JP2020194741A - All-solid-state lithium secondary battery and manufacturing method of all-solid-state lithium secondary battery - Google Patents
All-solid-state lithium secondary battery and manufacturing method of all-solid-state lithium secondary battery Download PDFInfo
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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
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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
- 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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Abstract
Description
本発明は、正極とリチウム負極との間に固体電解質層が介設された全固体リチウム二次電池及びこの全固体リチウム二次電池を製造する全固体リチウム二次電池の製造方法に関する。 The present invention relates to an all-solid-state lithium secondary battery in which a solid electrolyte layer is interposed between a positive electrode and a lithium negative electrode, and a method for manufacturing an all-solid-state lithium secondary battery for producing the all-solid-state lithium secondary battery.
従来、この種の全固体リチウム二次電池として、基板上に離間して正極集電体層と負極集電体層とが並設され、並設方向一方側に位置する第１接続部を除く正極集電体層の部分に積層された正極上に固体電解質層が積層され、並設方向他方側に位置する第２接続部を除く負極集電体層の部分と固体電解質層とを覆うようにリチウム負極が積層された全固体リチウム二次電池セルを複数備えたものが知られている（例えば、特許文献１参照）。 Conventionally, as an all-solid-state lithium secondary battery of this type, a positive electrode current collector layer and a negative electrode current collector layer are arranged side by side on a substrate, except for a first connection portion located on one side in the parallel arrangement direction. A solid electrolyte layer is laminated on the positive electrode laminated on the positive electrode current collector layer so as to cover the negative electrode current collector layer and the solid electrolyte layer except for the second connection portion located on the other side in the parallel arrangement direction. It is known that a plurality of all-solid-state lithium secondary battery cells in which a lithium negative electrode is laminated are provided (see, for example, Patent Document 1).
上記全固体リチウム二次電池では、各層内又は層間に少なからずパーティクルが存し、このパーティクル付近の層にはピンホールや微小クラック等の欠陥が形成される。この欠陥を介して正極集電体層と負極集電体層が導通して短絡するという異常が発生するため、全固体リチウム二次電池の製造の歩留りが低下するという問題がある。そこで、特許文献１記載の全固体リチウム二次電池の製造方法では、短絡を修復する修復工程を設けている。
In the above-mentioned all-solid-state lithium secondary battery, not a few particles are present in each layer or between layers, and defects such as pinholes and microcracks are formed in the layer near the particles. Through this defect, an abnormality occurs in which the positive electrode current collector layer and the negative electrode current collector layer are conductive and short-circuited, so that there is a problem that the production yield of the all-solid-state lithium secondary battery is lowered. Therefore, in the method for manufacturing an all-solid-state lithium secondary battery described in
然し、修復工程を設ける分、特許文献１記載の全固体リチウム二次電池の製造方法は手間のかかるものとなっており、全固体リチウム二次電池のコストに反映されるため、より簡便に製造できる全固体リチウム二次電池とその製造方法の実現が望まれる。
However, since the repair step is provided, the method for manufacturing the all-solid-state lithium secondary battery described in
本発明は、以上の点に鑑み、より簡便に製造できる全固体リチウム二次電池及び全固体リチウム二次電池の製造方法を提供することをその課題としている。 In view of the above points, it is an object of the present invention to provide a method for manufacturing an all-solid-state lithium secondary battery and an all-solid-state lithium secondary battery that can be manufactured more easily.
上記課題を解決するために、基板上に離間して正極集電体層と負極集電体層とが並設され、並設方向一方側に位置する第１接続部を除く正極集電体層の部分に積層された正極上に固体電解質層が積層され、並設方向他方側に位置する第２接続部を除く負極集電体層の部分と固体電解質層とを覆うようにリチウム負極が積層された全固体リチウム二次電池セルを複数備えた本発明の全固体リチウム二次電池は、各全固体リチウム二次電池セルが、正極集電体層の第１接続部及び負極集電体層の第２接続部の夫々に形成される導体層により並列接続され、全固体リチウム二次電池セルの一部は、電池として機能しない絶縁セルであり、残りの電池として機能する全固体リチウム二次電池セルには、正極集電体層の第１接続部及び負極集電体層の第２接続部を除いてリチウム負極を覆うように保護層が積層されていることを特徴とする。 In order to solve the above problems, the positive electrode current collector layer and the negative electrode current collector layer are arranged side by side on the substrate, and the positive electrode current collector layer excluding the first connection portion located on one side in the parallel arrangement direction. A solid electrolyte layer is laminated on the positive electrode laminated in the above portion, and a lithium negative electrode is laminated so as to cover a portion of the negative electrode current collector layer excluding the second connection portion located on the other side in the parallel arrangement direction and the solid electrolyte layer. In the all-solid-state lithium secondary battery of the present invention provided with a plurality of all-solid-state lithium secondary battery cells, each all-solid-state lithium secondary battery cell is a first connection portion of a positive electrode current collector layer and a negative electrode current collector layer. Some of the all-solid-state lithium secondary battery cells are isolated cells that do not function as batteries and are connected in parallel by the conductor layers formed in each of the second connection portions of the above, and all-solid-state lithium secondary batteries that function as the remaining batteries. The battery cell is characterized in that a protective layer is laminated so as to cover the lithium negative electrode except for the first connection portion of the positive electrode current collector layer and the second connection portion of the negative electrode current collector layer.
本発明の全固体リチウム二次電池によれば、電池として機能する全固体リチウム二次電池セル及び電池として機能しない絶縁セルの全てが、各セルの正極集電体層の第１接続部及び負極集電体層の第２接続部の夫々の上に積層される導体層により並列接続されるため、絶縁セルが一部存しても、正極集電体層及び負極集電体層を介して通電可能であり、全固体リチウム二次電池は電池として正常に機能する。従って、短絡した異常な全固体リチウム二次電池セルを正常なセルに修復する必要がなく、より簡便に全固体リチウム二次電池を製造できる。 According to the all-solid-state lithium secondary battery of the present invention, all of the all-solid-state lithium secondary battery cell that functions as a battery and the insulating cell that does not function as a battery are the first connection portion and the negative electrode of the positive electrode current collector layer of each cell. Since they are connected in parallel by conductor layers laminated on each of the second connection portions of the current collector layer, even if some insulating cells are present, they are connected via the positive electrode current collector layer and the negative electrode current collector layer. It can be energized and the all-solid lithium secondary battery functions normally as a battery. Therefore, it is not necessary to repair the short-circuited abnormal all-solid-state lithium secondary battery cell to a normal cell, and the all-solid-state lithium secondary battery can be manufactured more easily.
また、上記の課題を解決するために、基板上に正極集電体層を形成する正極集電体層形成工程と、負極集電体層が形成される側と反対側に位置する第１接続部を除く正極集電体層の部分に正極を積層する正極形成工程と、正極上に固体電解質層を積層する固体電解質層形成工程と、固体電解質層から離間して正極集電体層と並置されるように基板上に負極集電体層を形成する負極集電体層形成工程と、負極集電体層の正極集電体層と反対側に位置する第２接続部と正極集電体層の第１接続部との両方を除いて、正極集電体層及び負極集電体層を接続するようにリチウム負極を積層するリチウム負極形成工程と、リチウム負極が積層された全固体リチウム二次電池セルの正常・異常を短絡の有無により判定するセル判定工程とを含む本発明の全固体リチウム二次電池の製造方法は、セル判定工程で、短絡無しで正常と判定された正常セルに、正極集電体層の第１接続部及び負極集電体層の第２接続部を除いてリチウム負極を覆うように保護層を積層する保護層形成工程と、セル判定工程で、短絡有りで異常と判定された異常セルを絶縁化して絶縁セルにする絶縁化処理工程と、正常セル及び絶縁セルの全てを、各セルの正極集電体層の第１接続部及び負極集電体層の第２接続部の夫々の上に導体層を積層して並列接続するセル並列接続工程とを更に含むことを特徴とする。 Further, in order to solve the above problems, the positive electrode current collector layer forming step of forming the positive electrode current collector layer on the substrate and the first connection located on the side opposite to the side where the negative electrode current collector layer is formed are formed. A positive electrode forming step of laminating a positive electrode on a portion of the positive electrode current collector layer excluding a portion, a solid electrolyte layer forming step of laminating a solid electrolyte layer on the positive electrode, and a juxtaposition with the positive electrode current collector layer separated from the solid electrolyte layer. The negative electrode current collector layer forming step of forming the negative electrode current collector layer on the substrate, and the second connection portion and the positive electrode current collector located on the opposite side of the negative electrode current collector layer from the positive electrode current collector layer. A lithium negative electrode forming step in which a lithium negative electrode is laminated so as to connect a positive electrode current collector layer and a negative electrode current collector layer except for both the first connection portion of the layer, and an all-solid-state lithium two in which the lithium negative electrode is laminated. The method for manufacturing an all-solid-state lithium secondary battery of the present invention, which includes a cell determination step of determining the normality / abnormality of the next battery cell based on the presence or absence of a short circuit, is a normal cell determined to be normal without a short circuit in the cell determination step. In the protective layer forming step of laminating the protective layer so as to cover the lithium negative electrode and the cell determination step except for the first connection portion of the positive electrode current collector layer and the second connection portion of the negative electrode current collector layer, there is a short circuit. The insulation treatment step of insulating the abnormal cell determined to be abnormal to make it an insulating cell, and all of the normal cell and the insulating cell are connected to the first connection portion of the positive electrode current collector layer and the negative electrode current collector layer of each cell. It is characterized by further including a cell parallel connection step of laminating a conductor layer on each of the second connection portions and connecting them in parallel.
本発明の全固体リチウム二次電池の製造方法によれば、正常セル及び絶縁セルの全てを、各セルの正極集電体層の第１接続部及び負極集電体層の第２接続部の夫々の上に導体層を積層して並列接続するため、絶縁セルが一部存しても、正極集電体層及び負極集電体層を介して通電可能であり、全固体リチウム二次電池は電池として正常に機能する。従って、異常セルを正常なセルに修復する必要がなく、より簡便に全固体リチウム二次電池を製造できる。 According to the method for manufacturing an all-solid-state lithium secondary battery of the present invention, all of the normal cells and the insulating cells are connected to the first connection portion of the positive electrode current collector layer and the second connection portion of the negative electrode current collector layer of each cell. Since the conductor layers are laminated on each and connected in parallel, even if some insulating cells exist, they can be energized via the positive electrode current collector layer and the negative electrode current collector layer, and are all-solid-state lithium secondary batteries. Functions normally as a battery. Therefore, it is not necessary to repair the abnormal cell to a normal cell, and the all-solid-state lithium secondary battery can be manufactured more easily.
また、本発明の全固体リチウム二次電池の製造方法において、前記絶縁化処理工程が、異常セルをそのまま放置してリチウム負極を形成するリチウムを正極に移動させ、リチウム負極を消失させて絶縁セルにする工程であることが望ましい。これによれば、放置により短絡が進行してリチウム負極が消失するため、絶縁化のために特別な手段を講ずる必要がなく、全固体リチウム二次電池の製造が一層簡便になる。 Further, in the method for manufacturing an all-solid-state lithium secondary battery of the present invention, the insulation treatment step moves the lithium forming the lithium negative electrode to the positive electrode while leaving the abnormal cell as it is, and eliminates the lithium negative electrode to eliminate the insulating cell. It is desirable that this is the process of According to this, since the short circuit progresses and the lithium negative electrode disappears when left unattended, it is not necessary to take special measures for insulation, and the production of the all-solid-state lithium secondary battery becomes easier.
また、本発明の全固体リチウム二次電池の製造方法において、前記絶縁化処理工程が、異常セルのリチウム負極を大気と反応させて不導体にして絶縁セルにする工程であることが望ましい。これによれば、異常セルは、リチウム負極を大気に晒すだけで酸化、炭酸化等によりリチウム負極が不導体となって絶縁セルとなるため、絶縁化のために特別な手段を講ずる必要がない。このため、全固体リチウム二次電池の製造が一層簡便になる。 Further, in the method for manufacturing an all-solid-state lithium secondary battery of the present invention, it is desirable that the insulation treatment step is a step of reacting the lithium negative electrode of the abnormal cell with the atmosphere to make it non-conductor and make it an insulating cell. According to this, in the abnormal cell, the lithium negative electrode becomes a non-conductor due to oxidation, carbonation, etc. just by exposing the lithium negative electrode to the atmosphere, and becomes an insulating cell. Therefore, it is not necessary to take special measures for insulation. .. Therefore, the production of the all-solid-state lithium secondary battery becomes easier.
図１を参照して、電池として機能する正常な全固体リチウム二次電池セルＬＢＣ１（以下、正常セルＬＢＣ１と記すことがある）には、基板１上に離間して正極集電体層２と負極集電体層３とが並設されている。正極集電体層２は、並設方向一方側に位置する端部に接続部２１を有し、負極集電体層３は、並設方向他方側に位置する端部に接続部３１を有している。基板１の形状は特に限定されず、板状、シート状、フィルム状等が例示される。また、材料についても特に限定されず、ガラス、マイカ、アルミナ等が例示される。更に、基板１の厚さについても特に限定されず、１μｍ〜５０μｍの範囲が例示される。正極集電体層２及び負極集電体層３は、導電性を有し、集電体として広く用いられる材料から形成でき、モリブデン、ニッケル、クロム、アルミニウム、銅、金、チタン、バナジウム等の単体又は２種以上の合金が例示される。正極集電体層２及び負極集電体層３の厚さについても特に限定されず、１μｍ〜１５μｍの範囲が例示される。
With reference to FIG. 1, a normal all-solid-state lithium secondary battery cell LBC1 (hereinafter, may be referred to as a normal cell LBC1) that functions as a battery is separated from the
また、正常な全固体リチウム二次電池セルＬＢＣ１には、接続部２１を除く正極集電体層２の部分に正極４が積層され、正極４上に固体電解質層５が積層されている。正極４の材料は、リチウムイオンの吸蔵及び放出が可能である限り特に限定されない。例えば、ＬｉＣｏＯ２，ＬｉＮｉＯ２，ＬｉＭｎ２，ＬｉＭｎ２Ｏ４，ＬｉＦｅＰＯ４，ＴｉＳ２，ＬｉＭ１ｘＭ２ｙＯｚ（Ｍ１，Ｍ２は遷移金属、ｘ，ｙ，ｚは任意の実数）等を採用できる。固体電解質層５を形成する固体電解質については特に限定されず、Ｌｉ３ＰＯ４，Ｌｉ２Ｓ，Ｌｉ３ＰＯ４，ＬｉＰＯＮ等の無機固定電解質が例示される。正極４及び固体電解質層５の厚さについても特に限定されず、１μｍ〜３μｍの範囲が例示される。
Further, in the normal all-solid-state lithium secondary battery cell LBC1, the
更に、正常な全固体リチウム二次電池セルＬＢＣ１には、接続部３１を除く負極集電体層３の部分と固体電解質層５とを覆うようにリチウム負極６が積層されると共に、正極集電体層２の第１接続部２１及び負極集電体層３の第２接続部３１を除いてリチウム負極６を覆うように保護層７が積層されている。リチウム負極６の厚さについては特に限定されず、１μｍ〜３μｍ程度が例示される。保護層７を形成する材料についても特に限定されず、ポリテトラフルオロエチレン、シリカ等が例示される。基板１の表面から保護層７の表面までの厚さとしては、１５μｍ程度が例示される。
Further, in the normal all-solid-state lithium secondary battery cell LBC1, the lithium
各層２，３，４，５，６，７は、材料によって異なるが、スパッタリング法等のＰＶＤの他、ＣＶＤ等のドライコーティングによって形成可能である。また、各層２，３，４，５，６，７は、スクリーン印刷、オフセット印刷、インクジェット印刷等の後、乾燥するウェットコーティングによっても形成可能である。この場合、固体電解質層５を形成する固体電解質として、上記の他に、ポリエチレンオキシド、ポリプロピレンオキシド、ポリプロピレンオキシド誘導体等の高分子材料中にＬｉＰＥ６，ＬｉＣｌＯ４等のリチウム塩からなる溶質を含有させた混合物や、上記溶質を有機溶媒に溶解させた非水電解質を含浸させたゲル状のもの等も採用可能である。また、各層２，３，４，５，６，７の形成に際し、マスキング及びその除去を適宜行う。
Each
また、全固体リチウム二次電池セルの正常・異常は、短絡の有無によって判定でき、短絡の有無は、正極集電体層２と負極集電体層３との間の電圧測定によって行える。正常な全固体リチウム二次電池セルの場合、測定される電圧は、通常、２〜３Ｖ程度である。この電圧範囲が測定された場合、短絡無しの正常セルＬＢＣ１であると判定し、上記電圧範囲を下回る場合、短絡有りの異常セルであると判定する。尚、上記電圧範囲は、特に限定的ではなく、固体電解質層５を形成する固体電解質や、正極４を形成する材料等によって異なる。
Further, the normality / abnormality of the all-solid-state lithium secondary battery cell can be determined by the presence or absence of a short circuit, and the presence or absence of a short circuit can be determined by measuring the voltage between the positive electrode
図２を参照して、図１に示す正常な全固体リチウム二次電池セルＬＢＣ１を含む、本発明の全固体リチウム二次電池の一実施形態を説明する。上記の如く、各層２，３，４，５，６内又は層２，３，４，５，６間にパーティクルが存することに起因する短絡が発生して異常セルが製造される場合がある。そこで、本実施形態の全固体リチウム二次電池ＬＢでは、異常セルを正常セルＬＢＣ１に修復することなく絶縁させて電池として機能しない絶縁セルＬＢＣ２として、正常な全固体リチウム二次電池セルＬＢＣ１と共に組み込む。即ち、正常な全固体リチウム二次電池セルＬＢＣ１及び絶縁セルＬＢＣ２の全てが、各セルＬＢＣ１，ＬＢＣ２の正極集電体層２及び負極集電体層３の、図１に示す第１接続部２１及び第２接続部３１の夫々の上に積層される導体層８，９によって並列接続される。導体層８，９を形成する材料については、導電性を有する限り特に限定されず、銅、ニッケル等の単体又は合金等が例示される。
An embodiment of the all-solid-state lithium secondary battery of the present invention including the normal all-solid-state lithium secondary battery cell LBC1 shown in FIG. 1 will be described with reference to FIG. As described above, an abnormal cell may be manufactured due to a short circuit caused by the presence of particles in each of the
また、全固体リチウム二次電池ＬＢでは、絶縁セルＬＢＣ２は、短絡の発生により絶縁して電池として機能しないセルであるため、絶縁セルＬＢＣ２には保護層７は設けず、正常セルＬＢＣ１のみに保護層７を積層することができる。上記の如く、本実施形態の全固体リチウム二次電池ＬＢでは、正常な全固体リチウム二次電池セルＬＢＣ１及び絶縁セルＬＢＣ２の全てが、各セルＬＢＣ１，ＬＢＣ２の正極集電体層２の第１接続部２１及び負極集電体層３の第２接続部３１の夫々の上に積層される導体層８，９によって並列接続されるため、絶縁セルＬＢＣ２が一部存しても、正極集電体層２及び負極集電体層３を介して通電可能であり、全固体リチウム二次電池ＬＢは電池として正常に機能する。従って、異常セルを正常セルＬＢＣ１に修復する必要がなく、全固体リチウム二次電池ＬＢは、要求される電力を供給することができ、しかも製造がより簡便なものである。
Further, in the all-solid-state lithium secondary battery LB, since the insulating cell LBC2 is a cell that is insulated due to the occurrence of a short circuit and does not function as a battery, the insulating cell LBC2 is not provided with the
次に、図１〜３を参照して、本発明の全固体リチウム二次電池の製造方法の一実施形態を説明する。本実施形態では、まず、正極集電体層形成工程Ｓ１で、基板１上に正極集電体層２を形成し、次いで、正極形成工程Ｓ２で、負極集電体層３が形成される側と反対側に位置する第１接続部２１を除く正極集電体層２の部分に正極４を積層する。この後、固体電解質層形成工程Ｓ３で、正極４上に固体電解質層５を積層し、次いで、負極集電体層形成工程Ｓ４で、固体電解質層５から離間して正極集電体層２と並置されるように基板１上に負極集電体層３を形成する。この後、リチウム負極形成工程Ｓ５で、負極集電体層３の正極集電体層２と反対側に位置する第２接続部３１と正極集電体層２の第１接続部２１との両方を除いて、正極集電体層２及び負極集電体層３を接続するようにリチウム負極６を積層する。次いで、セル判定工程Ｓ６で、リチウム負極６が積層された全固体リチウム二次電池セルの正常・異常を判定する。セル判定工程Ｓ６での全固体リチウム二次電池セルの正常・異常の判定は、上記の如く、短絡の有無により行う。
Next, an embodiment of the method for manufacturing an all-solid-state lithium secondary battery of the present invention will be described with reference to FIGS. In the present embodiment, first, the positive electrode
本実施形態では、セル判定工程Ｓ６で、短絡無しで正常と判定された正常セルＬＢＣ１に対しては、保護層形成工程Ｓ７で、正極集電体層２の第１接続部２１及び負極集電体層３の第２接続部３１を除いてリチウム負極６を覆うように保護層７を積層する。一方、セル判定工程Ｓ６で、短絡有りで異常と判定された異常セルに対しては、絶縁化処理工程Ｓ８で、絶縁化する処理を行い、絶縁セルＬＢＣ２にする。上記の如く、正極集電体層２と負極集電体層３との間の電圧測定によって所定の電圧範囲（通常、２〜３Ｖ程度）を下回る場合、短絡が発生していると考えられるため、絶縁化処理としては、異常セルをそのままで放置してリチウム負極６を形成するリチウムを正極４に移動させ、リチウム負極６を消失させて絶縁セルＬＢＣ２にする処理が例示される。放置時間は、セルの大きさ、固体電解質の材質等によって異なるが、２４時間程度が例示される。この場合、放置により短絡が進行してリチウム負極６が消失するため、絶縁化のために特別な手段を講ずる必要がない。
In the present embodiment, for the normal cell LBC1 which is determined to be normal without a short circuit in the cell determination step S6, the
また、絶縁化処理としては、異常セルを大気に晒し、リチウム負極６を形成するリチウムを大気中の酸素や二酸化炭素と反応させて酸化リチウムや炭酸リチウムにして不導体にして絶縁セルＬＢＣ２にする処理も例示される。この場合、異常セルは、リチウム負極６を大気に晒すだけで酸化、炭酸化等によりリチウム負極６が不導体となって絶縁セルＬＢＣ２となるため、絶縁化のために特別な手段を講ずる必要がない。
Further, as an insulation treatment, the abnormal cell is exposed to the atmosphere, and the lithium forming the lithium
そして、本実施形態では、セル並列接続工程Ｓ９で、正常セルＬＢＣ１と絶縁セルＬＢＣ２の全てを、各セルＬＢＣ１，ＬＢＣ２の正極集電体層２の第１接続部２１及び負極集電体層３の第２接続部３１の夫々の上に導体層８，９を積層して並列接続し、全固体リチウム二次電池ＬＢを製造する。
Then, in the present embodiment, in the cell parallel connection step S9, all of the normal cell LBC1 and the insulating cell LBC2 are connected to the
上記の如く、本実施形態では、正常セルＬＢＣ１及び絶縁セルＬＢＣ２の全てを、各セルＬＢＣ１，ＬＢＣ２の正極集電体層２の第１接続部２１及び負極集電体層３の第２接続部３１の夫々の上に導体層８，９を積層して並列接続するため、絶縁セルＬＢＣ２が一部存しても、正極集電体層２及び負極集電体層３を介して通電可能であり、全固体リチウム二次電池ＬＢは電池として正常に機能する。従って、絶縁セルＬＢＣ２を正常セルＬＢＣ１に修復する必要がなく、より簡便に全固体リチウム二次電池ＬＢを製造できる。そして、異常セルの放置又はリチウム負極６を大気に晒すかのいずれの絶縁化処理も、絶縁化のために特別な手段を講ずる必要がないため、全固体リチウム二次電池ＬＢの製造が一層簡便になる。
As described above, in the present embodiment, all of the normal cell LBC1 and the insulating cell LBC2 are connected to the
尚、各層２，３，４，５，６，７は、材料によって異なるが、スパッタリング法等のＰＶＤの他、ＣＶＤ等のドライコーティングによって形成可能である。また、各層２，３，４，５，６，７の形成に際してマスキングやその除去を適宜行う。尚、各層２，３，４，５，６，７は、スクリーン印刷、オフセット印刷、インクジェット印刷等の後、乾燥するウェットコーティングによっても形成可能である。
Although the
以上、本発明を一実施形態に関して説明したが、本発明は上記実施形態に限定されない。例えば、全固体リチウム二次電池セルの大きさや形状等は、設置される部位によって適宜なものとすることができる。また、異常セルに対する絶縁化処理の処理条件もセルの大きさや短絡の程度等に応じて適宜変更することができ、更に、処理方法は上記実施形態に限定されることはなく、電池として機能しなくなる処理であれば他の処理方法も採用可能である。 Although the present invention has been described above with respect to one embodiment, the present invention is not limited to the above embodiment. For example, the size and shape of the all-solid-state lithium secondary battery cell can be appropriately adjusted depending on the installation site. Further, the processing conditions for the insulation treatment for the abnormal cell can be appropriately changed according to the size of the cell, the degree of short circuit, and the like, and the treatment method is not limited to the above embodiment and functions as a battery. Other processing methods can be adopted as long as the processing disappears.
ＬＢ…全固体リチウム二次電池、ＬＢＣ１…正常な全固体リチウム二次電池セル（正常セル）、ＬＢＣ２…絶縁セル、１…基板、２…正極集電体層、２１…第１接続部、３…負極集電体層、３１…第２接続部、４…正極、５…固体電解質層、６…リチウム負極、７…保護層、８，９…導体層、Ｓ１…正極集電体層形成工程、Ｓ２…正極形成工程、Ｓ３…固体電解質層形成工程、Ｓ４…負極集電体層形成工程、Ｓ５…リチウム負極形成工程、Ｓ６…セル判定工程、Ｓ７…保護層形成工程、Ｓ８…絶縁化処理工程、Ｓ９…セル並列接続工程。 LB ... All-solid-state lithium secondary battery, LBC1 ... Normal all-solid-state lithium secondary battery cell (normal cell), LBC2 ... Insulation cell, 1 ... Substrate, 2 ... Positive electrode current collector layer, 21 ... First connection, 3 ... Negative electrode current collector layer, 31 ... Second connection, 4 ... Positive electrode, 5 ... Solid electrolyte layer, 6 ... Lithium negative electrode, 7 ... Protective layer, 8, 9 ... Conductor layer, S1 ... Positive electrode current collector layer forming step , S2 ... Positive electrode forming step, S3 ... Solid electrolyte layer forming step, S4 ... Negative electrode current collector layer forming step, S5 ... Lithium negative electrode forming step, S6 ... Cell determination step, S7 ... Protective layer forming step, S8 ... Insulation treatment Step, S9 ... Cell parallel connection step.
Claims (4)
各全固体リチウム二次電池セルが、正極集電体層の第１接続部及び負極集電体層の第２接続部の夫々に形成される導体層により並列接続され、
全固体リチウム二次電池セルの一部は、電池として機能しない絶縁セルであり、
残りの電池として機能する全固体リチウム二次電池セルには、正極集電体層の第１接続部及び負極集電体層の第２接続部を除いてリチウム負極を覆うように保護層が積層されていることを特徴とする全固体リチウム二次電池。 The positive electrode current collector layer and the negative electrode current collector layer are arranged side by side on the substrate, and are laminated on the positive electrode current collector layer portion excluding the first connection portion located on one side in the parallel arrangement direction. An all-solid lithium secondary battery in which a solid electrolyte layer is laminated and a lithium negative electrode is laminated so as to cover a portion of the negative electrode current collector layer excluding the second connection portion located on the other side in the parallel arrangement direction and the solid electrolyte layer. In an all-solid-state lithium secondary battery equipped with multiple cells,
Each all-solid-state lithium secondary battery cell is connected in parallel by a conductor layer formed in each of the first connection portion of the positive electrode current collector layer and the second connection portion of the negative electrode current collector layer.
Some of the all-solid-state lithium secondary battery cells are insulated cells that do not function as batteries.
In the all-solid-state lithium secondary battery cell that functions as the remaining battery, a protective layer is laminated so as to cover the lithium negative electrode except for the first connection portion of the positive electrode current collector layer and the second connection portion of the negative electrode current collector layer. An all-solid-state lithium secondary battery characterized by being used.
セル判定工程で、短絡無しで正常と判定された正常セルに、正極集電体層の第１接続部及び負極集電体層の第２接続部を除いてリチウム負極を覆うように保護層を積層する保護層形成工程と、
セル判定工程で、短絡有りで異常と判定された異常セルを絶縁化して絶縁セルにする絶縁化処理工程と、
正常セル及び絶縁セルの全てを、各セルの正極集電体層の第１接続部及び負極集電体層の第２接続部の夫々の上に導体層を積層して並列接続するセル並列接続工程とを更に含むことを特徴とする全固体リチウム二次電池の製造方法。 In the positive electrode current collector layer forming step of forming the positive electrode current collector layer on the substrate and the portion of the positive electrode current collector layer excluding the first connection portion located on the side opposite to the side where the negative electrode current collector layer is formed. A positive electrode forming step of laminating the positive electrode, a solid electrolyte layer forming step of laminating a solid electrolyte layer on the positive electrode, and a negative electrode current collector on the substrate so as to be separated from the solid electrolyte layer and juxtaposed with the positive electrode current collector layer. Except for both the negative electrode current collector layer forming step of forming the layer and both the second connection portion of the negative electrode current collector layer located on the opposite side of the positive electrode current collector layer and the first connection portion of the positive electrode current collector layer. The presence or absence of a short circuit between the lithium negative electrode forming step in which the lithium negative electrode is laminated so as to connect the positive electrode current collector layer and the negative electrode current collector layer and the normality / abnormality of the all-solid-state lithium secondary battery cell in which the lithium negative electrode is laminated. In the method for manufacturing an all-solid-state lithium secondary battery, which includes a cell determination step of determining by
In the cell determination step, a protective layer is applied to a normal cell determined to be normal without a short circuit so as to cover the lithium negative electrode except for the first connection portion of the positive electrode current collector layer and the second connection portion of the negative electrode current collector layer. Protective layer forming process to be laminated and
In the cell determination process, an insulation treatment process that insulates an abnormal cell that is determined to be abnormal due to a short circuit into an insulated cell,
Cell parallel connection in which all normal cells and insulating cells are connected in parallel by laminating a conductor layer on each of the first connection portion of the positive electrode current collector layer and the second connection portion of the negative electrode current collector layer of each cell. A method for manufacturing an all-solid-state lithium secondary battery, which further comprises a step.
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| JP2004022250A (en) * | 2002-06-13 | 2004-01-22 | Matsushita Electric Ind Co Ltd | All solid battery |
| JP2012138299A (en) * | 2010-12-27 | 2012-07-19 | Ulvac Japan Ltd | Method for manufacturing all-solid lithium secondary battery, and method for inspecting all-solid lithium secondary battery |
| JP2012138298A (en) * | 2010-12-27 | 2012-07-19 | Ulvac Japan Ltd | Method for manufacturing thin film lithium secondary battery, and thin film lithium secondary battery |
| JP2017027770A (en) * | 2015-07-22 | 2017-02-02 | トヨタ自動車株式会社 | Inspection method for all-solid secondary battery and method of manufacturing all-solid secondary battery using the inspection method |
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2019
- 2019-05-29 JP JP2019100678A patent/JP7285696B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004022250A (en) * | 2002-06-13 | 2004-01-22 | Matsushita Electric Ind Co Ltd | All solid battery |
| JP2012138299A (en) * | 2010-12-27 | 2012-07-19 | Ulvac Japan Ltd | Method for manufacturing all-solid lithium secondary battery, and method for inspecting all-solid lithium secondary battery |
| JP2012138298A (en) * | 2010-12-27 | 2012-07-19 | Ulvac Japan Ltd | Method for manufacturing thin film lithium secondary battery, and thin film lithium secondary battery |
| JP2017027770A (en) * | 2015-07-22 | 2017-02-02 | トヨタ自動車株式会社 | Inspection method for all-solid secondary battery and method of manufacturing all-solid secondary battery using the inspection method |
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