JP2020119696A - Secondary battery - Google Patents

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JP2020119696A
JP2020119696A JP2019008481A JP2019008481A JP2020119696A JP 2020119696 A JP2020119696 A JP 2020119696A JP 2019008481 A JP2019008481 A JP 2019008481A JP 2019008481 A JP2019008481 A JP 2019008481A JP 2020119696 A JP2020119696 A JP 2020119696A
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negative electrode
current collector
electrode current
secondary battery
active material
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JP7054456B2 (en
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誠 大福
Makoto Ofuku
誠 大福
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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

Abstract

To provide a secondary battery which can prevent the formation of sulfide in an electrode body containing a substance including sulfur and which has a negative electrode current collector made of metal (Al) of the same kind as that of a terminal for external connection.SOLUTION: A secondary battery herein disclosed comprises an electrode body of such a structure that positive and negative electrodes are alternately laminated with a solid electrolyte layer interposed therebetween. The electrode body has at least a part containing a substance including sulfur. The negative electrode has: a negative electrode current collector made of Al; and a negative electrode active material layer formed on at least one face of the negative electrode current collector. In the negative electrode current collector, a plated layer containing Ni and/or Cr is formed on the face where the negative electrode active material layer is formed. In an end of the negative electrode current collector, a negative electrode current collector uncoated part is formed, which does not have the plated layer nor the negative electrode active material layer. To the negative electrode current collector uncoated part, a terminal made of Al for external connection is joined.SELECTED DRAWING: Figure 1

Description

本発明は、二次電池に関する。詳しくは、二次電池の負極を構成する負極集電体の構造に関する。 The present invention relates to a secondary battery. Specifically, it relates to the structure of a negative electrode current collector that constitutes the negative electrode of a secondary battery.

リチウムイオン二次電池、ナトリウムイオン二次電池等の二次電池は、既存の電池に比べて軽量かつエネルギー密度が高いことから、近年、パソコンや携帯端末等のいわゆるポータブル電源さらには車両駆動用電源として好ましく用いられている。この用途のリチウムイオン二次電池等の二次電池は、特に、電気自動車（ＥＶ）、ハイブリッド自動車（ＨＶ）、プラグインハイブリッド自動車（ＰＨＶ）等の車両の駆動用高出力電源として、益々の普及が期待されている。 Rechargeable batteries such as lithium-ion rechargeable batteries and sodium-ion rechargeable batteries are lighter in weight and have higher energy density than existing batteries. It is preferably used as Secondary batteries such as lithium-ion secondary batteries for this purpose are increasingly popular as high-output power sources for driving vehicles such as electric vehicles (EV), hybrid vehicles (HV), and plug-in hybrid vehicles (PHV). Is expected.

この種の二次電池の一形態として、液状の電解質（電解液）に代えて粉末状の固体電解質を使用する形態の電池（いわゆる、全固体電池）が挙げられる。この種の二次電池は、典型的には、正極と、負極とが、固体電解質層を介在させつつ重ね合わせられた構造の電極体を備える。 An example of this type of secondary battery is a battery (so-called all-solid battery) in which a powdery solid electrolyte is used instead of a liquid electrolyte (electrolyte solution). This type of secondary battery typically includes an electrode body having a structure in which a positive electrode and a negative electrode are stacked with a solid electrolyte layer interposed therebetween.

この種の二次電池の負極を構成する集電体としては、一般に銅（Ｃｕ）製の集電体が採用されている。しかし、Ｃｕ製負極集電体は、固体電解質層、正極および負極（以下、特に正負を区別しないときは「電極」という。）のいずれかに硫黄を含有する材料（例えば、硫化物を含む硫黄系固体電解質）が存在する場合、当該硫黄成分とＣｕとの反応によって新たに硫化物を生じさせる虞があるという問題がある。当該発生した硫化物は、負極集電体と負極活物質層との界面における電子伝導抵抗（以下、「界面抵抗」という。）を増大させる要因となるため好ましくない。
かかる問題点に関して特許文献１には、Ｃｕ製の負極集電体本体の表面に、ＷＣ（タングステンカーバイド）、Ｔｉ、Ｃｒ等でコーティングを施したものが開示されている。特許文献１に開示されるようなコーティングをＣｕからなる負極集電体の表面に施すことにより、該負極集電体と硫黄を含有する材料との接触を妨げることによって、特に負極における界面抵抗が増大することを抑制し、電池性能を向上させることができる、等の利点がある。 A current collector made of copper (Cu) is generally used as a current collector that constitutes the negative electrode of this type of secondary battery. However, the Cu negative electrode current collector is a material containing sulfur (for example, sulfur containing sulfide) in any of the solid electrolyte layer, the positive electrode and the negative electrode (hereinafter referred to as “electrode” when positive and negative are not particularly distinguished). If a system solid electrolyte is present, there is a problem that a sulfide may be newly generated by the reaction between the sulfur component and Cu. The generated sulfide is not preferable because it becomes a factor of increasing the electron conduction resistance (hereinafter, referred to as “interface resistance”) at the interface between the negative electrode current collector and the negative electrode active material layer.
Regarding such a problem, Patent Document 1 discloses a negative electrode current collector body made of Cu having a surface coated with WC (tungsten carbide), Ti, Cr or the like. By applying the coating as disclosed in Patent Document 1 to the surface of the negative electrode current collector made of Cu to prevent the contact between the negative electrode current collector and the material containing sulfur, the interfacial resistance particularly in the negative electrode is increased. There is an advantage that the increase can be suppressed and the battery performance can be improved.

特開２０１２−４９０２３号公報JP, 2012-49023, A

しかしながら、引用文献１に開示されている技術では、上記コーティングによって、Ｃｕからなる負極集電体と、硫黄を含有する材料との直接的な接触は妨げられているものの、該負極集電体の加工工程（特に、切断処理）において生じる微細なＣｕ片が負極集電体上に残存し得る。したがって、該Ｃｕ片と、硫黄を含有する材料とが反応し、生成した硫化物によって界面抵抗が増大する可能性を完全に払拭することは困難である。さらに、負極集電体の全面にコーティングを施すと、コーティングに用いられた金属（例えば、Ｔｉ）と、外部接続用の端子（以下、単に「端子」ともいう。）の材料である金属（例えば、Ａｌ）とが異なり、これらの接続部分においては、異なる金属が直接接触することとなる。このような場合、異なる金属間の再結晶温度の差に起因して、コーティングが施された負極集電体と、端子とを、効率的に超音波溶接できなくなる虞がある。これらのことにより、二次電池の電池性能を向上し、かつ、良好な状態で維持することが妨げられ得るため、好ましくない。
そこで本発明は、これらの問題点を根本から解決するべく、硫黄を含む物質を含有する電極体を備えた二次電池であって、銅と硫黄成分との反応が全く生じ得ない構成の負極集電体を備えた二次電池を提供することを目的とする。 However, in the technique disclosed in Patent Document 1, although the above-mentioned coating prevents direct contact between the negative electrode current collector made of Cu and the material containing sulfur, the negative electrode current collector of the negative electrode current collector is prevented. Fine Cu pieces generated in the processing step (particularly, the cutting treatment) may remain on the negative electrode current collector. Therefore, it is difficult to completely eliminate the possibility that the Cu piece reacts with the sulfur-containing material and the sulfide produced increases the interface resistance. Further, when the whole surface of the negative electrode current collector is coated, a metal (for example, Ti) used for the coating and a metal (for example, simply referred to as a “terminal” hereinafter) for external connection (for example, Ti) is used. , Al), different metals come into direct contact at these connecting portions. In such a case, due to the difference in recrystallization temperature between different metals, there is a possibility that the coated negative electrode current collector and the terminal cannot be efficiently ultrasonically welded. These are not preferable because they can prevent the secondary battery from improving its battery performance and maintaining it in a good state.
Therefore, in order to solve these problems from the fundamental, the present invention is a secondary battery provided with an electrode body containing a substance containing sulfur, the negative electrode having a configuration in which reaction between copper and sulfur components cannot occur at all. It is an object to provide a secondary battery provided with a current collector.

本発明者は、負極集電体をＡｌで構成することに着目した。そして、硫黄成分と反応し難い金属元素からなるメッキ層を、集電体表面における負極活物質層（負極合材層）が塗布される部分に形成することによって、Ａｌからなる負極集電体を採用し得ることを見出した。
さらに、外部接続用の端子をＡｌで形成するとともに、Ａｌ製の負極集電体における当該端子と接続させる部分に相当する負極集電体未塗工部(即ち、負極活物質層が塗布されていない部分)には上記メッキ層を形成させないことによって、同種金属間、即ちＡｌ対Ａｌの超音波溶接が行え、Ａｌ製の負極集電体と端子との間で容易且つ強固な接合が実現されることを導き出し、本発明を完成するに至った。 The present inventor has noticed that the negative electrode current collector is made of Al. Then, by forming a plating layer made of a metal element that hardly reacts with the sulfur component on the portion of the surface of the current collector where the negative electrode active material layer (negative electrode mixture layer) is applied, the negative electrode current collector made of Al is obtained. It has been found that it can be adopted.
Further, the external connection terminal is formed of Al, and the negative electrode current collector uncoated portion (that is, the negative electrode active material layer is applied) corresponding to the portion of the negative electrode current collector made of Al to be connected to the terminal. By not forming the above-mentioned plating layer on the (non-existing portion), ultrasonic welding of the same kind of metal, that is, Al to Al can be performed, and easy and strong bonding is realized between the negative electrode current collector made of Al and the terminal. This led to the completion of the present invention.

即ち、上記目的を実現するべく、ここに開示される二次電池は、シート状の正極と、シート状の負極とが、固体電解質層を介在させつつ交互に重ね合わされた構造の電極体を備え、該電極体の少なくとも一部において硫黄を含む物質を含有する二次電池である。
上記負極は、Ａｌからなる負極集電体と、該負極集電体の少なくとも一方の面上に形成された負極活物質層とを備えている。また、上記負極集電体における上記負極活物質層が形成された面上には、Ｎｉおよび／またはＣｒからなるメッキ層が形成されている。
そして、上記負極集電体の端部に、上記メッキ層および負極活物質層のいずれも有さない負極集電体未塗工部が形成されており、その負極集電体未塗工部には、Ａｌからなる外部接続用端子が接合されていることを特徴とする。 That is, in order to achieve the above object, the secondary battery disclosed herein includes an electrode body having a structure in which a sheet-shaped positive electrode and a sheet-shaped negative electrode are alternately stacked with a solid electrolyte layer interposed therebetween. A secondary battery containing a substance containing sulfur in at least a part of the electrode body.
The negative electrode includes a negative electrode current collector made of Al and a negative electrode active material layer formed on at least one surface of the negative electrode current collector. A plating layer made of Ni and/or Cr is formed on the surface of the negative electrode current collector on which the negative electrode active material layer is formed.
And, at the end of the negative electrode current collector, a negative electrode current collector uncoated portion having neither the plating layer nor the negative electrode active material layer is formed, and the negative electrode current collector uncoated portion is formed. Is characterized in that an external connection terminal made of Al is joined.

かかる構成の二次電池では、電極体中に硫黄を含む物質(例えば、硫化物を含む硫黄系固体電解質)を含有する二次電池においてＡｌからなる負極集電体を採用した結果、上述したような銅製の負極集電体を採用した場合の問題が根本から解消されている。また、負極活物質層が形成されている部分に上記メッキ層が形成されているため、集電体本体の構成金属と硫黄成分の反応による硫化物の形成が防止され、当該硫化物による負極における界面抵抗の増大を抑制することができる。
また、ここで開示される二次電池では、上記負極集電体未塗工部とＡｌ製の外部接続用端子との同種金属間（Ａｌ対Ａｌ）で接合が行えるため、Ａｌ製の負極集電体と外部接続用の端子との間で効率的な接合を実現することができ、これらによって、二次電池の電池性能を向上することができる。 In the secondary battery having such a configuration, as a result of employing the negative electrode current collector made of Al in the secondary battery containing a substance containing sulfur in the electrode body (for example, a sulfur-based solid electrolyte containing sulfide), as described above. The problem of using a copper negative electrode current collector has been fundamentally solved. Further, since the plating layer is formed in the portion where the negative electrode active material layer is formed, the formation of sulfide due to the reaction between the constituent metal of the current collector body and the sulfur component is prevented and It is possible to suppress an increase in interface resistance.
Further, in the secondary battery disclosed herein, since the uncoated portion of the negative electrode current collector and the external connection terminal made of Al can be bonded between the same metals (Al to Al), the negative electrode collector made of Al is formed. Efficient joining can be realized between the electric body and the terminal for external connection, and these can improve the battery performance of the secondary battery.

一実施形態に係る二次電池を構成する電極体を模式的に示す要部断面図である。It is a principal part sectional view which shows typically the electrode body which comprises the secondary battery which concerns on one Embodiment. 一実施形態に係る二次電池を構成する負極を一方の面から見た平面図である。FIG. 3 is a plan view of a negative electrode forming the secondary battery according to the embodiment as viewed from one side.

以下、図面を参照しながら、本発明による一実施形態を説明する。なお、以下に説明する図面において、同じ作用を奏する部材、部位には同じ符号を付し、重複する説明は省略または簡略化することがある。また、各図における寸法関係（長さ、幅、厚さ等）は実際の寸法関係を反映するものではない。また、本明細書において特に言及している事項以外の事柄であって本発明の実施に必要な事柄は、当該分野における従来技術に基づく当業者の設計事項として把握され得る。 An embodiment according to the present invention will be described below with reference to the drawings. In the drawings described below, members and parts having the same function are denoted by the same reference numerals, and duplicate description may be omitted or simplified. Further, the dimensional relationships (length, width, thickness, etc.) in each drawing do not reflect the actual dimensional relationships. Further, matters other than the matters particularly referred to in this specification and necessary for carrying out the present invention can be grasped as design matters of a person skilled in the art based on conventional technology in the field.

本明細書において「二次電池」とは、繰り返し充放電可能な蓄電デバイス一般をいい、リチウムイオン二次電池等のいわゆる蓄電池ならびに電気二重層キャパシタ等の蓄電素子を包含する用語である。また、「リチウムイオン二次電池」とは、電荷担体としてリチウムイオンを利用し、正負極間のリチウムイオンの移動により充放電が行われる二次電池をいう。また、「全固体電池」とは、固体電解質を備えた二次電池をいう。
また、本明細書において、「硫黄を含む物質」とは、電池を使用する際に、集電体（特に、負極集電体）と反応し得る硫黄を生じさせる物質をいう。
以下、扁平形状の全固体リチウムイオン二次電池を例にして、本発明について詳細に説明する。なお、以下で説明する実施形態は、本発明をかかる実施形態に記載されたものに限定することを意図したものではない。 In the present specification, the term “secondary battery” generally refers to a power storage device that can be repeatedly charged and discharged, and is a term that includes so-called storage batteries such as lithium ion secondary batteries and power storage elements such as electric double layer capacitors. The term “lithium ion secondary battery” refers to a secondary battery that utilizes lithium ions as charge carriers and is charged and discharged by the movement of lithium ions between the positive and negative electrodes. Further, the “all-solid-state battery” refers to a secondary battery provided with a solid electrolyte.
In addition, in the present specification, the “substance containing sulfur” refers to a substance that produces sulfur capable of reacting with the current collector (particularly, the negative electrode current collector) when the battery is used.
Hereinafter, the present invention will be described in detail by taking a flat-shaped all-solid-state lithium-ion secondary battery as an example. It should be noted that the embodiments described below are not intended to limit the present invention to those described in the embodiments.

本実施形態に係る全固体リチウムイオン二次電池は、図示しないラミネートフィルムによって電極体２０を内部に封止する形態の密閉構造の二次電池である。
図１は、本実施形態に係る全固体リチウムイオン二次電池を構成する電極体２０の要部断面図を示している。また、図２は、電極体２０を構成する負極５０の一方の面を示す平面図である。
図１に示すように、本実施形態に係る電極体２０は、シート状の正極３０と、シート状の負極５０とが、シート幅広面方向（図中のＺ方向）に、正負極間に固体電解質層４０を介在させつつ交互に積層されて形成される積層電極体２０である。 The all-solid-state lithium-ion secondary battery according to this embodiment is a secondary battery having a sealed structure in which the electrode body 20 is sealed inside by a laminate film (not shown).
FIG. 1 shows a cross-sectional view of a main part of an electrode body 20 constituting an all-solid-state lithium-ion secondary battery according to this embodiment. Further, FIG. 2 is a plan view showing one surface of the negative electrode 50 forming the electrode body 20.
As shown in FIG. 1, in the electrode body 20 according to the present embodiment, a sheet-shaped positive electrode 30 and a sheet-shaped negative electrode 50 are solid-stated between the positive and negative electrodes in the sheet wide surface direction (Z direction in the drawing). The laminated electrode body 20 is formed by alternately laminating the electrolyte layers 40.

図１および図２に示されるように、この積層電極体２０における負極５０は、負極集電体５２および負極活物質層５４を備えている。負極集電体５２はアルミニウム（Ａｌ）で構成されている。
負極活物質層５４は、負極活物質並びに固体電解質を含有する層であり、さらに必要に応じて、導電材やバインダ（結合剤）等を含有してもよい。負極活物質として、この種の電池で従来公知の物質を使用することができる。例えば、グラファイト、メソカーボンマイクロビーズ、カーボンブラック等の炭素系の負極活物質が挙げられる。また、ケイ素（Ｓｉ）又はスズ（Ｓｎ）を構成元素とする負極活物質を使用してもよい。なお、負極活物質層５４に含有される固体電解質としては、後述する固体電解質層４０に含有される固体電解質と同種の材料を用いることができる。 As shown in FIGS. 1 and 2, the negative electrode 50 in this laminated electrode body 20 includes a negative electrode current collector 52 and a negative electrode active material layer 54. The negative electrode current collector 52 is made of aluminum (Al).
The negative electrode active material layer 54 is a layer containing a negative electrode active material and a solid electrolyte, and may further contain a conductive material, a binder (binder) and the like, if necessary. As the negative electrode active material, a conventionally known material can be used in this type of battery. Examples thereof include carbonaceous negative electrode active materials such as graphite, mesocarbon microbeads, and carbon black. Further, a negative electrode active material containing silicon (Si) or tin (Sn) as a constituent element may be used. As the solid electrolyte contained in the negative electrode active material layer 54, the same material as the solid electrolyte contained in the solid electrolyte layer 40 described later can be used.

図１に示されるように、負極集電体５２における負極活物質層５４が形成された面上には、メッキ層５８が形成されている。
本実施形態に係るメッキ層５８はクロム（Ｃｒ）および／またはニッケル（Ｎｉ）を構成金属元素とするメッキ層である。メッキ層５８の形成方法としては、従来公知の方法を特に制限なく使用することができる。例えば、Ａｌからなる負極集電体５２に適当な前処理（例えば、ジンケート処理等）を行い、次いでメッキ処理（例えば、電気メッキ処理、無電解メッキ処理等）を行う方法が挙げられる。メッキ処理の内容自体は，本発明を構成するものではなく、詳細な説明は省略する。 As shown in FIG. 1, a plating layer 58 is formed on the surface of the negative electrode current collector 52 on which the negative electrode active material layer 54 is formed.
The plating layer 58 according to this embodiment is a plating layer containing chromium (Cr) and/or nickel (Ni) as constituent metal elements. As a method of forming the plating layer 58, a conventionally known method can be used without particular limitation. For example, there may be mentioned a method in which the negative electrode current collector 52 made of Al is subjected to an appropriate pretreatment (eg, zincate treatment) and then a plating treatment (eg, electroplating treatment, electroless plating treatment, etc.). The content of the plating process itself does not constitute the present invention, and detailed description thereof will be omitted.

負極集電体５２の一方の端部には、メッキ層５８および負極活物質層５４のいずれも有さない負極集電体未塗工部５２ａが形成されている。即ち、本実施形態では、負極集電体未塗工部５２ａは、図面中における左方向（Ｌ方向）に突出し、重ね合わせられて外部接続用端子５６（即ち、負極集電タブ）と後述する溶接手段によって接合された接合部Ｍを形成している。かかる外部接続用端子５６の他端側は、図示しないラミネートフィルム製外装体から電池外部に引き出されており、外部の回路や素子等と電気的に接続可能に配置されるものであるが、かかる外部の接続構造は本発明を特徴付ける部分ではないため、詳細な説明は省略する。 At one end of the negative electrode current collector 52, a negative electrode current collector uncoated portion 52a having neither the plating layer 58 nor the negative electrode active material layer 54 is formed. That is, in the present embodiment, the negative electrode current collector uncoated portion 52a projects in the left direction (L direction) in the drawing and is overlapped to be described later as the external connection terminal 56 (that is, the negative electrode current collecting tab). A joint portion M joined by welding means is formed. The other end of the external connection terminal 56 is drawn out of the battery from a laminate film exterior body (not shown) and is arranged so as to be electrically connectable to an external circuit or element. Since the external connection structure is not a feature of the present invention, detailed description thereof will be omitted.

また、図１に示されるように、本実施形態に係る正極３０は、正極集電体３２および正極活物質層３４を備えている。特に限定するものではないが、正極集電体３２は、通常はＡｌで構成されている。
正極集電体の少なくとも一方の面に形成される正極活物質層３４を構成する材料等は従来の一般的なこの種の二次電池の正極に用いられるものと同様のものを制限なく使用可能である。正極の構成は、特に本発明を特徴づけるものではないため、詳細な説明は省略する。なお、図示していないが、積層された各正極集電体３２の図面中における右方向（Ｒ方向）の端部には、それぞれ、負極と同様に正極集電体未塗工部が形成され、重ね合わせられて外部接続用端子（即ち、正極集電タブ）と適当な溶接手段によって接合されている。 Further, as shown in FIG. 1, the positive electrode 30 according to this embodiment includes a positive electrode current collector 32 and a positive electrode active material layer 34. Although not particularly limited, the positive electrode current collector 32 is usually made of Al.
As the material for forming the positive electrode active material layer 34 formed on at least one surface of the positive electrode current collector, the same material as that used for the positive electrode of the conventional general secondary battery of this type can be used without limitation. Is. Since the configuration of the positive electrode does not particularly characterize the present invention, detailed description thereof will be omitted. Although not shown, a positive electrode current collector uncoated portion is formed at the end of each stacked positive electrode current collector 32 in the right direction (R direction) in the drawing, similarly to the negative electrode. , Which are superposed and joined to the external connection terminal (that is, the positive electrode current collecting tab) by a suitable welding means.

積層電極体２０において、正負極間に形成される固体電解質層４０は、少なくとも固体電解質を含有する。本実施形態に係る電極体２０は、該電極体の少なくとも一部において硫黄を含む物質を含有するものであるが、かかる硫黄を含む物質としての好適例として、正負極活物質層３４，５４や固体電解質層４０に含有され得る従来公知の硫化物固体電解質が挙げられる。硫化物系固体電解質の例として、Ｌｉ２Ｓ−ＳｉＳ２系、Ｌｉ２Ｓ−Ｐ２Ｓ３系、Ｌｉ２Ｓ−Ｐ２Ｓ５系、Ｌｉ２ＳＧｅＳ２系、Ｌｉ２Ｓ−Ｂ２Ｓ３系、等のガラスまたはガラスセラミックスが挙げられる。 In the laminated electrode body 20, the solid electrolyte layer 40 formed between the positive and negative electrodes contains at least a solid electrolyte. The electrode body 20 according to the present embodiment contains a substance containing sulfur in at least a part of the electrode body. As a preferable example of the substance containing sulfur, the positive and negative electrode active material layers 34, 54 and Examples include conventionally known sulfide solid electrolytes that can be contained in the solid electrolyte layer 40. Examples of the sulfide-based solid electrolyte include Li 2 S-SiS 2 system, Li 2 S-P 2 S 3 system, Li 2 S-P 2 S 5 system, Li 2 SGeS 2 system, Li 2 S-B 2 S. Examples include glass and glass ceramics such as 3 series.

上述したような、構成の積層電極体は、上記メッキ層付きＡｌ集電体を用意すること以外、通常のこの種の全固体電池に用いられる積層電極体と同様に構築することができる。即ち、大まかに言えば、Ａｌからなる負極集電体５２の表面の一部分（即ち、負極活物質層５４が形成される部分）に、予めＮｉおよび／またはＣｒからなるメッキ層５８を形成する。次いで、該メッキ層５８の上に負極活物質層５４を形成して負極５０を作製する。次いで、当該負極５０と別途用意した正極３０とを、固体電解質層４０を介在させつつ交互に重ね合わせることにより、積層電極体２０を構築することができる。
その後、図１に示されるように、積層された負極５０それぞれの負極集電体未塗工部５２ａが積層方向に重ね合わせられ、別途用意した外部接続用端子（負極集電タブ）５６と超音波溶接等の溶接手段によって接合されて、接合部Ｍが形成される。正極側も同様に積層方向に重ね合わせられた正極集電体未塗工部と外部接続用端子（正極集電タブ）とを超音波溶接等の溶接手段によって接合する。
そして、適当な外装体によって構築した電極体を封止することにより、所望する二次電池を製造することができる。 The laminated electrode body having the above-described configuration can be constructed in the same manner as the laminated electrode body used in a normal all-solid-state battery of this type, except that the Al current collector with a plated layer is prepared. That is, roughly speaking, the plating layer 58 made of Ni and/or Cr is previously formed on a part of the surface of the negative electrode current collector 52 made of Al (that is, the portion where the negative electrode active material layer 54 is formed). Next, the negative electrode active material layer 54 is formed on the plated layer 58 to produce the negative electrode 50. Then, the negative electrode 50 and the separately prepared positive electrode 30 are alternately superposed with the solid electrolyte layer 40 interposed therebetween, whereby the laminated electrode body 20 can be constructed.
Thereafter, as shown in FIG. 1, the negative electrode current collector uncoated portions 52a of the laminated negative electrodes 50 are overlapped in the stacking direction, and the external connection terminals (negative electrode current collecting tab) 56 and a The joining portion M is formed by joining by welding means such as sonic welding. Similarly, on the positive electrode side, the uncoated portion of the positive electrode current collector and the external connection terminal (positive electrode current collecting tab), which are stacked in the stacking direction, are joined by welding means such as ultrasonic welding.
Then, a desired secondary battery can be manufactured by sealing the electrode body constructed with an appropriate outer package.

本実施形態に係る二次電池においては、負極活物質層が形成されている部分にメッキ層を形成することによって、負極集電体と、電極体中に含有される硫黄を含む物質とが反応してＡｌの硫化物が形成されることを防止でき、負極において界面抵抗の増大を抑制することができる。さらに、Ａｌ製の負極集電体に上述する未塗工部を形成することによって、負極集電体をＡｌからなる外部接続用端子と同種金属間において効率的に超音波溶接等の溶接手段によって接合することができる。これらによって、電池性能が向上された二次電池を提供することができる。 In the secondary battery according to the present embodiment, the negative electrode current collector and the substance containing sulfur contained in the electrode body react with each other by forming the plating layer in the portion where the negative electrode active material layer is formed. As a result, the formation of Al sulfide can be prevented, and the increase in interfacial resistance in the negative electrode can be suppressed. Furthermore, by forming the above-mentioned uncoated portion on the negative electrode current collector made of Al, the negative electrode current collector can be efficiently welded between the external connection terminal made of Al and the same metal by welding means such as ultrasonic welding. Can be joined. By these, a secondary battery having improved battery performance can be provided.

２０ 電極体
３０ 正極
３２ 正極集電体
３４ 正極活物質層
４０ 固体電解質層
５０ 負極
５２ 負極集電体
５２ａ 負極集電体未塗工部
５４ 負極活物質層
５６ 外部接続用端子（負極集電タブ）
５８ メッキ層
Ｍ 接合部
Ｌ 左方向
Ｒ 右方向
Ｚ 幅広面方向 20 electrode body 30 positive electrode 32 positive electrode current collector 34 positive electrode active material layer 40 solid electrolyte layer 50 negative electrode 52 negative electrode current collector 52a negative electrode current collector uncoated portion 54 negative electrode active material layer 56 external connection terminal (negative electrode current collecting tab) )
58 Plating layer M Joint L Left direction R Right direction Z Wide surface direction

Claims (1)

シート状の正極と、シート状の負極とが、固体電解質層を介在させつつ交互に重ね合わされた構造の電極体を備え、該電極体の少なくとも一部において硫黄を含む物質を含有する二次電池であって、
前記負極は、Ａｌからなる負極集電体と、該負極集電体の少なくとも一方の面上に形成された負極活物質層とを備えており、
前記負極集電体における前記負極活物質層が形成された面上には、Ｎｉおよび／またはＣｒからなるメッキ層が形成されており、
ここで、前記負極集電体の端部に、前記メッキ層および前記負極活物質層のいずれも有さない負極集電体未塗工部が形成されており、
該負極集電体未塗工部には、Ａｌからなる外部接続用端子が接合されている、二次電池。
A secondary battery including an electrode body having a structure in which a sheet-shaped positive electrode and a sheet-shaped negative electrode are alternately stacked with a solid electrolyte layer interposed, and a substance containing sulfur is contained in at least a part of the electrode body. And
The negative electrode includes a negative electrode current collector made of Al and a negative electrode active material layer formed on at least one surface of the negative electrode current collector,
A plating layer made of Ni and/or Cr is formed on a surface of the negative electrode current collector on which the negative electrode active material layer is formed,
Here, at the end of the negative electrode current collector, a negative electrode current collector uncoated portion having neither the plating layer nor the negative electrode active material layer is formed,
A secondary battery in which an external connection terminal made of Al is joined to the uncoated portion of the negative electrode current collector.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5693269A (en) * 1979-12-24 1981-07-28 Chloride Silent Power Ltd Cathode current collector for sodium sulfur battery
US5518839A (en) * 1995-04-12 1996-05-21 Olsen; Ib I. Current collector for solid electrochemical cell
JPH08306390A (en) * 1995-04-28 1996-11-22 Sony Corp Nonaqueous electrolyte secondary battery
JP2007328952A (en) * 2006-06-06 2007-12-20 Toshiba Corp Non-aqueous electrolyte battery, battery pack, and automobile
JP2012049023A (en) * 2010-08-27 2012-03-08 Toyota Motor Corp Battery
JP2012164571A (en) * 2011-02-08 2012-08-30 Sumitomo Electric Ind Ltd Negative electrode body and lithium ion battery
JP2015088330A (en) * 2013-10-30 2015-05-07 トヨタ自動車株式会社 Sulfur-including all-solid battery
JP2016009526A (en) * 2014-06-20 2016-01-18 古河電気工業株式会社 Negative electrode current collector for all-solid battery and all-solid battery
JP2020091997A (en) * 2018-12-05 2020-06-11 昭和電工株式会社 Lithium ion secondary battery

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5693269A (en) * 1979-12-24 1981-07-28 Chloride Silent Power Ltd Cathode current collector for sodium sulfur battery
US5518839A (en) * 1995-04-12 1996-05-21 Olsen; Ib I. Current collector for solid electrochemical cell
JPH08306390A (en) * 1995-04-28 1996-11-22 Sony Corp Nonaqueous electrolyte secondary battery
JP2007328952A (en) * 2006-06-06 2007-12-20 Toshiba Corp Non-aqueous electrolyte battery, battery pack, and automobile
JP2012049023A (en) * 2010-08-27 2012-03-08 Toyota Motor Corp Battery
JP2012164571A (en) * 2011-02-08 2012-08-30 Sumitomo Electric Ind Ltd Negative electrode body and lithium ion battery
JP2015088330A (en) * 2013-10-30 2015-05-07 トヨタ自動車株式会社 Sulfur-including all-solid battery
JP2016009526A (en) * 2014-06-20 2016-01-18 古河電気工業株式会社 Negative electrode current collector for all-solid battery and all-solid battery
JP2020091997A (en) * 2018-12-05 2020-06-11 昭和電工株式会社 Lithium ion secondary battery

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