less.
図３に示すように、正極集電体層２１は外縁の一部に正極集電タブ２１ａを備えることが好ましい。タブ２１ａにより、第１の集電体層１１と正極集電体層２１とを容易に電気的に接続することができるとともに、正極集電体層２１同士を容易に電気的に並列に接続することができる。 As shown in FIG. 3, the positive electrode current collector layer 21 is preferably provided with a positive electrode current collection tab 21 a at a part of the outer edge. The first current collector layer 11 and the positive electrode current collector layer 21 can be easily electrically connected by the tab 21a, and the positive electrode current collector layers 21 are easily electrically connected in parallel. be able to.
１．２．２．正極材層２２
正極材層２２は、少なくとも活物質を含む層であり、活物質に加えて、さらに任意に固体電解質、バインダー及び導電助剤等を含ませることができる。活物質は公知の活物質を用いればよい。公知の活物質のうち、所定のイオンを吸蔵放出する電位（充放電電位）の異なる２つの物質を選択し、貴な電位を示す物質を正極活物質とし、卑な電位を示す物質を後述の負極活物質として、それぞれ用いることができる。例えば、リチウムイオン電池を構成する場合は、正極活物質としてコバルト酸リチウム、ニッケル酸リチウム、ＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２、マンガン酸リチウム、スピネル系リチウム化合物等の各種のリチウム含有複合酸化物を用いることができる。正極活物質は表面がニオブ酸リチウム層やチタン酸リチウム層やリン酸リチウム層等の酸化物層で被覆されていてもよい。また、固体電解質は無機固体電解質が好ましい。有機ポリマー電解質と比較してイオン伝導度が高いためである。また、有機ポリマー電解質と比較して、耐熱性に優れるためである。さらに、有機ポリマー電解質と比較して、釘刺し時に発電要素２０に加わる圧力が高圧となり、本開示の全固体電池１００による効果が一層顕著となるためである。例えば、ランタンジルコン酸リチウム等の酸化物固体電解質やＬｉ２Ｓ−Ｐ２Ｓ５等の硫化物固体電解質が挙げられる。特に、Ｌｉ２Ｓ−Ｐ２Ｓ５を含む硫化物固体電解質が好ましく、Ｌｉ２Ｓ−Ｐ２Ｓ５を５０モル％以上含む硫化物固体電解質がより好ましい。バインダーはブタジエンゴム（ＢＲ）、アクリレートブタジエンゴム（ＡＢＲ）、ポリフッ化ビニリデン（ＰＶｄＦ）等の種々のバインダーを用いることができる。導電助剤としてはアセチレンブラックやケッチェンブラック等の炭素材料やニッケル、アルミニウム、ステンレス鋼等の金属材料を用いることができる。正極材層２２における各成分の含有量は従来と同様とすればよい。正極材層２２の形状も従来と同様とすればよい。特に、全固体電池１００を容易に構成できる観点から、シート状の正極材層２２が好ましい。この場合、正極材層２２の厚みは、例えば０．１μｍ以上１ｍｍ以下であることが好ましく、１μｍ以上１５０μｍ以下であることがより好ましい。
1.2.2. Positive electrode layer 22
The positive electrode material layer 22 is a layer containing at least an active material, and in addition to the active material, a solid electrolyte, a binder, a conductive auxiliary agent, and the like can be optionally added. A known active material may be used as the active material. Among the known active materials, two substances having different potentials (charge / discharge potentials) for occluding and releasing predetermined ions are selected, a substance showing a noble potential is used as a positive electrode active material, and a substance showing a false potential is described later. Each can be used as a negative electrode active material. For example, when configuring a lithium ion battery, various types of cathode active materials such as lithium cobaltate, lithium nickelate, LiNi 1/3 Co 1/3 Mn 1/3 O 2 , lithium manganate, spinel lithium compounds, etc. Lithium-containing composite oxides can be used. The surface of the positive electrode active material may be coated with an oxide layer such as a lithium niobate layer, a lithium titanate layer, or a lithium phosphate layer. In addition, the solid electrolyte is preferably an inorganic solid electrolyte. This is because the ion conductivity is higher than that of the organic polymer electrolyte. Moreover, it is because it is excellent in heat resistance compared with the organic polymer electrolyte. Furthermore, as compared with the organic polymer electrolyte, the pressure applied to the power generation element 20 at the time of nailing is high, and the effect of the all-solid battery 100 of the present disclosure is more remarkable. For example, oxide solid electrolytes such as lithium lanthanum zirconate and sulfide solid electrolytes such as Li 2 S-P 2 S 5 can be mentioned. In particular, a sulfide solid electrolyte containing Li 2 S-P 2 S 5 is preferable, and a sulfide solid electrolyte containing 50 mol% or more of Li 2 S-P 2 S 5 is more preferable. As the binder, various binders such as butadiene rubber (BR), acrylate butadiene rubber (ABR) and polyvinylidene fluoride (PVdF) can be used. As the conductive additive, carbon materials such as acetylene black and ketjen black, and metal materials such as nickel, aluminum and stainless steel can be used. The content of each component in the positive electrode material layer 22 may be the same as that in the prior art. The shape of the positive electrode material layer 22 may be the same as that in the prior art. In particular, the sheet-like positive electrode material layer 22 is preferable from the viewpoint that the all-solid battery 100 can be easily configured. In this case, the thickness of the positive electrode material layer 22 is, for example, preferably 0.1 μm or more and 1 mm or less, and more preferably 1 μm or more and 150 μm or less.
１．２．３．固体電解質層２３
固体電解質層２３は、少なくとも固体電解質を含む層であり、任意にバインダーを含ませることができる。固体電解質は上述した無機固体電解質が好ましい。バインダーは正極材層２２に用いられるバインダーと同様のものを適宜選択して用いることができる。固体電解質層２３における各成分の含有量は従来と同様とすればよい。固体電解質層２３の形状も従来と同様とすればよい。特に、全固体電池１００を容易に構成できる観点から、シート状の固体電解質層２３が好ましい。この場合、固体電解質層２３の厚みは、例えば０．１μｍ以上１ｍｍ以下であることが好ましく、１μｍ以上１００μｍ以下であることがより好ましい。
1.2.3. Solid electrolyte layer 23
The solid electrolyte layer 23 is a layer containing at least a solid electrolyte, and may optionally contain a binder. The solid electrolyte is preferably the above-mentioned inorganic solid electrolyte. As the binder, one similar to the binder used for the positive electrode material layer 22 can be appropriately selected and used. The content of each component in the solid electrolyte layer 23 may be the same as that in the prior art. The shape of the solid electrolyte layer 23 may be the same as in the prior art. In particular, the sheet-like solid electrolyte layer 23 is preferable from the viewpoint that the all-solid battery 100 can be easily configured. In this case, the thickness of the solid electrolyte layer 23 is, for example, preferably 0.1 μm or more and 1 mm or less, and more preferably 1 μm or more and 100 μm or less.
１．２．４．負極材層２４
負極材層２４は、少なくとも活物質を含む層であり、活物質に加えて、さらに任意に固体電解質、バインダー及び導電助剤等を含ませることができる。活物質は公知の活物質を用いればよい。公知の活物質のうち、所定のイオンを吸蔵放出する電位（充放電電位）の異なる２つの物質を選択し、貴な電位を示す物質を上述の正極活物質とし、卑な電位を示す物質を負極活物質として、それぞれ用いることができる。例えば、リチウムイオン電池を構成する場合は、負極活物質としてグラファイトやハードカーボン等の炭素材料や、チタン酸リチウム等の各種酸化物、ＳｉやＳｉ合金、或いは、金属リチウムやリチウム合金を用いることができる。固体電解質、バインダー及び導電助剤は正極材層２２に用いられる固体電解質と同様のものを適宜選択して用いることができる。負極材層２４における各成分の含有量は従来と同様とすればよい。負極材層２４の形状も従来と同様とすればよい。特に、全固体電池１００を容易に構成できる観点から、シート状の負極材層２４が好ましい。この場合、負極材層２４の厚みは、例えば０．１μｍ以上１ｍｍ以下であることが好ましく、１μｍ以上１００μｍ以下であることがより好ましい。ただし、負極の容量が正極の容量よりも大きくなるように、負極材層２４の厚みを決定することが好ましい。
1.2.4. Negative electrode material layer 24
The negative electrode material layer 24 is a layer containing at least an active material, and in addition to the active material, a solid electrolyte, a binder, a conductive auxiliary agent, and the like can be optionally added. A known active material may be used as the active material. Among the known active materials, two substances having different potentials (charge / discharge potentials) for occluding and releasing predetermined ions are selected, a substance exhibiting a noble potential is used as the above-mentioned positive electrode active substance, and a substance showing a negative potential is selected. Each can be used as a negative electrode active material. For example, when constructing a lithium ion battery, carbon materials such as graphite and hard carbon, various oxides such as lithium titanate, Si and Si alloys, metallic lithium and lithium alloys may be used as the negative electrode active material. it can. The solid electrolyte, the binder, and the conductive auxiliary agent can be appropriately selected and used as the solid electrolyte used for the positive electrode material layer 22. The content of each component in the negative electrode material layer 24 may be the same as that in the prior art. The shape of the negative electrode material layer 24 may be the same as in the prior art. In particular, the sheet-like negative electrode material layer 24 is preferable from the viewpoint that the all-solid battery 100 can be easily configured. In this case, the thickness of the negative electrode material layer 24 is, for example, preferably 0.1 μm or more and 1 mm or less, and more preferably 1 μm or more and 100 μm or less. However, it is preferable to determine the thickness of the negative electrode material layer 24 so that the capacity of the negative electrode is larger than the capacity of the positive electrode.
１．２．５．負極集電体層２５
負極集電体層２５は、金属箔や金属メッシュ等により構成すればよい。特に金属箔が好ましい。負極集電体層２５を構成する金属としては、Ｃｕ、Ｎｉ、Ｆｅ、Ｔｉ、Ｃｏ、Ｚｎ、ステンレス鋼等が挙げられる。負極集電体層２５は、その表面に、接触抵抗を調整するための何らかのコート層を有していてもよい。例えば、導電材と樹脂とを含むコート層等である。負極集電体層２５の厚みは特に限定されるものではない。負極集電体２５の厚みは特に限定されるものではない。例えば０．１μｍ以上１ｍｍ以下であることが好ましく、１μｍ以上１００μｍ以下であることがより好ましい。
1.2.5. Negative electrode current collector layer 25
The negative electrode current collector layer 25 may be made of metal foil, metal mesh or the like. In particular, metal foils are preferred. As a metal which comprises the negative electrode collector layer 25, Cu, Ni, Fe, Ti, Co, Zn, stainless steel etc. are mentioned. The negative electrode current collector layer 25 may have any coating layer on its surface for adjusting the contact resistance. For example, a coat layer or the like containing a conductive material and a resin. The thickness of the negative electrode current collector layer 25 is not particularly limited. The thickness of the negative electrode current collector 25 is not particularly limited. For example, the thickness is preferably 0.1 μm or more and 1 mm or less, and more preferably 1 μm or more and 100 μm or less.
図３に示すように、負極集電体層２５は外縁の一部に負極集電タブ２５ａを備えることが好ましい。タブ２５ａにより、第２の集電体層１２と負極集電体層２５とを容易に電気的に接続することができるとともに、負極集電体層２５同士を容易に電気的に並列に接続することができる。 As shown in FIG. 3, it is preferable that the negative electrode current collector layer 25 be provided with a negative electrode current collection tab 25 a at a part of the outer edge thereof. The second current collector layer 12 and the negative electrode current collector layer 25 can be easily electrically connected by the tab 25a, and the negative electrode current collector layers 25 are easily electrically connected in parallel. be able to.
１．４．短絡電流分散体及び発電要素の配置や接続形態
１．４．１．発電要素の配置
全固体電池１００において、発電要素２０の積層数は特に限定されるものではなく、目的とする電池の出力に応じて、適宜決定すればよい。この場合、複数の発電要素２０が互いに直接接触するように積層されていてもよいし、複数の発電要素２０が何らかの層（例えば絶縁層）や間隔（空気層）を介して積層されていてもよい。電池の出力密度を向上させる観点からは、図１に示すように、複数の発電要素２０が互いに直接接触するように積層されていることが好ましい。また、図１、３に示すように、２つの発電要素２０ａ、２０ｂが、負極集電体２５を共用していることが好ましい。このようにすることで、電池の出力密度が一層向上する。さらに、図１に示すように、全固体電池１００においては、複数の発電要素２０の積層方向と、発電要素２０における各層２１〜２５の積層方向とを一致させることが好ましい。このようにすることで、全固体電池１００の拘束が容易となり、電池の出力密度が一層向上する。
1.4. Arrangement and connection form of short circuit current dispersion body and power generation element 1.4.1. Arrangement of Power Generation Elements In the all-solid-state battery 100, the number of stacked power generation elements 20 is not particularly limited, and may be determined appropriately according to the output of the target battery. In this case, the plurality of power generation elements 20 may be stacked so as to be in direct contact with each other, or even if the plurality of power generation elements 20 are stacked via some layer (for example, insulating layer) or spacing (air layer) Good. From the viewpoint of improving the power density of the battery, as shown in FIG. 1, it is preferable that the plurality of power generation elements 20 be stacked so as to be in direct contact with each other. Further, as shown in FIGS. 1 and 3, it is preferable that the two power generation elements 20 a and 20 b share the negative electrode current collector 25. By doing this, the power density of the battery is further improved. Furthermore, as shown in FIG. 1, in the all-solid battery 100, it is preferable to make the stacking direction of the plurality of power generation elements 20 coincide with the stacking direction of the layers 21 to 25 in the power generation element 20. By so doing, restraint of the all-solid battery 100 is facilitated, and the power density of the battery is further improved.
１．４．２．発電要素同士の電気的接続
全固体電池１００においては、複数の発電要素２０、２０、…同士が電気的に並列に接続される。このように並列に接続された発電要素においては、一の発電要素が短絡した場合に、他の発電要素から当該一の発電要素へと集中して電子が流れ込む。すなわち、電池短絡時にジュール発熱が大きくなり易い。言い換えれば、このように並列接続された複数の発電要素２０、２０、…を備える全固体電池１００において、短絡電流分散体１０を設けることによる効果がより顕著となる。発電要素２０同士を電気的に接続するための部材としては、従来公知の部材を用いればよい。例えば、上述したように、正極集電体層２１に正極集電タブ２１ａを設け、負極集電体層２５に負極集電タブ２５ａを設け、当該タブ２１ａ、２５ａを介して発電要素２０同士を電気的に並列に接続することができる。
1.4.2. Electrical Connection of Power Generation Elements In the all-solid-state battery 100, a plurality of power generation elements 20, 20,... Are electrically connected in parallel. In such power generation elements connected in parallel, when one power generation element is shorted, electrons flow from the other power generation element to the one power generation element in a concentrated manner. That is, Joule heat is likely to increase at the time of battery short circuit. In other words, in the all-solid-state battery 100 including the plurality of power generation elements 20, 20, ... connected in parallel in this manner, the effect by providing the short circuit current dispersion 10 becomes more remarkable. A conventionally known member may be used as a member for electrically connecting the power generation elements 20 with each other. For example, as described above, the positive electrode current collector layer 21 is provided with the positive electrode current collector tab 21a, the negative electrode current collector layer 25 is provided with the negative electrode current collector tab 25a, and the power generation elements 20 are connected to each other through the tabs 21a and 25a. It can be electrically connected in parallel.
１．４．３．短絡電流分散体と発電要素との電気的接続
全固体電池１００において、短絡電流分散体１０の第１の集電体層１１が発電要素２０の正極集電体層２１と電気的に接続されており、短絡電流分散体１０の第２の集電体層１２が発電要素２０の負極集電体層２５と電気的に接続されている。このように、短絡電流分散体１０と発電要素２０とを電気的に接続することで、例えば、短絡電流分散体１０及び一部の発電要素（例えば、発電要素２０ａ）の短絡時に、他の発電要素（例えば発電要素２０ｂ）から短絡電流分散体１０へと大きな回り込み電流を流すことができる。短絡電流分散体１０と発電要素２０とを電気的に接続するための部材としては、従来公知の部材を用いればよい。例えば、上述したように、第１の集電体層１１に第１の集電タブ１１ａを設け、第２の集電体層１２に第２の集電タブ１２ａを設け、当該タブ１１ａ、１２ａを介して短絡電流分散体１０と発電要素２０とを電気的に接続することができる。
1.4.3. Electrical Connection Between Short-Circuit Current Dispersion and Power Generation Element In the all-solid-state battery 100, the first current collector layer 11 of the short-circuit current dispersion 10 is electrically connected to the positive electrode current collector layer 21 of the power generation element 20. The second current collector layer 12 of the short circuit current dispersion 10 is electrically connected to the negative electrode current collector layer 25 of the power generation element 20. Thus, by electrically connecting the short circuit current dispersion body 10 and the power generation element 20, for example, when the short circuit current dispersion body 10 and some of the power generation elements (eg, the power generation element 20a) are shorted, other power generation is performed. A large wraparound current can flow from the element (e.g., power generation element 20b) to the short circuit current dispersion 10. As a member for electrically connecting the short circuit current dispersion body 10 and the power generation element 20, a conventionally known member may be used. For example, as described above, the first current collector tab 11a is provided on the first current collector layer 11, and the second current collector tab 12a is provided on the second current collector layer 12, and the tabs 11a and 12a are provided. Can electrically connect the short circuit current dispersion body 10 and the power generation element 20.
１．４．４．短絡電流分散体と発電要素との位置関係
短絡電流分散体１０と複数の発電要素２０、２０、…とは、互いに積層されていればよい。この場合、短絡電流分散体１０と発電要素２０とを直接積層してもよいし、上記の課題を解決できる範囲において他の層（絶縁層や空気層等）を介して間接的に積層してもよい。短絡電流分散体１０と発電要素２０とを直接積層する場合、上記した課題が生じることは言うまでもない。本開示の全固体電池による効果がより顕著となるのは、このように短絡電流分散体１０が発電要素２０に直接積層されて隣接する場合といえる。一方、間接的に積層した場合でも上記の課題を生じ得る。すなわち、短絡電流分散体１０が他の層を介して間接的に発電要素２０と積層されていたとしても、短絡電流分散体１０が発電要素２０に近接する場合、短絡電流分散体１０と発電要素２０との間を十分に断熱できない可能性がある。短絡電流分散体１０は、複数の発電要素２０、２０、…の外側に積層されていてもよいし、複数の発電要素２０、２０、…の間に積層されていてもよいし、複数の発電要素２０、２０、…の外側と複数の発電要素２０、２０、…の間との双方に積層されていてもよい。特に、図１に示すように、短絡電流分散体１０と複数の発電要素２０、２０、…とを積層した場合において、短絡電流分散体１０が複数の発電要素２０、２０、…よりも外側に少なくとも設けられていることが好ましい。これにより、釘刺し時、短絡電流分散体１０が発電要素２０、２０、…よりも先に短絡し、発電要素２０から短絡電流分散体１０へと回り込み電流を発生させることができ、発電要素２０の内部における発熱を抑制できる。
1.4.4. The positional relationship between the short circuit current dispersion and the power generation element The short circuit current dispersion 10 and the plurality of power generation elements 20, 20, ... may be stacked on each other. In this case, the short circuit current dispersion 10 and the power generation element 20 may be stacked directly, or may be stacked indirectly via another layer (such as an insulating layer or an air layer) as long as the above problems can be solved. It is also good. It goes without saying that when the short circuit current dispersion 10 and the power generation element 20 are directly stacked, the above-mentioned problem arises. The effect of the all-solid-state battery of the present disclosure is more pronounced when the short-circuit current dispersion 10 is thus directly stacked on the power generation element 20 and adjacent thereto. On the other hand, even in the case of laminating indirectly, the above-mentioned problems can occur. That is, even if the short circuit current dispersion 10 is indirectly laminated to the power generation element 20 through another layer, the short circuit current dispersion 10 and the power generation element when the short circuit current dispersion 10 is close to the power generation element 20 There is a possibility that sufficient insulation can not be made between 20 and 20. The short-circuit current dispersion 10 may be stacked outside the plurality of power generation elements 20, 20, ..., or may be stacked between the plurality of power generation elements 20, 20, ... It may be laminated both on the outside of the elements 20, 20,... And between the plurality of power generation elements 20, 20,. In particular, as shown in FIG. 1, when the short circuit current dispersion 10 and the plurality of power generation elements 20, 20,... Are stacked, the short circuit current dispersion 10 is outside the plurality of power generation elements 20, 20,. It is preferable to at least provide. As a result, at the time of nailing, the short circuit current dispersion body 10 can be shorted earlier than the power generation elements 20, 20,..., And a wraparound current can be generated from the power generation element 20 to the short circuit current dispersion body It is possible to suppress heat generation inside the
釘刺しによる電池の短絡が発生し易いのは、釘が発電要素２０の正極集電体層２１から負極集電体層２５に向かって（或いは、負極集電体層２５から正極集電体層２１に向かって）刺された場合である。この点、全固体電池１００においては、釘刺し方向と、各層の積層方向とが一致することが好ましい。より具体的には、全固体電池１００において、発電要素２０における正極集電体層２１と正極材層２２と固体電解質層２３と負極材層２４と負極集電体層２５との積層方向、複数の発電要素２０の積層方向、短絡電流分散体１０における第１の集電体層１１と絶縁層１３と第２の集電体層１２との積層方向、及び、短絡電流分散体１０と複数の発電要素２０、２０、…との積層方向、が同じ方向であることが好ましい。 A short circuit of the battery due to nail penetration is likely to occur because the nail is directed from the positive electrode current collector layer 21 of the power generation element 20 to the negative electrode current collector layer 25 (or from the negative electrode current collector layer 25 to the positive electrode current collector layer 21) It is a case where it is stabbed. In this respect, in the all-solid-state battery 100, it is preferable that the nailing direction and the stacking direction of each layer coincide with each other. More specifically, in the all-solid-state battery 100, the lamination direction of the positive electrode current collector layer 21, the positive electrode material layer 22, the solid electrolyte layer 23, the negative electrode material layer 24, and the negative electrode current collector layer 25 in the power generation element 20; Stacking direction of the power generating element 20, the stacking direction of the first current collector layer 11, the insulating layer 13 and the second current collector layer 12 in the short circuit current dispersion 10, and the short circuit current dispersion 10 and a plurality of It is preferable that the stacking direction of the power generation elements 20, 20,... Be the same direction.
１．４．５．短絡電流分散体と発電要素との大きさの関係
全固体電池１００においては、短絡電流分散体１０が、発電要素２０のできるだけ多くの部分を覆っていることで、釘刺し時に、発電要素２０よりも先に短絡電流分散体１０を短絡させ易くなる。この観点からは、例えば、全固体電池１００においては、短絡電流分散体１０と複数の発電要素２０、２０、…との積層方向から見た時に、短絡電流分散体１０の外縁が発電要素２０、２０、…の外縁よりも外側に存在していることが好ましい。或いは、図１に示すように、複数の発電要素２０、２０、…の積層方向と発電要素２０における各層２１〜２５の積層方向とが同じである場合において、短絡電流分散体１０と複数の発電要素２０、２０、…との積層方向から見た時に、短絡電流分散体１０の外縁が正極材層２２、固体電解質層２３及び負極材層２４の外縁よりも外側に存在することが好ましい。ただし、この場合、短絡電流分散体１０の第１の集電体層１１と発電要素２０の負極集電体層２５とが短絡しないようにする。すなわち、短絡電流分散体１０と発電要素２０との間に絶縁体等を設け、短絡電流分散体１０を大きくしても、短絡電流分散体１０と発電要素２０との短絡を防止可能とする。
1.4.5. Relationship between Size of Short-Circuit Current Dispersion and Power Generation Element In the all solid battery 100, the short-circuit current dispersion 10 covers as much of the power generation element 20 as possible. Also, the short circuit current dispersion 10 can be easily shorted earlier. From this point of view, for example, in the all solid battery 100, the outer edge of the short circuit current dispersion 10 is the power generating element 20 when viewed from the stacking direction of the short circuit current dispersion 10 and the plurality of power generating elements 20, 20,. Preferably, they are present outside the outer edge of 20,. Alternatively, as shown in FIG. 1, when the stacking direction of the plurality of power generation elements 20, 20,... And the stacking direction of each layer 21 to 25 in the power generation element 20 are the same, the short circuit current dispersion 10 and the plurality of power generation When viewed in the stacking direction of the elements 20, 20, ..., it is preferable that the outer edge of the short circuit current dispersion 10 be present outside the outer edges of the positive electrode material layer 22, the solid electrolyte layer 23, and the negative electrode material layer 24. However, in this case, the first current collector layer 11 of the short circuit current dispersion 10 and the negative electrode current collector layer 25 of the power generation element 20 are prevented from short circuiting. That is, even if an insulator or the like is provided between the short circuit current dispersion 10 and the power generation element 20 to enlarge the short circuit current dispersion 10, the short circuit between the short circuit current dispersion 10 and the power generation element 20 can be prevented.
一方で、電池のエネルギー密度をより高める観点及び上記した短絡電流分散体１０と発電要素２０との短絡を容易に防止できる観点からは、短絡電流分散体１０をできるだけ小さくするとよい。すなわち、この観点からは、全固体電池１００においては、短絡電流分散体１０と複数の発電要素２０、２０、…との積層方向から見た時に、短絡電流分散体１０の外縁が発電要素２０、２０、…の外縁よりも内側に存在することが好ましい。或いは、複数の発電要素２０、２０、…の積層方向と発電要素２０における各層２１〜２５の積層方向とが同じである場合において、短絡電流分散体１０と複数の発電要素２０、２０、…との積層方向から見た時に、短絡電流分散体１０の外縁が正極材層２２、固体電解質層２３及び負極材層２４の外縁よりも内側に存在することが好ましい。 On the other hand, from the viewpoint of further increasing the energy density of the battery and from the viewpoint of easily preventing the short circuit between the short circuit current dispersion 10 and the power generation element 20 described above, the short circuit current dispersion 10 may be made as small as possible. That is, from this point of view, in the all solid battery 100, the outer edge of the short circuit current dispersion 10 is the power generating element 20 when viewed from the stacking direction of the short circuit current dispersion 10 and the plurality of power generating elements 20, 20,. It is preferable to exist inside the outer edge of 20,. Alternatively, in the case where the stacking direction of the plurality of power generation elements 20, 20,... And the stacking direction of the layers 21 to 25 in the power generation element 20 are the same, the short circuit current dispersion 10 and the plurality of power generation elements 20, 20,. It is preferable that the outer edge of the short circuit current dispersion 10 exists inside the outer edges of the positive electrode material layer 22, the solid electrolyte layer 23 and the negative electrode material layer 24 when viewed from the stacking direction of the above.
以上の通り、全固体電池１００においては、釘刺し時の短絡電流分散体１０及び発電要素２０の短絡時、釘を刺している最中の高圧時において短絡電流分散体１０の短絡抵抗を小さなものとすることができ、釘貫通後の低圧時において短絡電流分散体１０の短絡抵抗を大きなものとすることができる。よって釘刺し時、釘を刺し込んでいる最中において、回り込み電流を短絡電流分散体１０へと多く分散させる一方、釘貫通後は、短絡電流分散体１０の抵抗が大きくなることで、短絡電流分散体１０に流れ込む回り込み電流量を少なくでき、短絡電流分散体１０の温度上昇を抑制できる。すなわち、短絡電流分散体１０が過度に温度上昇することを抑制でき、近接する発電要素２０の温度上昇も抑制できる。 As described above, in the all-solid-state battery 100, the short-circuit resistance of the short-circuit current dispersion 10 is small at the time of high-pressure during nailing when the short-circuit current dispersion 10 and the power generating element 20 are shorted when nailing. The short circuit resistance of the short circuit current dispersion 10 can be made large at the time of low pressure after penetration of the nail. Therefore, at the time of piercing the nail, during the piercing of the nail, a large amount of sneak current is dispersed to the short circuit current dispersion 10, while after penetration of the nail, the resistance of the short circuit current dispersion 10 is increased. The amount of sneak current flowing into the dispersion 10 can be reduced, and the temperature rise of the short circuit current dispersion 10 can be suppressed. That is, excessive temperature rise of the short circuit current dispersion 10 can be suppressed, and temperature rise of the adjacent power generation element 20 can also be suppressed.
２．全固体電池２００
図４に全固体電池２００の層構成を概略的に示す。図４に示すように、全固体電池２００においては、短絡電流分散体１０に加えて、短絡電流分散体１１０が設けられている。図５に短絡電流分散体１１０の構成を概略的に示す。図５（Ａ）が外観斜視図、図５（Ｂ）がＶＢ−ＶＢ断面図である。短絡電流分散体１１０以外の構成については、全固体電池１００と同様である。
2. All solid battery 200
The layer configuration of the all-solid battery 200 is schematically shown in FIG. As shown in FIG. 4, in the all solid state battery 200, in addition to the short circuit current dispersion 10, a short circuit current dispersion 110 is provided. The structure of the short circuit current dispersion 110 is schematically shown in FIG. FIG. 5A is an external perspective view, and FIG. 5B is a cross-sectional view taken along the line VB-VB. The configuration other than the short circuit current dispersion 110 is the same as that of the all solid battery 100.
図４に示すように、全固体電池２００は、短絡電流分散体として、発電要素２０に近接する第１の短絡電流分散体１０と、第１の短絡電流分散体１０に対して発電要素２０が備えられる側とは反対側に設けられた第２の短絡電流分散体１１０と、を備えている。ここで、上述したように、第１の短絡電流分散体１０においては、第１の集電体層１１及び第２の集電体層１２の５ＭＰａにおける接触抵抗Ｒ１と１００ＭＰａにおける接触抵抗Ｒ２との比（Ｒ１／Ｒ２）が１．６以上である。一方、第２の短絡電流分散体１１０においては、第１の集電体層１１’及び第２の集電体層１２’の５ＭＰａにおける接触抵抗Ｒ１’と１００ＭＰａにおける接触抵抗Ｒ２’との比（Ｒ１’／Ｒ２’）は１．６未満である点に特徴がある。 As shown in FIG. 4, the all-solid-state battery 200 includes, as a short circuit current dispersion, a first short circuit current dispersion 10 adjacent to the power generation element 20 and a power generation element 20 with respect to the first short circuit current dispersion 10. And a second short circuit current dispersion body 110 provided on the side opposite to the provided side. Here, as described above, in the first short circuit current dispersion 10, the contact resistance R 1 at 5 MPa and the contact resistance R 2 at 100 MPa of the first current collector layer 11 and the second current collector layer 12. The ratio (R 1 / R 2 ) to is 1.6 or more. On the other hand, in the second short circuit current dispersion 110, the contact resistance R 1 'at 5 MPa and the contact resistance R 2 ' at 100 MPa of the first current collector layer 11 'and the second current collector layer 12'. It is characterized in that the ratio (R 1 ′ / R 2 ′) is less than 1.6.
第１の集電体層１１’及び第２の集電体層１２’ は、金属箔や金属メッシュ等により構成すればよい。特に金属箔が好ましい。集電体層１１、１２を構成する金属としては、Ｃｕ、Ｎｉ、Ａｌ、Ｆｅ、Ｔｉ、Ｚｎ、Ｃｏ、Ｃｒ、Ａｕ、Ｐｔ、ステンレス鋼等が挙げられる。集電体層１１や集電体層１２は、その表面に、接触抵抗を調整するための何らかのコート層を有していてもよい。例えば、導電材と樹脂とを含むコート層である。 The first current collector layer 11 'and the second current collector layer 12' may be made of metal foil, metal mesh or the like. In particular, metal foils are preferred. As a metal which comprises the collector layers 11 and 12, Cu, Ni, Al, Fe, Ti, Zn, Co, Cr, Au, Pt, stainless steel etc. are mentioned. The current collector layer 11 and the current collector layer 12 may have any coating layer for adjusting the contact resistance on their surfaces. For example, it is a coat layer containing a conductive material and a resin.
第１の集電体層１１’及び第２の集電体層１２’は、上記したような各種材料から、低圧時（５ＭＰａ）における接触抵抗Ｒ１’と高圧時（１００ＭＰａ）における接触抵抗Ｒ２’との比（Ｒ１’／Ｒ２’）が１．６未満となる組み合わせを採用すればよい。好ましくは、比（Ｒ１／Ｒ２）が１．５以下、より好ましくは１．１以下となる組み合わせを採用する。例えば、第１の集電体層としてアルミニウム箔を、第２の集電体層として銅箔を用いた場合、上記の比（Ｒ１’／Ｒ２’）が１．１以下となり得る。 From the various materials described above, the first current collector layer 11 ′ and the second current collector layer 12 ′ have a contact resistance R 1 ′ at low pressure (5 MPa) and a contact resistance R at high pressure (100 MPa). A combination in which the ratio to 2 ′ (R 1 ′ / R 2 ′) is less than 1.6 may be employed. Preferably, a combination in which the ratio (R 1 / R 2 ) is 1.5 or less, more preferably 1.1 or less is employed. For example, when an aluminum foil is used as the first current collector layer and a copper foil is used as the second current collector layer, the above ratio (R 1 ′ / R 2 ′) can be 1.1 or less.
上述した全固体電池１００においては、釘刺し等の短絡時、釘を差し込んでいる最中の高圧時において、短絡電流分散体１０へと多くの回り込み電流を流すことができるものの、釘貫通後の低圧時においては短絡電流分散体１０の抵抗が増大することから、短絡電流分散体１０へと流れ込む回り込み電流の量は少なくなる。しかしながら、釘貫通後においても、短絡電流分散体に多くの回り込み電流を流したい場合がある。この場合において、短絡電流分散体１０のみを設けた場合、釘貫通後において、短絡電流分散体に流すべき回り込み電流が、短絡抵抗の小さい発電要素２０へと流れ込む虞がある。すなわち、短絡電流分散体１０の過度の温度上昇は抑えられるものの、それとは別に、発電要素２０の温度が上昇してしまう虞がある。一方で、上述したように、発電要素２０に近接する短絡電流分散体１０については、できるだけ温度上昇を抑える必要がある。 In the all solid state battery 100 described above, although it is possible to flow a large amount of sneak current to the short circuit current dispersion 10 at the time of high voltage while inserting the nail at the time of shorting such as nailing, etc. At low pressure, the resistance of the short circuit current dispersion 10 increases, so the amount of sneak current flowing into the short circuit current dispersion 10 is reduced. However, even after penetration of a nail, it may be desirable to flow a large amount of sneak current into the short circuit current dispersion. In this case, when only the short circuit current dispersion 10 is provided, there is a possibility that the sneak current to be supplied to the short circuit current dispersion may flow into the power generation element 20 having a small short circuit resistance after penetrating the nail. That is, although the excessive temperature rise of the short circuit current dispersion body 10 is suppressed, there is a possibility that the temperature of the power generation element 20 may rise separately. On the other hand, as described above, the temperature rise of the short circuit current dispersion 10 close to the power generation element 20 needs to be suppressed as much as possible.
これに対し、全固体電池２００においては、釘刺し等により短絡電流分散体１０、１１０が短絡した際、釘貫通後に短絡電流分散体１０の抵抗が増大した場合でも、その後、引き続いて、短絡電流分散体１１０へと多くの回り込み電流を流すことができる。すなわち、発電要素２０と近接する短絡電流分散体１０の過度の温度上昇を抑えることで短絡電流分散体１０との接触による発電要素２０の過度の温度上昇を抑えつつ、短絡電流分散体１１０へと多くの回り込み電流を流すことで、回り込み電流による発電要素２０の温度上昇を抑えることもできる。 On the other hand, in the all solid battery 200, when the short circuit current dispersions 10, 110 are short circuited by nailing or the like, even if the resistance of the short circuit current dispersion 10 increases after the nail penetrates, the short circuit current continues thereafter. Many wraparound currents can flow into the dispersion 110. That is, by suppressing the excessive temperature rise of the short circuit current dispersion body 10 adjacent to the power generation element 20, the excessive temperature rise of the power generation element 20 due to the contact with the short circuit current dispersion body 10 is suppressed. By flowing a large amount of wraparound current, it is also possible to suppress the temperature rise of the power generation element 20 due to the wraparound current.
３．全固体電池の製造方法
短絡電流分散体１０、１１０は、第１の集電体層（例えば、金属箔）と第２の集電体層（例えば、金属箔）とについて、上記した低圧における接触抵抗と高圧における接触抵抗との関係を満たすものを選定し、これら集電体層の間に絶縁層（例えば、絶縁フィルム）を配置することで、容易に作製できる。図２、３に示すように、第２の集電体層１２（１２’）の両面に絶縁層１３、１３を配置し、さらに絶縁層１３、１３の第２の集電体層１２（１２’）とは反対側の面に第１の集電体層１１、１１（１１’、１１’）を配置してもよい。ここで、短絡電流分散体１０、１１０は、その形状を保持するために、接着剤や樹脂などを用いて各層を互いに貼り合わせてもよい。この場合、接着剤等は、各層の全面に塗布する必要はなく、各層の表面の一部に塗布すればよい。
3. Method of Manufacturing All-Solid-State Battery The short-circuit current dispersions 10, 110 contact the first current collector layer (for example, metal foil) and the second current collector layer (for example, metal foil) at the low pressure described above. It can be easily produced by selecting one satisfying the relationship between the resistance and the contact resistance at high pressure, and arranging an insulating layer (for example, an insulating film) between these current collector layers. As shown in FIGS. 2 and 3, the insulating layers 13 and 13 are disposed on both sides of the second current collector layer 12 (12 ′), and the second current collector layer 12 (12 The first current collector layers 11 and 11 (11 'and 11') may be disposed on the surface opposite to '). Here, in order to maintain the shape of the short-circuit current dispersions 10 and 110, layers may be bonded to each other using an adhesive, a resin, or the like. In this case, the adhesive or the like does not have to be applied to the entire surface of each layer, and may be applied to part of the surface of each layer.
発電要素２０については、公知の方法により作製できる。例えば、全固体電池を製造する場合は、正極集電体層２１の表面に正極材を湿式にて塗工して乾燥させることで正極材層２２を形成し、負極集電体層２５の表面に負極材を湿式にて塗工して乾燥させることで負極材層２４を形成し、正極材層２１と負極材層２４との間に固体電解質等を含む電解質層２３を転写し、プレス成形して一体化することで発電要素２０を作製できる。この時のプレス圧は特に限定されるものではないが、例えば２ｔｏｎ／ｃｍ２以上とすることが好ましい。 The power generation element 20 can be manufactured by a known method. For example, in the case of manufacturing an all solid battery, the positive electrode material is wet coated on the surface of the positive electrode current collector layer 21 and dried to form the positive electrode material layer 22, and the surface of the negative electrode current collector layer 25 The negative electrode material is wet coated and dried to form the negative electrode material layer 24, and the electrolyte layer 23 containing a solid electrolyte or the like is transferred between the positive electrode material layer 21 and the negative electrode material layer 24, and press-formed. The power generation element 20 can be manufactured by integrating the two. The pressing pressure at this time is not particularly limited, but is preferably, for example, 2 ton / cm 2 or more.
このようにして作製した短絡電流分散体１０を複数の発電要素２０に対して積層するとともに、第１の集電体層１１に設けられたタブ１１ａを正極集電体層２１のタブ２１ａと接続し、第２の集電体層１２に設けられたタブ１２ａを負極集電体層２５のタブ２５ａと接続し、正極集電体層２１のタブ２１ａ同士を接続し、負極集電体層２５のタブ２５ａ同士を接続することで、短絡電流分散体１０と発電要素２０とを電気的に接続するとともに、複数の発電要素２０同士を電気的に並列に接続することができる。また、必要に応じて、短絡電流分散体１１０を短絡電流分散体１０に対して発電要素２０が備えられる側とは反対側に積層し、上記と同様に集電体層１１、１２を発電要素２０に電気的に接続する。このようにして電気的に接続された積層体をラミネートフィルムやステンレス鋼缶等の電池ケース内に真空封入することによって、全固体電池を作製できる。尚、これらの作製手順はあくまでも一例であり、これ以外の手順によっても全固体電池を作製可能である。例えば、湿式法に替えて乾式法によって正極材層等を形成することも可能である。 The short circuit current dispersion 10 thus produced is laminated on a plurality of power generation elements 20, and the tab 11a provided on the first current collector layer 11 is connected to the tab 21a of the positive electrode current collector layer 21. And the tabs 12a of the second current collector layer 12 are connected to the tabs 25a of the negative electrode current collector layer 25, and the tabs 21a of the positive electrode current collector layer 21 are connected to each other. By connecting the tabs 25a to each other, the short circuit current dispersion 10 and the power generation element 20 can be electrically connected, and the plurality of power generation elements 20 can be electrically connected in parallel. In addition, if necessary, the short-circuit current dispersion 110 is laminated on the short-circuit current dispersion 10 on the side opposite to the side on which the power generation element 20 is provided, and the current collector layers 11 and 12 are generated similarly to the above. Connect electrically to 20. An all-solid battery can be produced by vacuum-sealing the laminate thus electrically connected in a battery case such as a laminate film or a stainless steel can. Note that these preparation procedures are merely an example, and all-solid-state batteries can be prepared by other procedures. For example, it is possible to form the positive electrode material layer or the like by a dry method instead of the wet method.
以上の通り、従来の全固体電池の製造方法を応用することで、本開示の全固体電池１００、２００を容易に製造することができる。 As described above, by applying the conventional method of manufacturing an all-solid-state battery, all-solid-state batteries 100, 200 of the present disclosure can be easily manufactured.
４．補足事項
上記説明においては、２つの第１の集電体層と２つの絶縁層と１つの第２の集電体層とによって短絡電流分散体が構成される形態について示したが、本開示の全固体電池はこの形態に限定されるものではない。短絡電流分散体は、第１の集電体層と第２の集電体層との間に絶縁層を有するものであればよく、各層の数は特に限定されない。
4. Supplementary Matters In the above description, the form in which the short circuit current dispersion is configured by the two first current collector layers, the two insulating layers, and the one second current collector layer has been described. The all solid state battery is not limited to this form. The short-circuit current dispersion may be any one having an insulating layer between the first current collector layer and the second current collector layer, and the number of each layer is not particularly limited.
上記説明においては、２つの発電要素が、１つの負極集電体層を共用する形態について示したが、本開示の全固体電池はこの形態に限定されるものではない。発電要素は単電池として機能するものであればよく、正極集電体層と正極材層と固体電解質層と負極材層と負極集電体層とが積層されていればよい。 In the above description, the two power generation elements are shown to share one negative electrode current collector layer, but the all solid state battery of the present disclosure is not limited to this form. The power generation element only needs to function as a unit cell, and the positive electrode current collector layer, the positive electrode material layer, the solid electrolyte layer, the negative electrode material layer, and the negative electrode current collector layer may be stacked.
上記説明においては、全固体電池において短絡電流分散体が複数の発電要素の積層方向の両外側に一つずつ備えられる形態について示したが、短絡電流分散体の数はこれに限定されるものではない。全固体電池において外側に複数の短絡電流分散体が備えられていてもよい。また、複数の発電要素の積層方向外側に限らず、短絡電流分散体が複数の発電要素の間に設けられていてもよい。 In the above description, in the all-solid-state battery, the short circuit current dispersions are provided one by one on both outer sides in the stacking direction of the plurality of power generation elements, but the number of the short circuit current dispersions is limited to this Absent. A plurality of short circuit current dispersions may be provided on the outside of the all solid state battery. In addition, the short circuit current dispersion may be provided between the plurality of power generation elements as well as the outside in the stacking direction of the plurality of power generation elements.
上記説明においては、複数の発電要素が積層された形態について示したが、全固体電池において発電要素が複数積層されていない形態（単電池のみからなる形態）においても、ある程度の効果が奏されるものと考えられる。ただし、釘刺し時等の短絡によるジュール発熱は、一つの発電要素よりも、複数の発電要素が積層された形態において大きくなりやすい。すなわち、複数の発電要素が積層された形態において、短絡電流分散体を設けることによる効果がより顕著となるといえ、この点が、本開示の全固体電池における優位な点の一つである。 In the above description, the form in which the plurality of power generation elements are stacked is described, but even in the form in which the plurality of power generation elements are not stacked in the all solid battery It is considered to be a thing. However, Joule heat due to a short circuit at the time of nailing or the like tends to be larger in a form in which a plurality of power generation elements are stacked than one power generation element. That is, in the form in which the plurality of power generation elements are stacked, it can be said that the effect by providing the short circuit current dispersion becomes more remarkable, which is one of the advantageous points in the all solid state battery of the present disclosure.
上記説明においては、短絡電流分散体や発電要素から集電タブが突出するものとして説明した。しかしながら、本開示の全固体電池において集電タブはなくてもよい。例えば、面積の大きな集電体層を用い、短絡電流分散体と発電要素との積層体において、複数の集電体層の外縁を突出させるものとし、当該突出させた集電層の間に導電材を挟みこむことで、タブを設けずとも、集電体層同士の電気的な接続が可能である。或いは、タブではなく、導線等によって集電体層同士を電気的に接続してもよい。 In the above description, it has been described that the current collection tab protrudes from the short circuit current dispersion body or the power generation element. However, the current collection tab may not be present in the all solid state battery of the present disclosure. For example, in the laminate of the short-circuit current dispersion and the power generation element, the outer edges of the plurality of current collector layers are made to project by using the current collector layer having a large area, and conduction is performed between the projected current collector layers. By sandwiching the material, it is possible to electrically connect the current collector layers without providing a tab. Alternatively, the current collector layers may be electrically connected to each other by conducting wires or the like instead of the tabs.
全固体電池は電解液系電池に比べて発電要素内の隙間が少なく、釘刺し時に釘が発電要素を貫通する際、発電要素にかかる圧力が高い。よって、発電要素の短絡抵抗が小さくなり、短絡部に多くの回り込み電流が流れ込み易くなると考えられる。さらに、全固体電池においては、発電要素内の内部抵抗を低減すべく、発電要素に対して拘束圧力を付与する場合がある。この場合、発電要素の積層方向（正極集電体層が負極集電体層に向かう方向）に拘束圧力が付与されることとなり、釘刺し時、釘による圧力と拘束圧力とが加算されて発電要素に印加されることから、正極集電体層と負極集電体層とが接触して短絡し易く、また、発電要素の短絡抵抗が小さくなり易いものと考えられる。そのため、短絡電流分散体を設けて回りこみ電流を分散させることによる効果が顕著となるものと考えられる。また、短絡電流分散体を構成する集電体層同士の接触抵抗が低圧時と高圧時とで大きく異なることによって奏される効果が一層顕著となるものと考えられる。一方、電解液系電池は、通常、電池ケース内が電解液で満たされ、各層が電解液に浸漬されて、各層の隙間に電解液が供給されるものであり、釘刺し時に釘によって印加される圧力が、全固体電池の場合と比較して小さくなる。また、釘刺し時、釘を刺し込んでいる最中の荷重と釘貫通後の荷重との差も小さい。そのため、上記した短絡電流分散体を設ける効果が、全固体電池の場合と比べて、相対的に小さくなるものと考えられる。 The all-solid-state battery has a smaller gap in the power generation element compared to the electrolyte battery, and the pressure applied to the power generation element is high when the nail penetrates the power generation element when nailing. Therefore, it is considered that the short circuit resistance of the power generation element is reduced, and a large amount of sneak current easily flows into the short circuit portion. Furthermore, in the all-solid-state battery, in order to reduce internal resistance in the power generation element, a restraint pressure may be applied to the power generation element. In this case, the restraint pressure is applied in the stacking direction of the power generation element (the direction in which the positive electrode current collector layer is directed to the negative electrode current collector layer), and when nailing, the pressure by the nail and the restraint pressure are added to generate power. It is considered that since the positive electrode current collector layer and the negative electrode current collector layer are in contact with each other to cause a short circuit easily because the voltage is applied to the element, the short circuit resistance of the power generation element tends to be small. Therefore, it is considered that the effect of providing the short circuit current dispersion to disperse the wraparound current becomes remarkable. Further, it is considered that the effect exerted by the contact resistances of the current collector layers constituting the short circuit current dispersion being largely different at the low pressure and the high pressure becomes more remarkable. On the other hand, in the case of an electrolyte battery, the inside of the battery case is usually filled with the electrolyte, and each layer is immersed in the electrolyte so that the electrolyte is supplied to the gap between the layers. The pressure is reduced compared to the case of the all solid state battery. In addition, at the time of nail stabbing, the difference between the load during piercing the nail and the load after penetrating the nail is small. Therefore, the effect of providing the above-mentioned short circuit current dispersion is considered to be relatively small compared to the case of the all solid battery.
尚、バイポーラ電極を介して発電要素同士を電気的に直列に接続した場合は、一部の発電要素に釘を刺すと、他の発電要素から当該一部の発電要素へと釘を介して回り込み電流が流れるものと考えられる。すなわち、接触抵抗の高い釘を介して回り込むこととなり、その電流量は小さい。また、バイポーラ電極を介して発電要素同士を電気的に直列に接続した場合、発電要素のすべてに釘が刺さった場合に回り込み電流が最も大きくなると考えられるが、このような場合、発電要素の放電が既に十分に進行しているものと考えられ、一部の発電要素の温度が局所的に上昇するといったことは生じ難い。この点、発電要素を電気的に並列に接続した場合と比較して、短絡電流分散体による効果が小さくなるものと考えられる。よって、本開示の技術は、発電要素同士を電気的に並列に接続した電池において特に顕著な効果を発揮するものといえる。 In addition, when the power generation elements are electrically connected in series via the bipolar electrode, when a nail is pierced to a part of the power generation elements, it wraps around from the other power generation element to the power generation element. It is considered that current flows. That is, it will turn around via a nail with high contact resistance, and the amount of current is small. In addition, when the power generation elements are electrically connected in series via the bipolar electrode, it is considered that the sneaking current is largest when all the power generation elements are pierced, but in such a case, the discharge of the power generation elements However, it is unlikely that the temperature of some of the power generating elements will rise locally. In this respect, it is considered that the effect of the short circuit current dispersion is reduced as compared with the case where the power generation elements are electrically connected in parallel. Therefore, it can be said that the technology of the present disclosure exerts a particularly remarkable effect in a battery in which power generation elements are electrically connected in parallel.
種々の金属箔を用意し、金属箔同士を押し付ける圧力を変化させた場合における、金属箔同士の接触抵抗の変化を評価した。 Various metal foils were prepared, and the change in contact resistance between the metal foils was evaluated in the case where the pressure for pressing the metal foils was changed.
１．金属箔の種類
評価に用いた金属箔の種類は以下の通りである。
・ アルミニウム箔（厚さ１５μｍ、ＵＡＣＪ社製、１Ｎ３０）
・ 銅箔（厚さ１２μｍ、古河電工社製、電解銅箔）
・ ステンレス鋼（ＳＵＳ）箔（厚さ１５μｍ、ＳＵＳ３０４）
・ 炭素コート銅箔Ａ（厚さ１６μｍ、昭和電工社製、ＣＤＸ）
・ 炭素コートアルミニウム箔Ａ（厚さ１９μｍ、昭和電工社製、ＳＤＸ）
・ 炭素コート銅箔Ｂ（下記参照）
・ 炭素コートアルミニウム箔Ｂ（下記参照）
1. Types of metal foils The types of metal foils used for the evaluation are as follows.
-Aluminum foil (thickness 15 μm, manufactured by UACJ, 1N30)
・ Copper foil (12 μm in thickness, manufactured by Furukawa Electric Co., electrolytic copper foil)
-Stainless steel (SUS) foil (thickness 15 μm, SUS 304)
-Carbon coated copper foil A (thickness 16 μm, Showa Denko KK, CDX)
-Carbon coated aluminum foil A (19 μm in thickness, manufactured by Showa Denko, SDX)
-Carbon coated copper foil B (see below)
-Carbon coated aluminum foil B (see below)
炭素コート銅箔Ｂ及び炭素コートアルミニウム箔Ｂは以下の通りに作製した。すなわち、導電材としてファーネスブラック（平均一次粒子径６６ｎｍ、東海カーボン社製）と、その他のフィラーとしてアルミナ（昭和電工社製ＣＢ−Ｐ０２）と、ポリマーとしてＰＶＤＦ（クレハ社製ＫＦポリマーＬ♯９１３０）とを、体積比が１０：６０：３０となるようにＮＭＰと混合し、ペーストを作製した。ペーストを上記の銅箔又はアルミニウム箔に対して塗工し、加熱炉で乾燥させ、銅箔及びアルミニウム箔のそれぞれの表面に炭素コート層を形成した。乾燥後の炭素コート膜の厚みは１０μｍであった。 Carbon coated copper foil B and carbon coated aluminum foil B were produced as follows. That is, furnace black (average primary particle diameter 66 nm, manufactured by Tokai Carbon Co., Ltd.) as a conductive material, alumina (CB-P02 manufactured by Showa Denko) as another filler, and PVDF (KF polymer L # 9130 manufactured by Kureha Co., Ltd.) as a polymer Were mixed with NMP so that the volume ratio was 10:60:30, to prepare a paste. The paste was applied to the above-described copper foil or aluminum foil and dried in a heating furnace to form a carbon coat layer on each surface of the copper foil and the aluminum foil. The thickness of the carbon coat film after drying was 10 μm.
２．金属箔の組み合わせパターン
下記表１に示す組み合わせ１〜５に対して、所定の圧力下における接触抵抗を測定した。
2. Metal foil combination pattern For the combinations 1 to 5 shown in Table 1 below, the contact resistance under a predetermined pressure was measured.
３．接触抵抗の測定方法
図６に示す装置を用いて、金属箔同士を所定の圧力で互いに押し付けつつ、金属箔同士の接触抵抗を測定した。具体的には、φ１１．２８ｍｍのＳＫ材ブロックとベークライト板とで２枚の金属箔を挟み（金属箔間の一部にポリイミド系フィルム（厚さ２５μｍ、東レ・デュポン社製カプトン１００Ｈ）を設置）、オートグラフにて所定の圧力をかけた際の接触抵抗を、抵抗計（Ｈｉｏｋｉ社製ＲＭ３５４２）にて測定した。下記表１に示す組み合わせ１〜６について、５ＭＰａにおける接触抵抗と、１００ＭＰａにおける接触抵抗とを示す。
3. Measurement Method of Contact Resistance The contact resistance of the metal foils was measured using the apparatus shown in FIG. 6 while pressing the metal foils with each other at a predetermined pressure. Specifically, two metal foils are sandwiched between a SK material block of φ 11.28 mm and a Bakelite plate (a polyimide film (25 μm thick, Kapton 100H manufactured by Toray Dupont Co., Ltd.) is provided between metal foils) The contact resistance when a predetermined pressure was applied was measured with an autograph using a resistance meter (RM3542 manufactured by Hioki). About the combinations 1-6 shown in following Table 1, the contact resistance in 5 Mpa and the contact resistance in 100 Mpa are shown.
表１に示す結果から明らかなように、金属箔（集電体層）の組み合わせによって、５ＭＰａにおける接触抵抗と１００ＭＰａにおける接触抵抗との比は大きく異なる。これは、例えば、金属箔の種類によって柔らかさ（展性）が異なり、金属箔の柔らかさ（展性）によって金属箔同士の密着性が異なることから、このことが低圧下から高圧下における接触抵抗の変化に影響を与えているものと考えられる。また、炭素コート箔については、圧力が高い場合、炭素粒子間の抵抗が下がり、接触抵抗が下がると考えられる。また、炭素コートに含まれる樹脂の弾性が大きいため、圧力が抜けると炭素粒子間の接触圧力が下がる為、炭素コート内の電子伝導性が低下する。結果低圧力下で接触抵抗が高くなると考えられる。 As is clear from the results shown in Table 1, the ratio of the contact resistance at 5 MPa to the contact resistance at 100 MPa is largely different depending on the combination of the metal foils (current collector layers). This is because, for example, the softness (the malleability) differs depending on the type of the metal foil, and the adhesion between the metal foils differs depending on the softness (the malleability) of the metal foil. It is thought that the change in resistance is affected. In the case of a carbon-coated foil, when the pressure is high, it is considered that the resistance between carbon particles is reduced and the contact resistance is reduced. In addition, since the resin contained in the carbon coat has high elasticity, the contact pressure between the carbon particles is lowered when the pressure is released, so that the electron conductivity in the carbon coat is lowered. As a result, the contact resistance is considered to be high under low pressure.
本発明に係る全固体電池は、例えば、車搭載用の大型電源として好適に利用できる。 The all-solid-state battery according to the present invention can be suitably used, for example, as a large-sized power supply for vehicle mounting.
１０ 短絡電流分散体
１１ 第１の集電体層
１１ａ 第１の集電タブ
１２ 第２の集電体層
１２ａ 第２の集電タブ
１３ 絶縁層
２０ 発電要素
２１ 正極集電体層
２１ａ 正極集電タブ
２２ 正極材層
２３ 固体電解質層
２４ 負極材層
２５ 負極集電体層
２５ａ 負極集電タブ
１００ 全固体電池
DESCRIPTION OF SYMBOLS 10 short circuit current dispersion 11 1st current collection layer 11a 1st current collection tab 12 2nd current collection layer 12a 2nd current collection tab 13 insulating layer 20 electric power generation element 21 positive electrode current collection layer 21a positive electrode current collection layer Charge tab 22 positive electrode material layer 23 solid electrolyte layer 24 negative electrode material layer 25 negative electrode collector layer 25a negative electrode current collector tab 100 all solid battery
Claims (1)
前記短絡電流分散体において、第１の集電体層と第２の集電体層と前記第１の集電体層及び前記第２の集電体層の間に設けられた絶縁層とが積層されており、
前記発電要素において、正極集電体層と正極材層と固体電解質層と負極材層と負極集電体層とが積層されており、
前記第１の集電体層が前記正極集電体層と電気的に接続されており、
前記第２の集電体層が前記負極集電体層と電気的に接続されており、
複数の前記発電要素同士が電気的に並列に接続されており、
前記発電要素に近接する前記短絡電流分散体に備えられる前記第１の集電体層及び前記第２の集電体層の５ＭＰａにおける接触抵抗Ｒ１と１００ＭＰａにおける接触抵抗Ｒ２との比（Ｒ１／Ｒ２）が１．６以上である、
全固体電池。 An all-solid-state battery in which at least one short circuit current dispersion and a plurality of power generation elements are stacked,
In the short-circuit current dispersion, a first current collector layer, a second current collector layer, and an insulating layer provided between the first current collector layer and the second current collector layer Are stacked,
In the power generation element, a positive electrode current collector layer, a positive electrode material layer, a solid electrolyte layer, a negative electrode material layer, and a negative electrode current collector layer are stacked,
The first current collector layer is electrically connected to the positive electrode current collector layer;
The second current collector layer is electrically connected to the negative electrode current collector layer;
The plurality of power generation elements are electrically connected in parallel,
Contact resistance R 1 at 5 MPa and contact resistance R 2 at 100 MPa of the first current collector layer and the second current collector layer provided in the short circuit current dispersion adjacent to the power generation element (R (R) 1 / R 2 ) is 1.6 or more,
All solid state battery.
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| US10714789B2 (en) | 2017-11-07 | 2020-07-14 | Toyota Jidosha Kabushiki Kaisha | All-solid state battery |
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