JP2023074022A - Manufacturing method of all-solid battery - Google Patents
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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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Abstract
Description
本開示は、全固体電池の製造方法に関する。 The present disclosure relates to a method for manufacturing an all-solid-state battery.
全固体電池は、正極と負極の間に介在する電解質として、有機溶媒を含む電解液に替えて固体電解質を用いるという点で注目されている。 All-solid-state batteries are attracting attention in that they use a solid electrolyte instead of an electrolyte solution containing an organic solvent as an electrolyte interposed between a positive electrode and a negative electrode.
特許文献１には、集電体と、集電体に隣接して積層された電池ユニットとを接着するための接着手段を有する全固体電池が開示されている。 Patent Literature 1 discloses an all-solid-state battery having an adhesive means for bonding a current collector and a battery unit laminated adjacent to the current collector.
全固体電池のエネルギー密度の向上が求められる。負極と固体電解質層と正極を積層した電極積層体において、電極積層体を一括裁断して側面を面一にした後に側面をテープ等の絶縁層で固定しようとすると絶縁層が正極の面上にはみ出して、正極の面上の余分な絶縁層により電極積層体に局所荷重がかかる場合がある。
また、正極の面上の余分な絶縁層により、全固体電池の寸法が大きくなり全固体電池のエネルギー密度が低下する。
Improvements in the energy density of all-solid-state batteries are required. In an electrode laminate obtained by laminating a negative electrode, a solid electrolyte layer, and a positive electrode, if the side surface is fixed with an insulating layer such as tape after the electrode laminate is cut together to make the side surface flush, the insulating layer may be stuck on the surface of the positive electrode. A local load may be applied to the electrode stack due to the excess insulating layer on the surface of the positive electrode that protrudes.
Also, the extra insulating layer on the face of the positive electrode increases the size of the all-solid-state battery and reduces the energy density of the all-solid-state battery.
本開示は、上記実情に鑑みてなされたものであり、全固体電池のエネルギー密度を向上させることができる全固体電池の製造方法を提供することを主目的とする。 The present disclosure has been made in view of the above circumstances, and a main object thereof is to provide a method for manufacturing an all-solid-state battery that can improve the energy density of the all-solid-state battery.
本開示の全固体電池の製造方法は、第１集電体の両面に、第１電極層、固体電解質層、第２電極層、第２集電体をこの順に有する全固体電池の製造方法であって、
前記第１集電体の両面に、前記第１電極層、前記固体電解質層、前記第２電極層をこの順で積層した積層体を得る工程と、
前記積層体の積層方向の少なくとも１つの側面を裁断により面一とする工程と、
前記第２集電体の面上の前記積層体を配置する予定の領域に隣接する領域に絶縁層を配置し、当該第２集電体と当該絶縁層の接合体を形成する工程と、
前記第２集電体の面上の前記積層体を配置する予定の領域に前記第２電極層が当該第２集電体と接するように前記積層体を配置し、且つ、前記絶縁層と前記積層体の面一である側面と、を接着する工程と、を備えることを特徴とする。
The method for manufacturing an all-solid-state battery of the present disclosure is a method for manufacturing an all-solid-state battery having a first electrode layer, a solid electrolyte layer, a second electrode layer, and a second current collector in this order on both sides of a first current collector. There is
obtaining a laminate in which the first electrode layer, the solid electrolyte layer, and the second electrode layer are laminated in this order on both sides of the first current collector;
a step of cutting at least one side surface of the laminate in the stacking direction to make it flush;
disposing an insulating layer in a region adjacent to a region where the laminate is to be disposed on the surface of the second current collector, and forming a bonded body of the second current collector and the insulating layer;
The laminate is arranged so that the second electrode layer is in contact with the second current collector in a region where the laminate is to be arranged on the surface of the second current collector, and the insulating layer and the and a step of adhering the side surfaces of the laminate that are flush with each other.
本開示は、全固体電池のエネルギー密度を向上させることができる全固体電池の製造方法を提供することができる。 INDUSTRIAL APPLICABILITY The present disclosure can provide a method for manufacturing an all-solid-state battery that can improve the energy density of the all-solid-state battery.
本開示の全固体電池の製造方法は、第１集電体の両面に、第１電極層、固体電解質層、第２電極層、第２集電体をこの順に有する全固体電池の製造方法であって、
前記第１集電体の両面に、前記第１電極層、前記固体電解質層、前記第２電極層をこの順で積層した積層体を得る工程と、
前記積層体の積層方向の少なくとも１つの側面を裁断により面一とする工程と、
前記第２集電体の面上の前記積層体を配置する予定の領域に隣接する領域に絶縁層を配置し、当該第２集電体と当該絶縁層の接合体を形成する工程と、
前記第２集電体の面上の前記積層体を配置する予定の領域に前記第２電極層が当該第２集電体と接するように前記積層体を配置し、且つ、前記絶縁層と前記積層体の面一である側面と、を接着する工程と、を備えることを特徴とする。
The method for manufacturing an all-solid-state battery of the present disclosure is a method for manufacturing an all-solid-state battery having a first electrode layer, a solid electrolyte layer, a second electrode layer, and a second current collector in this order on both sides of a first current collector. There is
obtaining a laminate in which the first electrode layer, the solid electrolyte layer, and the second electrode layer are laminated in this order on both sides of the first current collector;
a step of cutting at least one side surface of the laminate in the stacking direction to make it flush;
disposing an insulating layer in a region adjacent to a region where the laminate is to be disposed on the surface of the second current collector, and forming a bonded body of the second current collector and the insulating layer;
The laminate is arranged so that the second electrode layer is in contact with the second current collector in a region where the laminate is to be arranged on the surface of the second current collector, and the insulating layer and the and a step of adhering the side surfaces of the laminate that are flush with each other.
図１は、本開示の全固体電池の製造方法の一例を示すフローチャートである。１１は、第１集電体、１２は、第１電極層、１３は、固体電解質層、１４は、第２電極層、１５は、第２集電体、１６は、絶縁層を示す。
本開示の全固体電池の製造方法は、図１に示すように、（１）積層体取得工程と、（２）裁断工程と、（３）接合体形成工程と、（４）接着工程と、を備える。
なお、（３）接合体形成工程は、（４）接着工程前に行えばよく、（１）積層体取得工程よりも前に行ってもよく、同時であってもよく、後に行ってもよく、（２）裁断工程よりも前に行ってもよく、同時であってもよく、後に行ってもよい。
FIG. 1 is a flow chart showing an example of a method for manufacturing an all-solid-state battery of the present disclosure. 11 is a first current collector, 12 is a first electrode layer, 13 is a solid electrolyte layer, 14 is a second electrode layer, 15 is a second current collector, and 16 is an insulating layer.
The method for manufacturing an all-solid-state battery of the present disclosure includes, as shown in FIG. 1, (1) a laminate obtaining step, (2) a cutting step, (3) a bonded body forming step, (4) a bonding step, Prepare.
Note that the (3) joined body forming step may be performed before the (4) bonding step, and may be performed before, at the same time as, or after the laminate obtaining step (1). , (2) may be performed before, at the same time as, or after the cutting step.
（１）積層体取得工程
積層体取得工程は、前記第１集電体の両面に、前記第１電極層、前記固体電解質層、前記第２電極層をこの順で積層した積層体を得る工程である。
第１電極層は正極層又は負極層であることができる。第１電極層が正極層であるとき、その対極層である第２電極層は負極層であり、第１電極層が負極層であるときの第２電極層は正極層である。
第１集電体の両面に、前記第１電極層、前記固体電解質層、前記第２電極層をこの順で積層する方法は、特に限定されず、従来公知の方法を適宜採用することができる。
(1) Laminate Acquisition Step The laminate acquisition step is a step of obtaining a laminate in which the first electrode layer, the solid electrolyte layer, and the second electrode layer are laminated in this order on both sides of the first current collector. is.
The first electrode layer can be a positive electrode layer or a negative electrode layer. When the first electrode layer is the positive electrode layer, the second electrode layer, which is the counter electrode layer, is the negative electrode layer, and when the first electrode layer is the negative electrode layer, the second electrode layer is the positive electrode layer.
The method of laminating the first electrode layer, the solid electrolyte layer, and the second electrode layer in this order on both surfaces of the first current collector is not particularly limited, and conventionally known methods can be appropriately employed. .
（２）裁断工程
裁断工程は、前記積層体の積層方向の少なくとも１つの側面を裁断により面一とする工程である。
裁断方法は特に限定されず、レーザー照射等が挙げられる。
面一とする側面は、少なくとも１つの側面であればよく、１つの側面のみであってもよい。
(2) Cutting Step The cutting step is a step of making at least one side surface of the laminate in the stacking direction flush by cutting.
The cutting method is not particularly limited, and examples thereof include laser irradiation.
The side surface to be made flush may be at least one side surface, or may be only one side surface.
（３）接合体形成工程
接合体形成工程は、前記第２集電体の面上の前記積層体を配置する予定の領域に隣接する領域に絶縁層を配置し、当該第２集電体と当該絶縁層の接合体を形成する工程である。
接合方法は、特に限定されず、絶縁層が接着性を有する場合は、第２集電体と絶縁層を接着してもよい。
全固体電池において、第２集電体は、積層体と対向しない領域と積層体と対向する領域を有する。すなわち、第２集電体の面方向の寸法は、積層体の面方向の寸法よりも大きい。
絶縁層を配置する位置は、第２集電体の面上の前記積層体を配置する予定の領域に隣接する領域であれば特に限定されず、後述する接着工程において、積層体の面一とした側面と接着可能な位置であってもよい。
絶縁層の厚み（積層方向の高さ）は、積層体の厚み（積層方向の高さ）と同じであってもよく、異なっていてもよいが、積層体の厚み±第２電極層の厚みの範囲であってもよい。絶縁層の厚みが積層体の厚みよりも大きい場合、プレス及び加熱等によって、絶縁層の厚みが積層体の厚みと同程度となるようにしてもよい。これにより、積層体と絶縁層の高さを合わせることができる。
(3) Joined Body Forming Step In the joined body forming step, an insulating layer is arranged in a region adjacent to a region where the laminated body is to be arranged on the surface of the second current collector, and the second current collector and This is a step of forming a bonded body of the insulating layers.
The bonding method is not particularly limited, and if the insulating layer has adhesiveness, the second current collector and the insulating layer may be bonded.
In the all-solid-state battery, the second current collector has a region that does not face the laminate and a region that faces the laminate. That is, the dimension in the plane direction of the second current collector is larger than the dimension in the plane direction of the laminate.
The position where the insulating layer is arranged is not particularly limited as long as it is a region adjacent to the region where the laminate is to be arranged on the surface of the second current collector. It may be a position where it can be adhered to the side surface.
The thickness of the insulating layer (height in the lamination direction) may be the same as or different from the thickness of the laminate (height in the lamination direction). may be in the range of When the thickness of the insulating layer is greater than the thickness of the laminate, the thickness of the insulating layer may be made approximately the same as the thickness of the laminate by pressing, heating, or the like. Thereby, the height of the laminate and the insulating layer can be matched.
絶縁層の材料は、絶縁性を有する材料であればよく、接着性を有する材料であってもよく、接着剤であってもよい。絶縁層に用いられる接着剤は、固体で、接着機能を有するものであれば特に限定されない。接着剤の種類は、例えば、タック性を有する樹脂、及び、ホットメルト剤等が挙げられる。タック性を有する樹脂としては、例えば、アクリル系樹脂、ゴム系樹脂、シリコーン系樹脂、及び、ウレタン系樹脂等が挙げられる。ホットメルト剤としては、融点が１４０℃以下の樹脂であれば特に限定されず、例えば、エチレン－酢酸ビニル系樹脂、ポリエチレンナフタレート樹脂等が挙げられる。 The insulating layer may be made of any material as long as it has insulating properties, may be an adhesive material, or may be an adhesive. The adhesive used for the insulating layer is not particularly limited as long as it is solid and has an adhesive function. Types of adhesives include, for example, tacky resins and hot-melt agents. Examples of tacky resins include acrylic resins, rubber resins, silicone resins, and urethane resins. The hot melt agent is not particularly limited as long as it has a melting point of 140° C. or lower, and examples thereof include ethylene-vinyl acetate resins and polyethylene naphthalate resins.
（４）接着工程
接着工程は、前記第２集電体の面上の前記積層体を配置する予定の領域に前記第２電極層が当該第２集電体と接するように前記積層体を配置し、且つ、前記絶縁層と前記積層体の面一である側面と、を接着する工程である。
絶縁層は、第２集電体の面上に積層体を配置する際の位置決め部材として用いることができる。
接着方法は、特に限定されず、絶縁層と積層体を、接着剤を介して接着してもよいし、絶縁層自体が接着性を有する場合は、そのまま積層体と絶縁層を接着してもよい。
(4) Adhesion step In the adhesion step, the laminate is arranged on the surface of the second current collector so that the second electrode layer is in contact with the second current collector in a region where the laminate is to be arranged. and bonding the insulating layer and the flush side surface of the laminate.
The insulating layer can be used as a positioning member when arranging the laminate on the surface of the second current collector.
The bonding method is not particularly limited, and the insulating layer and the laminate may be bonded via an adhesive, or when the insulating layer itself has adhesiveness, the laminate and the insulating layer may be bonded as they are. good.
［電極層］
電極層は、電極活物質を含み、必要に応じて固体電解質、導電材、結着材等を含む。
電極層は、正極層又は負極層である。電極活物質の種類が互いに異なる２つの電極層を用意することにより、一方を正極層、もう一方を負極層として用いてもよい。
電極活物質としては、全固体電池の活物質として使用可能な材料をいずれも採用可能であり、後述する正極活物質及び負極活物質として例示するものと同様のものを採用することができる。
固体電解質としては、後述する固体電解質層において例示するものと同様のものを例示することができる。
導電材及び結着剤としては、後述する正極層において例示するものと同様のものを例示することができる。
電極層の厚みについては特に限定されるものではないが、例えば、１０～１００μｍであってもよく、１０～２０μｍであってもよい。
[Electrode layer]
The electrode layer contains an electrode active material and, if necessary, a solid electrolyte, a conductive material, a binder, and the like.
The electrode layer is a positive electrode layer or a negative electrode layer. By preparing two electrode layers with mutually different types of electrode active materials, one may be used as a positive electrode layer and the other as a negative electrode layer.
As the electrode active material, any material that can be used as an active material for an all-solid-state battery can be used, and the same materials as those exemplified as the positive electrode active material and the negative electrode active material described later can be used.
As the solid electrolyte, the same ones as those exemplified in the solid electrolyte layer described later can be exemplified.
As the conductive material and the binder, the same materials as those exemplified in the positive electrode layer to be described later can be exemplified.
Although the thickness of the electrode layer is not particularly limited, it may be, for example, 10 to 100 μm or 10 to 20 μm.
［集電体］
集電体としては、後述する正極集電体及び負極集電体として例示するものと同様のものを採用することができる。
[Current collector]
As the current collector, the same ones as those exemplified as the positive electrode current collector and the negative electrode current collector to be described later can be employed.
［全固体電池］
本開示の全固体電池は、正極層及び正極集電体を含む正極、固体電解質層、負極層及び負極集電体を含む負極を備えていてもよい。
全固体電池は、第１集電体の両面に第１電極層と、固体電解質層と、第２電極層と、第２集電体をこの順に有する。
第１電極層と第２電極層は、一方が正極層であり、もう一方が負極層である。第１集電体は、第１電極層が正極層であれば正極集電体であり、負極層であれば、負極集電体である。第２集電体は、第２電極層が正極層であれば正極集電体であり、負極層であれば、負極集電体である。
全固体電池は、正極集電体、正極層、固体電解質層、負極層、負極集電体、負極層、固体電解質層、正極層及び、正極集電体がこの順に積層された電池ユニットであってもよい。
全固体電池は、負極集電体、負極層、固体電解質層、正極層、正極集電体、正極層、固体電解質層、負極層、及び負極集電体がこの順に積層された電池ユニットであってもよい。
全固体電池は、２つ以上の電池ユニットの積層体であってもよい。
[All-solid battery]
The all-solid-state battery of the present disclosure may include a positive electrode including a positive electrode layer and a positive current collector, and a negative electrode including a solid electrolyte layer, a negative electrode layer, and a negative current collector.
An all-solid battery has a first electrode layer, a solid electrolyte layer, a second electrode layer, and a second current collector in this order on both sides of a first current collector.
One of the first electrode layer and the second electrode layer is a positive electrode layer, and the other is a negative electrode layer. The first current collector is a positive electrode current collector if the first electrode layer is a positive electrode layer, and is a negative electrode current collector if the first electrode layer is a negative electrode layer. The second current collector is a positive electrode current collector if the second electrode layer is a positive electrode layer, and is a negative electrode current collector if the second electrode layer is a negative electrode layer.
An all-solid-state battery is a battery unit in which a positive electrode current collector, a positive electrode layer, a solid electrolyte layer, a negative electrode layer, a negative electrode current collector, a negative electrode layer, a solid electrolyte layer, a positive electrode layer, and a positive electrode current collector are laminated in this order. may
An all-solid-state battery is a battery unit in which a negative electrode current collector, a negative electrode layer, a solid electrolyte layer, a positive electrode layer, a positive electrode current collector, a positive electrode layer, a solid electrolyte layer, a negative electrode layer, and a negative electrode current collector are laminated in this order. may
An all-solid-state battery may be a stack of two or more battery units.
［正極］
正極は、正極層、及び正極集電体を含む。
[Positive electrode]
The positive electrode includes a positive electrode layer and a positive current collector.
［正極層］
正極層は、正極活物質を含み、任意成分として、固体電解質、導電材、及びバインダー等が含まれていてもよい。
[Positive electrode layer]
The positive electrode layer contains a positive electrode active material, and may contain a solid electrolyte, a conductive material, a binder, and the like as optional components.
正極活物質の種類について特に制限はなく、全固体電池の活物質として使用可能な材料をいずれも採用可能である。正極活物質は、例えば、金属リチウム（Ｌｉ）、リチウム合金、ＬｉＣｏＯ２、ＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２、ＬｉＮｉｘＣｏ１－ｘＯ２（０＜ｘ＜１）、ＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２、ＬｉＭｎＯ２、異種元素置換Ｌｉ－Ｍｎスピネル、チタン酸リチウム、リン酸金属リチウム、ＬｉＣｏＮ、Ｌｉ２ＳｉＯ３、及びＬｉ４ＳｉＯ４、遷移金属酸化物、ＴｉＳ２、Ｓｉ、ＳｉＯ２、Ｓｉ合金及びリチウム貯蔵性金属間化合物等を挙げることができる。異種元素置換Ｌｉ－Ｍｎスピネルは、例えばＬｉＭｎ１．５Ｎｉ０．５Ｏ４、ＬｉＭｎ１．５Ａｌ０．５Ｏ４、ＬｉＭｎ１．５Ｍｇ０．５Ｏ４、ＬｉＭｎ１．５Ｃｏ０．５Ｏ４、ＬｉＭｎ１．５Ｆｅ０．５Ｏ４、及びＬｉＭｎ１．５Ｚｎ０．５Ｏ４等である。チタン酸リチウムは、例えばＬｉ４Ｔｉ５Ｏ１２等である。リン酸金属リチウムは、例えばＬｉＦｅＰＯ４、ＬｉＭｎＰＯ４、ＬｉＣｏＰＯ４、及びＬｉＮｉＰＯ４等である。遷移金属酸化物は、例えばＶ２Ｏ５、及びＭｏＯ３等である。リチウム貯蔵性金属間化合物は、例えばＭｇ２Ｓｎ、Ｍｇ２Ｇｅ、Ｍｇ２Ｓｂ、及びＣｕ３Ｓｂ等である。
リチウム合金としては、Ｌｉ－Ａｕ、Ｌｉ－Ｍｇ、Ｌｉ－Ｓｎ、Ｌｉ－Ｓｉ、Ｌｉ－Ａｌ、Ｌｉ－Ｂ、Ｌｉ－Ｃ、Ｌｉ－Ｃａ、Ｌｉ－Ｇａ、Ｌｉ－Ｇｅ、Ｌｉ－Ａｓ、Ｌｉ－Ｓｅ、Ｌｉ－Ｒｕ、Ｌｉ－Ｒｈ、Ｌｉ－Ｐｄ、Ｌｉ－Ａｇ、Ｌｉ－Ｃｄ、Ｌｉ－Ｉｎ、Ｌｉ－Ｓｂ、Ｌｉ－Ｉｒ、Ｌｉ－Ｐｔ、Ｌｉ－Ｈｇ、Ｌｉ－Ｐｂ、Ｌｉ－Ｂｉ、Ｌｉ－Ｚｎ、Ｌｉ－Ｔｌ、Ｌｉ－Ｔｅ、及びＬｉ－Ａｔ等が挙げられる。Ｓｉ合金としては、Ｌｉ等の金属との合金等が挙げられ、その他、Ｓｎ、Ｇｅ、及びＡｌからなる群より選ばれる少なくとも一種の金属との合金であってもよい。
正極活物質の形状は特に限定されるものではないが、粒子状であってもよい。正極活物質が粒子状である場合、正極活物質は一次粒子であってもよく、二次粒子であってもよい。
正極活物質の表面には、Ｌｉイオン伝導性酸化物を含有するコート層が形成されていても良い。正極活物質と、固体電解質との反応を抑制できるからである。
Ｌｉイオン伝導性酸化物としては、例えば、ＬｉＮｂＯ３、Ｌｉ４Ｔｉ５Ｏ１２、及び、Ｌｉ３ＰＯ４等が挙げられる。コート層の厚さは、例えば、０．１ｎｍ以上であり、１ｎｍ以上であっても良い。一方、コート層の厚さは、例えば、１００ｎｍ以下であり、２０ｎｍ以下であっても良い。コート層は、例えば、正極活物質の表面の７０％以上を被覆していてもよく、９０％以上を被覆していてもよい。
There are no particular restrictions on the type of positive electrode active material, and any material that can be used as an active material for an all-solid-state battery can be used. Examples of positive electrode active materials include metallic lithium (Li), lithium alloys, LiCoO 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiNi x Co 1-x O 2 (0<x<1), LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiMnO 2 , heteroelement-substituted Li—Mn spinel, lithium titanate, lithium metal phosphate, LiCoN, Li 2 SiO 3 and Li 4 SiO 4 , transition metals Oxides, TiS 2 , Si, SiO 2 , Si alloys, lithium-storing intermetallic compounds, and the like can be mentioned. The hetero-element-substituted Li—Mn spinel is, for example, LiMn 1.5 Ni 0.5 O 4 , LiMn 1.5 Al 0.5 O 4 , LiMn 1.5 Mg 0.5 O 4 , LiMn 1.5 Co 0.5 O 4 . 5O4 , LiMn1.5Fe0.5O4 , and LiMn1.5Zn0.5O4 . _ Lithium titanate is, for example, Li 4 Ti 5 O 12 or the like. Lithium metal phosphates include, for example, LiFePO 4 , LiMnPO 4 , LiCoPO 4 and LiNiPO 4 . Transition metal oxides are, for example, V 2 O 5 and MoO 3 . Examples of lithium-storage intermetallic compounds include Mg 2 Sn, Mg 2 Ge, Mg 2 Sb, and Cu 3 Sb.
Lithium alloys include Li-Au, Li-Mg, Li-Sn, Li-Si, Li-Al, Li-B, Li-C, Li-Ca, Li-Ga, Li-Ge, Li-As, Li -Se, Li-Ru, Li-Rh, Li-Pd, Li-Ag, Li-Cd, Li-In, Li-Sb, Li-Ir, Li-Pt, Li-Hg, Li-Pb, Li-Bi , Li—Zn, Li—Tl, Li—Te, and Li—At. Examples of Si alloys include alloys with metals such as Li, and may be alloys with at least one metal selected from the group consisting of Sn, Ge, and Al.
Although the shape of the positive electrode active material is not particularly limited, it may be particulate. When the positive electrode active material is particulate, the positive electrode active material may be primary particles or secondary particles.
A coat layer containing a Li ion conductive oxide may be formed on the surface of the positive electrode active material. This is because the reaction between the positive electrode active material and the solid electrolyte can be suppressed.
Li ion conductive oxides include, for example, LiNbO 3 , Li 4 Ti 5 O 12 , Li 3 PO 4 and the like. The thickness of the coat layer is, for example, 0.1 nm or more, and may be 1 nm or more. On the other hand, the thickness of the coat layer is, for example, 100 nm or less, and may be 20 nm or less. The coat layer may cover, for example, 70% or more, or 90% or more, of the surface of the positive electrode active material.
固体電解質としては、固体電解質層において例示するものと同様のものを例示することができる。
正極層における固体電解質の含有量は、特に限定されないが、正極層の総質量を１００質量％としたとき、例えば１質量％～８０質量％の範囲内であってもよい。
As the solid electrolyte, the same ones as those exemplified in the solid electrolyte layer can be exemplified.
The content of the solid electrolyte in the positive electrode layer is not particularly limited, but may be in the range of, for example, 1% by mass to 80% by mass when the total mass of the positive electrode layer is 100% by mass.
導電材としては、公知のものを用いることができ、例えば、炭素材料、及び金属粒子等が挙げられる。炭素材料としては、例えば、アセチレンブラック、ファーネスブラック、ＶＧＣＦ、カーボンナノチューブ、及び、カーボンナノファイバーからなる群より選ばれる少なくとも一種を挙げることができる。中でも、電子伝導性の観点から、ＶＧＣＦ、カーボンナノチューブ、及び、カーボンナノファイバーからなる群より選ばれる少なくとも一種であってもよい。金属粒子としては、Ｎｉ、Ｃｕ、Ｆｅ、及びＳＵＳ等の粒子が挙げられる。
正極層における導電材の含有量は特に限定されるものではない。
As the conductive material, a known material can be used, and examples thereof include carbon materials, metal particles, and the like. Examples of carbon materials include at least one selected from the group consisting of acetylene black, furnace black, VGCF, carbon nanotubes, and carbon nanofibers. Among them, from the viewpoint of electron conductivity, at least one selected from the group consisting of VGCF, carbon nanotubes, and carbon nanofibers may be used. Metal particles include particles of Ni, Cu, Fe, SUS, and the like.
The content of the conductive material in the positive electrode layer is not particularly limited.
結着剤（バインダー）としては、アクリロニトリルブタジエンゴム（ＡＢＲ）、ブタジエンゴム（ＢＲ）、ポリフッ化ビニリデン（ＰＶｄＦ）、スチレンブタジエンゴム（ＳＢＲ）等を例示することができる。正極層におけるバインダーの含有量は特に限定されるものではない。 Examples of binders include acrylonitrile butadiene rubber (ABR), butadiene rubber (BR), polyvinylidene fluoride (PVdF), styrene butadiene rubber (SBR), and the like. The content of the binder in the positive electrode layer is not particularly limited.
正極層の厚みについては特に限定されるものではないが、例えば、１０～１００μｍであってもよく、１０～２０μｍであってもよい。 Although the thickness of the positive electrode layer is not particularly limited, it may be, for example, 10 to 100 μm or 10 to 20 μm.
正極層は、従来公知の方法で形成することができる。
例えば、正極活物質、及び、必要に応じ他の成分を溶媒中に投入し、撹拌することにより、正極層用スラリーを作製し、当該正極層用スラリーを支持体の一面上に塗布して乾燥させることにより、正極層が得られる。
溶媒は、例えば酢酸ブチル、酪酸ブチル、メシチレン、テトラリン、ヘプタン、及びＮ－メチル－２－ピロリドン（ＮＭＰ）等が挙げられる。
支持体の一面上に正極層用スラリーを塗布する方法は、特に限定されず、ドクターブレード法、メタルマスク印刷法、静電塗布法、ディップコート法、スプレーコート法、ロールコート法、グラビアコート法、及びスクリーン印刷法等が挙げられる。
支持体としては、自己支持性を有するものを適宜選択して用いることができ、特に限定はされず、例えばＣｕ及びＡｌなどの金属箔等を用いることができる。
The positive electrode layer can be formed by a conventionally known method.
For example, the positive electrode active material and, if necessary, other components are put into a solvent and stirred to prepare a positive electrode layer slurry, and the positive electrode layer slurry is applied to one surface of a support and dried. A positive electrode layer is obtained by letting it carry out.
Solvents include, for example, butyl acetate, butyl butyrate, mesitylene, tetralin, heptane, and N-methyl-2-pyrrolidone (NMP).
The method for applying the positive electrode layer slurry onto one surface of the support is not particularly limited, and includes a doctor blade method, a metal mask printing method, an electrostatic coating method, a dip coating method, a spray coating method, a roll coating method, and a gravure coating method. , and screen printing methods.
As the support, one having self-supporting properties can be appropriately selected and used, and there is no particular limitation. For example, metal foils such as Cu and Al can be used.
また、正極層の形成方法の別の方法として、正極活物質及び必要に応じ他の成分を含む正極合剤の粉末を加圧成形することにより正極層を形成してもよい。正極合剤の粉末を加圧成形する場合には、通常、１ＭＰａ以上２０００ＭＰａ以下程度のプレス圧を負荷する。
加圧方法としては、特に制限されないが、例えば、平板プレス、及びロールプレス等を用いて圧力を付加する方法等が挙げられる。
As another method of forming the positive electrode layer, the positive electrode layer may be formed by pressure-molding a powder of a positive electrode mixture containing the positive electrode active material and, if necessary, other components. When the positive electrode mixture powder is pressure-molded, a press pressure of about 1 MPa to 2000 MPa is normally applied.
The pressurizing method is not particularly limited, but examples thereof include a method of applying pressure using a flat plate press, a roll press, and the like.
［正極集電体］
正極集電体としては、全固体電池の集電体として使用可能な公知の金属を用いることができる。そのような金属としては、Ｃｕ、Ｎｉ、Ａｌ、Ｖ、Ａｕ、Ｐｔ、Ｍｇ、Ｆｅ、Ｔｉ、Ｃｏ、Ｃｒ、Ｚｎ、Ｇｅ、及びＩｎからなる群から選択される一又は二以上の元素を含む金属材料を例示することができる。正極集電体としては、例えばＳＵＳ、アルミニウム、ニッケル、鉄、チタンおよびカーボン等が挙げられる。
正極集電体の形態は特に限定されるものではなく、箔状、及びメッシュ状等、種々の形態とすることができる。正極集電体の厚さは、形状によって異なるものであるが、例えば１μｍ～５０μｍの範囲内であってもよく、５μｍ～２０μｍの範囲内であってもよい。
[Positive collector]
A known metal that can be used as a current collector for an all-solid battery can be used as the positive electrode current collector. Such metals include one or more elements selected from the group consisting of Cu, Ni, Al, V, Au, Pt, Mg, Fe, Ti, Co, Cr, Zn, Ge, and In. A metal material can be exemplified. Examples of positive electrode current collectors include SUS, aluminum, nickel, iron, titanium and carbon.
The shape of the positive electrode current collector is not particularly limited, and various shapes such as a foil shape and a mesh shape can be used. The thickness of the positive electrode current collector varies depending on the shape, and may be, for example, within the range of 1 μm to 50 μm, or within the range of 5 μm to 20 μm.
［負極］
負極は、負極層、及び、負極集電体を含む。
[Negative electrode]
The negative electrode includes a negative electrode layer and a negative electrode current collector.
［負極層］
負極層は、少なくとも負極活物質を含有し、必要に応じ、固体電解質、導電材、及び、結着剤等を含有する。
負極活物質としては、グラファイト、メソカーボンマイクロビーズ（ＭＣＭＢ）、高配向性熱分解グラファイト（ＨＯＰＧ）、ハードカーボン、ソフトカーボン、リチウム単体、リチウム合金、Ｓｉ単体、Ｓｉ合金、及びＬｉ４Ｔｉ５Ｏ１２等が挙げられる。リチウム合金及びＳｉ合金としては、正極活物質において例示したものと同様のものを用いることができる。
負極活物質の形状は特に限定されず、粒子状、及び板状等が挙げられる。負極活物質が粒子状である場合、負極活物質は一次粒子であってもよく、二次粒子であってもよい。
負極層に用いられる導電材、及び、結着剤は、正極層において例示したものと同様のものを用いることができる。負極層に用いられる固体電解質は、固体電解質層において例示するものと同様のものを例示することができる。
負極層の厚さは、特に限定されないが、例えば、１０～１００μｍであってもよく、１０～２０μｍであってもよい。
負極層における負極活物質の含有量は、特に限定されないが、例えば、２０質量％～９０質量％であってもよい。
[Negative electrode layer]
The negative electrode layer contains at least a negative electrode active material, and if necessary, a solid electrolyte, a conductive material, a binder, and the like.
Examples of negative electrode active materials include graphite, mesocarbon microbeads (MCMB), highly oriented pyrolytic graphite (HOPG), hard carbon, soft carbon, elemental lithium, lithium alloys, elemental Si, Si alloys, and Li4Ti5O . 12 and the like. As the lithium alloy and Si alloy, the same ones as those exemplified for the positive electrode active material can be used.
The shape of the negative electrode active material is not particularly limited, and may be particulate, plate-like, or the like. When the negative electrode active material is particulate, the negative electrode active material may be primary particles or secondary particles.
The conductive material and binder used for the negative electrode layer can be the same as those exemplified for the positive electrode layer. The solid electrolyte used for the negative electrode layer can be exemplified by the same solid electrolytes as those exemplified for the solid electrolyte layer.
The thickness of the negative electrode layer is not particularly limited, but may be, for example, 10 to 100 μm or 10 to 20 μm.
The content of the negative electrode active material in the negative electrode layer is not particularly limited, but may be, for example, 20% by mass to 90% by mass.
［負極集電体］
負極集電体の材料は、Ｌｉと合金化しない材料であってもよく、例えばＳＵＳ及び、銅及び、ニッケル等を挙げることができる。負極集電体の形態としては、例えば、箔状及び、板状等を挙げることができる。負極集電体の平面視形状は、特に限定されるものではないが、例えば、円状、楕円状、矩形状及び、任意の多角形状等を挙げることができる。また、負極集電体の厚さは、形状によって異なるものであるが、例えば１μｍ～５０μｍの範囲内であってもよく、５μｍ～２０μｍの範囲内であってもよい。
[Negative electrode current collector]
The material of the negative electrode current collector may be a material that does not alloy with Li, such as SUS, copper and nickel. Examples of the shape of the negative electrode current collector include a foil shape and a plate shape. The shape of the negative electrode current collector in a plan view is not particularly limited, but examples thereof include a circular shape, an elliptical shape, a rectangular shape, and an arbitrary polygonal shape. Further, the thickness of the negative electrode current collector varies depending on the shape, and may be, for example, within the range of 1 μm to 50 μm, or may be within the range of 5 μm to 20 μm.
［固体電解質層］
固体電解質層は、少なくとも固体電解質を含む。
固体電解質層に含有させる固体電解質としては、全固体電池に使用可能な公知の固体電解質を適宜用いることができ、硫化物系固体電解質、酸化物系固体電解質、水素化物系固体電解質、ハロゲン化物系固体電解質、及び、窒化物系固体電解質等の無機固体電解質が挙げられる。硫化物系固体電解質は、アニオン元素の主成分として、硫黄（Ｓ）を含有してもよい。酸化物系固体電解質は、アニオン元素の主成分として、酸素（Ｏ）を含有してもよい。水素化物系固体電解質は、アニオン元素の主成分として、水素（Ｈ）を含有してもよい。ハロゲン化物系固体電解質は、アニオン元素の主成分として、ハロゲン（Ｘ）を含有してもよい。窒化物系固体電解質は、アニオン元素の主成分として、窒素（Ｎ）を含有してもよい。
[Solid electrolyte layer]
The solid electrolyte layer contains at least a solid electrolyte.
As the solid electrolyte to be contained in the solid electrolyte layer, known solid electrolytes that can be used in all-solid-state batteries can be appropriately used, including sulfide-based solid electrolytes, oxide-based solid electrolytes, hydride-based solid electrolytes, and halide-based solid electrolytes. Examples include solid electrolytes and inorganic solid electrolytes such as nitride-based solid electrolytes. The sulfide-based solid electrolyte may contain sulfur (S) as the main component of the anion element. The oxide-based solid electrolyte may contain oxygen (O) as a main component of the anion element. The hydride-based solid electrolyte may contain hydrogen (H) as the main component of the anion element. The halide-based solid electrolyte may contain halogen (X) as the main component of the anion element. The nitride-based solid electrolyte may contain nitrogen (N) as a main component of the anion element.
硫化物系固体電解質は、硫化物ガラスであってもよく、結晶化硫化物ガラス（ガラスセラミックス）であってもよく、原料組成物に対する固相反応処理により得られる結晶質材料であってもよい。
硫化物系固体電解質の結晶状態は、例えば、硫化物系固体電解質に対してＣｕＫα線を使用した粉末Ｘ線回折測定を行うことにより確認することができる。
The sulfide-based solid electrolyte may be sulfide glass, crystallized sulfide glass (glass ceramics), or a crystalline material obtained by solid-phase reaction treatment of a raw material composition. .
The crystalline state of the sulfide-based solid electrolyte can be confirmed, for example, by subjecting the sulfide-based solid electrolyte to powder X-ray diffraction measurement using CuKα rays.
硫化物ガラスは、原料組成物（例えばＬｉ２ＳおよびＰ２Ｓ５の混合物）を非晶質処理することにより得ることができる。非晶質処理としては、例えば、メカニカルミリングが挙げられる。 Sulfide glass can be obtained by subjecting a raw material composition (for example, a mixture of Li 2 S and P 2 S 5 ) to amorphous processing. Examples of amorphous processing include mechanical milling.
ガラスセラミックスは、例えば、硫化物ガラスを熱処理することにより得ることができる。
熱処理温度は、硫化物ガラスの熱分析測定により観測される結晶化温度（Ｔｃ）よりも高い温度であればよく、通常、１９５℃以上である。一方、熱処理温度の上限は特に限定されない。
硫化物ガラスの結晶化温度（Ｔｃ）は、示差熱分析（ＤＴＡ）により測定することができる。
熱処理時間は、ガラスセラミックスの所望の結晶化度が得られる時間であれば特に限定されるものではないが、例えば１分間～２４時間の範囲内であり、中でも、１分間～１０時間の範囲内が挙げられる。
熱処理の方法は特に限定されるものではないが、例えば、焼成炉を用いる方法を挙げることができる。
Glass-ceramics can be obtained, for example, by heat-treating sulfide glass.
The heat treatment temperature may be any temperature higher than the crystallization temperature (Tc) observed by thermal analysis measurement of sulfide glass, and is usually 195° C. or higher. On the other hand, the upper limit of the heat treatment temperature is not particularly limited.
The crystallization temperature (Tc) of sulfide glass can be measured by differential thermal analysis (DTA).
The heat treatment time is not particularly limited as long as the desired crystallinity of the glass-ceramics is obtained. is mentioned.
The method of heat treatment is not particularly limited, but for example, a method using a kiln can be mentioned.
酸化物系固体電解質としては、例えば、Ｌｉ元素、Ｙ元素（Ｙは、Ｎｂ、Ｂ、Ａｌ、Ｓｉ、Ｐ、Ｔｉ、Ｚｒ、Ｍｏ、Ｗ、Ｓの少なくとも一種である）、および、Ｏ元素を含有する固体電解質が挙げられる。酸化物系固体電解質の具体例としては、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２、Ｌｉ７－ｘＬａ３（Ｚｒ２－ｘＮｂｘ）Ｏ１２（０≦ｘ≦２）、Ｌｉ５Ｌａ３Ｎｂ２Ｏ１２等のガーネット型固体電解質；（Ｌｉ，Ｌａ）ＴｉＯ３、（Ｌｉ，Ｌａ）ＮｂＯ３、（Ｌｉ，Ｓｒ）（Ｔａ，Ｚｒ）Ｏ３等のペロブスカイト型固体電解質；Ｌｉ（Ａｌ，Ｔｉ）（ＰＯ４）３、Ｌｉ（Ａｌ，Ｇａ）（ＰＯ４）３のナシコン型固体電解質；Ｌｉ３ＰＯ４、ＬＩＰＯＮ（Ｌｉ３ＰＯ４のＯの一部をＮで置換した化合物）等のＬｉ－Ｐ－Ｏ系固体電解質；Ｌｉ３ＢＯ３、Ｌｉ３ＢＯ３のＯの一部をＣで置換した化合物等のＬｉ－Ｂ－Ｏ系固体電解質が挙げられる。
Examples of the oxide-based solid electrolyte include Li element, Y element (Y is at least one of Nb, B, Al, Si, P, Ti, Zr, Mo, W, and S), and O element. A solid electrolyte to be contained can be mentioned. Specific examples of oxide-based solid electrolytes include Li 7 La 3 Zr 2 O 12 , Li 7-x La 3 (Zr 2-x Nb x )O 12 (0≦x≦2), Li 5 La 3 Nb 2 Garnet-type solid electrolytes such as O12 ; Perovskite-type solid electrolytes such as (Li, La) TiO3 , (Li, La) NbO3 , (Li, Sr) (Ta, Zr) O3 ; Li(Al, Ti) Nasicon- type solid electrolytes of (PO 4 ) 3 and Li ( Al, Ga)(
水素化物系固体電解質は、例えば、Ｌｉと、水素を含有する錯アニオンと、を有する。錯アニオンとしては、例えば、（ＢＨ４）－、（ＮＨ２）－、（ＡｌＨ４）－、および（ＡｌＨ６）３－等が挙げられる。
ハロゲン化物系固体電解質としては、例えば、Ｌｉ６－３ｚＹｚＸ６（ＸはＣｌおよびＢｒの少なくとも一種であり、ｚは０＜ｚ＜２を満たす）等が挙げられる。
窒化物系固体電解質としては、例えばＬｉ３Ｎ等が挙げられる。
A hydride-based solid electrolyte has, for example, Li and a complex anion containing hydrogen. Complex anions include, for example, (BH 4 ) − , (NH 2 ) − , (AlH 4 ) − , and (AlH 6 ) 3- .
Halide-based solid electrolytes include, for example, Li 6-3z Y z X 6 (X is at least one of Cl and Br, and z satisfies 0<z<2).
Nitride-based solid electrolytes include, for example, Li 3 N and the like.
固体電解質の形状は、取扱い性が良いという観点から粒子状であってもよい。
固体電解質の粒子の平均粒径は、特に限定されないが、例えば１０ｎｍ以上であり、１００ｎｍ以上であってもよい。一方、固体電解質の粒子の平均粒径は、例えば２５μｍ以下であり、１０μｍ以下であってもよい。
The shape of the solid electrolyte may be particulate from the viewpoint of ease of handling.
The average particle size of the particles of the solid electrolyte is not particularly limited, but is, for example, 10 nm or more, and may be 100 nm or more. On the other hand, the average particle size of the particles of the solid electrolyte is, for example, 25 μm or less, and may be 10 μm or less.
本開示において、粒子の平均粒径は、特記しない限り、レーザー回折・散乱式粒子径分布測定により測定される体積基準のメディアン径（Ｄ５０）の値である。また、本開示においてメディアン径（Ｄ５０）とは、粒径の小さい粒子から順に並べた場合に、粒子の累積体積が全体の体積の半分（５０％）となる径（体積平均径）である。 In the present disclosure, unless otherwise specified, the average particle diameter of particles is the value of the volume-based median diameter (D50) measured by laser diffraction/scattering particle size distribution measurement. In the present disclosure, the median diameter (D50) is the diameter (volume average diameter) at which the cumulative volume of particles is half (50%) of the total volume when the particles are arranged in order from the smallest particle size.
固体電解質は、１種単独で、又は２種以上のものを用いることができる。また、２種以上の固体電解質を用いる場合、２種以上の固体電解質を混合してもよく、又は２層以上の固体電解質それぞれの層を形成して多層構造としてもよい。
固体電解質層中の固体電解質の割合は、特に限定されるものではないが、例えば５０質量％以上であり、６０質量％以上１００質量％以下の範囲内であってもよく、７０質量％以上１００質量％以下の範囲内であってもよく、１００質量％であってもよい。
Solid electrolytes can be used singly or in combination of two or more. Moreover, when using two or more kinds of solid electrolytes, two or more kinds of solid electrolytes may be mixed, or two or more layers of each solid electrolyte may be formed to form a multilayer structure.
The proportion of the solid electrolyte in the solid electrolyte layer is not particularly limited. It may be within the range of mass % or less, and may be 100 mass %.
固体電解質層には、可塑性を発現させる等の観点から、結着剤を含有させることもできる。そのような結着剤としては、正極層に用いられる結着剤として例示した材料等を例示することができる。ただし、高出力化を図り易くするために、固体電解質の過度の凝集を防止し且つ均一に分散された固体電解質を有する固体電解質層を形成可能にする等の観点から、固体電解質層に含有させる結着剤は５質量％以下としてもよい。 The solid electrolyte layer may contain a binder from the viewpoint of developing plasticity. As such a binder, the materials exemplified as the binder used for the positive electrode layer can be exemplified. However, in order to facilitate high output, it is contained in the solid electrolyte layer from the viewpoint of preventing excessive aggregation of the solid electrolyte and making it possible to form a solid electrolyte layer having a uniformly dispersed solid electrolyte. The binder may be 5% by mass or less.
固体電解質層の厚みは特に限定されるものではなく、通常０．１μｍ以上１ｍｍ以下である。
固体電解質層を形成する方法としては、固体電解質を含む固体電解質層用スラリーを支持体上に塗布して乾燥する方法、及び、固体電解質を含む固体電解質材料の粉末を加圧成形する方法等が挙げられる。支持体は、正極層において例示したものと同様のものを挙げることができる。固体電解質材料の粉末を加圧成形する場合には、通常、１ＭＰａ以上２０００ＭＰａ以下程度のプレス圧を負荷する。
加圧方法としては、特に制限されないが、正極層の形成において例示した加圧方法が挙げられる。
The thickness of the solid electrolyte layer is not particularly limited, and is usually 0.1 μm or more and 1 mm or less.
Examples of the method for forming the solid electrolyte layer include a method of coating a solid electrolyte layer slurry containing a solid electrolyte on a support and drying the slurry, and a method of pressure molding a powder of a solid electrolyte material containing a solid electrolyte. mentioned. Examples of the support include those exemplified for the positive electrode layer. When the solid electrolyte material powder is pressure-molded, a press pressure of about 1 MPa to 2000 MPa is normally applied.
The pressurization method is not particularly limited, but includes the pressurization method exemplified in the formation of the positive electrode layer.
全固体電池は、必要に応じ、積層体を収容する外装体及び拘束部材等を備える。
外装体の材質は、電解質に安定なものであれば特に限定されないが、ポリプロピレン、ポリエチレン、及び、アクリル樹脂等の樹脂等が挙げられる。
拘束部材は、積層体に、積層方向の拘束圧力を与えることができればよく、全固体電池の拘束部材として使用可能な公知の拘束部材を用いることができる。例えば、積層体の両表面を挟む板状部と、２つの板状部を連結する棒状部と、棒状部に連結され、ねじ構造等により拘束圧力を調整する調整部を有する拘束部材が挙げられる。調整部によって、積層体に所望の拘束圧力を与えることができる。
拘束圧力は、特に限定されるものではないが、例えば、０．１ＭＰａ以上であってもよく、１ＭＰａ以上であってもよく、５ＭＰａ以上であってもよい。拘束圧力を大きくすることで、各層の接触を良好にしやすいという利点があるためである。一方、拘束圧力は、例えば、１００ＭＰａ以下であってもよく、５０ＭＰａ以下であってもよく、２０ＭＰａ以下であってもよい。拘束圧力が大きすぎると、拘束部材に高い剛性が求められ、拘束部材が大型化する可能性があるためである。
An all-solid-state battery is provided with an exterior body, a restraint member, etc. which accommodate a laminated body as needed.
The material of the exterior body is not particularly limited as long as it is stable in the electrolyte, and examples thereof include polypropylene, polyethylene, and resins such as acrylic resins.
The restraining member may be any known restraining member that can be used as a restraining member for an all-solid-state battery as long as it can apply a restraining pressure in the stacking direction to the laminate. For example, a restraining member having a plate-like portion that sandwiches both surfaces of the laminate, a rod-like portion that connects the two plate-like portions, and an adjusting portion that is connected to the rod-like portion and adjusts the restraining pressure by a screw structure or the like can be mentioned. . A desired restraining pressure can be applied to the laminate by the adjusting section.
The confining pressure is not particularly limited, but may be, for example, 0.1 MPa or higher, 1 MPa or higher, or 5 MPa or higher. This is because increasing the confining pressure has the advantage of facilitating good contact between the layers. On the other hand, the confining pressure may be, for example, 100 MPa or less, 50 MPa or less, or 20 MPa or less. This is because if the restraining pressure is too large, the restraining member is required to have a high rigidity, which may increase the size of the restraining member.
全固体電池としては、一次電池であっても良く、二次電池であっても良いが、中でも二次電池であってもよい。二次電池は繰り返し充放電が可能である。二次電池は、例えば車載用電池として有用である。また、全固体電池は、全固体リチウム二次電池、全固体リチウムイオン二次電池であってもよい。
全固体電池の形状としては、例えば、コイン型、ラミネート型、円筒型、及び角型等を挙げることができる。
全固体電池の用途は、特に限定されないが、例えば、ハイブリッド自動車（ＨＥＶ）、プラグインハイブリッド自動車（ＰＨＥＶ）、電気自動車（ＢＥＶ）、ガソリン自動車、ディーゼル自動車等の車両の電源が挙げられる。特に、ハイブリッド自動車、プラグインハイブリッド自動車または電気自動車の駆動用電源に用いられてもよい。また、本開示における全固体電池は、車両以外の移動体（例えば、鉄道、船舶、航空機）の電源として用いられてもよく、情報処理装置等の電気製品の電源として用いられてもよい。
The all-solid-state battery may be a primary battery, a secondary battery, or a secondary battery. A secondary battery can be repeatedly charged and discharged. A secondary battery is useful, for example, as an in-vehicle battery. Also, the all-solid battery may be an all-solid lithium secondary battery or an all-solid lithium ion secondary battery.
Examples of the shape of the all-solid-state battery include coin type, laminated type, cylindrical type, and rectangular type.
Applications of all-solid-state batteries are not particularly limited, but examples include power sources for vehicles such as hybrid vehicles (HEV), plug-in hybrid vehicles (PHEV), electric vehicles (BEV), gasoline vehicles, and diesel vehicles. In particular, it may be used as a drive power source for hybrid vehicles, plug-in hybrid vehicles, or electric vehicles. In addition, the all-solid-state battery according to the present disclosure may be used as a power source for mobile objects other than vehicles (for example, railroads, ships, and aircraft), and may be used as a power source for electric appliances such as information processing devices.
（実施例１）
［正極層の作製］
転動流動式コーティング装置（パウレック社製）を用いて、大気雰囲気下において正極活物質粒子（Ｌｉ１．１５Ｎｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２を主相とする粒子）にニオブ酸リチウムをコーティングし、大気雰囲気下で焼成を行うことで、ニオブ酸リチウムの被覆層を有する正極活物質粒子を得た。
ポリプロピレン製容器に、ＰＶｄＦ、上記正極活物質粒子、硫化物系固体電解質（Ｌｉ２Ｓ－Ｐ２Ｓ５系ガラスセラミック）、及び、ＶＧＣＦ（昭和電工社製）を加え、得られた正極層用スラリーを超音波分散装置（エスエムテー社製ＵＨ－５０）で３０秒間攪拌した。
次に、容器を振とう機（柴田科学社製ＴＴＭ－１）で３分間振とうさせ、正極層用スラリーをさらに超音波分散装置で３０秒間攪拌した。容器を振とう機で３分間振とうさせた後、アプリケーターを使用してブレード法にて正極層用スラリーをアルミニウム箔上に塗工した。その後、正極層用スラリーを自然乾燥させ、１００℃のホットプレート上で３０分間乾燥させることにより、アルミニウム箔（基材）上に正極合剤を得た。アルミニウム箔（基材）と正極合剤の積層体を４ｔ／ｃｍで緻密化してアルミニウム箔（基材）上に正極層を得た。なお、正極合剤を４ｔ／ｃｍで緻密化した際に得られる正極層の厚さが１５μｍになるように正極層用スラリーの塗布量を調整した。
(Example 1)
[Preparation of positive electrode layer]
Using a tumbling fluidized coating apparatus (manufactured by Powrex Corporation), positive electrode active material particles (particles having Li 1.15 Ni 1/3 Co 1/3 Mn 1/3 O 2 as the main phase) in an air atmosphere. By coating with lithium niobate and firing in an air atmosphere, positive electrode active material particles having a coating layer of lithium niobate were obtained.
A positive electrode layer obtained by adding PVdF, the positive electrode active material particles, a sulfide-based solid electrolyte (Li 2 SP 2 S 5 -based glass ceramic), and VGCF (manufactured by Showa Denko KK) to a polypropylene container. The slurry was stirred for 30 seconds with an ultrasonic dispersing device (UH-50 manufactured by SMT Co., Ltd.).
Next, the container was shaken for 3 minutes with a shaker (TTM-1 manufactured by Shibata Scientific Co., Ltd.), and the positive electrode layer slurry was further stirred for 30 seconds with an ultrasonic dispersion device. After shaking the container for 3 minutes with a shaker, the positive electrode layer slurry was applied onto an aluminum foil by a blade method using an applicator. After that, the positive electrode layer slurry was naturally dried and dried on a hot plate at 100° C. for 30 minutes to obtain a positive electrode mixture on an aluminum foil (base material). A laminate of the aluminum foil (base material) and the positive electrode mixture was densified at 4 t/cm to obtain a positive electrode layer on the aluminum foil (base material). The amount of the positive electrode layer slurry applied was adjusted so that the thickness of the positive electrode layer obtained when the positive electrode mixture was densified at 4 t/cm was 15 μm.
［負極の作製］
ポリプロピレン製容器に、ＰＶｄＦ、負極活物質粒子（Ｌｉ４Ｔｉ５Ｏ１２（ＬＴＯ）粒子）、及び、上記と同様の硫化物系固体電解質（Ｌｉ２Ｓ－Ｐ２Ｓ５系ガラスセラミック）を加え、得られた負極層用スラリーを超音波分散装置で３０分間攪拌した。アプリケーターを使用してブレード法にて負極層用スラリーを銅箔上に塗工した。その後、負極層用スラリーを自然乾燥させ、１００℃のホットプレート上で３０分間乾燥させることにより、銅箔（負極集電体）上に負極層を有する負極を得た。その後銅箔（負極集電体）の裏面も同様に負極層用スラリーを塗工し乾燥させ銅箔（負極集電体）の裏面にも負極層を形成した。
[Preparation of negative electrode]
PVdF, negative electrode active material particles (Li 4 Ti 5 O 12 (LTO) particles), and the same sulfide-based solid electrolyte (Li 2 SP 2 S 5 -based glass ceramic) as above were added to a polypropylene container. , the obtained negative electrode layer slurry was stirred for 30 minutes with an ultrasonic dispersing device. The negative electrode layer slurry was applied onto the copper foil by a blade method using an applicator. Thereafter, the negative electrode layer slurry was naturally dried and dried on a hot plate at 100° C. for 30 minutes to obtain a negative electrode having a negative electrode layer on a copper foil (negative electrode current collector). Thereafter, the negative electrode layer slurry was applied to the back surface of the copper foil (negative electrode current collector) in the same manner and dried to form a negative electrode layer on the back surface of the copper foil (negative electrode current collector).
［固体電解質層の作製］
ポリプロピレン製容器に、ヘプタン、ＢＲ、及び、硫化物系固体電解質（Ｌｉ２Ｓ－Ｐ２Ｓ５系ガラスセラミック）を加え、得られた固体電解質層用スラリーを超音波分散装置で３０秒間攪拌した。次に、容器を振とう機（柴田科学社製ＴＴＭ－１）で３０分間振とうさせ、固体電解質層用スラリーをさらに超音波分散装置で３０秒間攪拌した。容器を振とう機で３分間振とうさせた後、アプリケーターを使用してブレード法にて固体電解質層用スラリーをアルミニウム箔上に塗工した。その後、固体電解質層用スラリーを自然乾燥させ、１００℃のホットプレート上で３０分間乾燥させることにより、基材としてのアルミニウム箔上に固体電解質層を形成した。
[Preparation of Solid Electrolyte Layer]
Heptane, BR, and a sulfide-based solid electrolyte (Li 2 SP 2 S 5 -based glass ceramic) were added to a polypropylene container, and the obtained solid electrolyte layer slurry was stirred for 30 seconds with an ultrasonic dispersion device. . Next, the container was shaken for 30 minutes with a shaker (TTM-1 manufactured by Shibata Kagaku Co., Ltd.), and the solid electrolyte layer slurry was further stirred for 30 seconds with an ultrasonic dispersing device. After shaking the container with a shaker for 3 minutes, the slurry for the solid electrolyte layer was applied onto an aluminum foil by a blade method using an applicator. After that, the solid electrolyte layer slurry was naturally dried and dried on a hot plate at 100° C. for 30 minutes to form a solid electrolyte layer on an aluminum foil as a substrate.
［積層体の作製］
（１）積層体取得工程
各負極層と、各固体電解質層とが直接接触するように、負極の両面に固体電解質層を張合わせ、１．６ｔ／ｃｍでプレスし、その後、基材であるアルミニウム箔を各固体電解質層から剥がした。続いて、正極層と固体電解質層とが直接接触するように、各固体電解質層に正極層を張合わせ、１．６ｔ／ｃｍでプレスした。その後各正極層から基材であるアルミニウム箔をはがし積層体を得た。
[Preparation of laminate]
(1) Laminate obtaining step The solid electrolyte layers are laminated on both sides of the negative electrode so that each negative electrode layer and each solid electrolyte layer are in direct contact, pressed at 1.6 t / cm, and then a base material. The aluminum foil was peeled off from each solid electrolyte layer. Subsequently, the positive electrode layer was attached to each solid electrolyte layer so that the positive electrode layer and the solid electrolyte layer were in direct contact with each other, and pressed at 1.6 t/cm. After that, the aluminum foil as the substrate was peeled off from each positive electrode layer to obtain a laminate.
（２）裁断工程
得られた積層体を５ｔ／ｃｍ、１７０℃でプレスした。
その後、正極層サイズが７０．０ｍｍ×７１．０ｍｍになるように、レーザートリミングし、負極サイズが７２．０ｍｍ×７２．０ｍｍになるように積層体を裁断した。そして、積層体の１つの側面に負極端子を溶接した。
図２は裁断工程前の積層体の一例を示す図である。
図３は裁断工程後の積層体の一例を示す図である。
図３に示すように正極層サイズが７０．０ｍｍ×７０．０ｍｍになるように、積層体の負極端子を溶接した側面とは反対側の側面が面一となるように図２に示す裁断ラインで積層体を裁断し、総厚みが１３０μｍの積層体を得た。
(2) Cutting step The obtained laminate was pressed at 5 t/cm and 170°C.
After that, laser trimming was performed so that the positive electrode layer size was 70.0 mm×71.0 mm, and the laminate was cut so that the negative electrode layer size was 72.0 mm×72.0 mm. Then, a negative electrode terminal was welded to one side surface of the laminate.
FIG. 2 is a diagram showing an example of a laminate before the cutting process.
FIG. 3 is a diagram showing an example of the laminate after the cutting process.
As shown in FIG. 3, the cutting line shown in FIG. 2 so that the positive electrode layer size is 70.0 mm × 70.0 mm, and the side surface opposite to the side surface where the negative electrode terminal of the laminate is welded is flush. to obtain a laminate having a total thickness of 130 μm.
（３）接合体形成工程
図４は、実施例１の（３）接合体形成工程、（４）接着工程の概略を示す図である。２０は正極集電箔、２１は、両面テープＮｏ．５６０５、２２は、Ｑ５１、３０は、正極層、４０は、固体電解質層－負極層－負極集電体＋負極端子－負極層－固体電解質層の積層体、４１は、負極端子、５０は、正極層－固体電解質層－負極層－負極集電体＋負極端子－負極層－固体電解質層－正極層の積層体を示す。
帝人ディポン社製ポリエチレンナフタレートフィルムＱ５１（厚み５０μｍ）と日東電工社製両面テープＮｏ．５６０５（厚み５０μｍ）との２層の積層体（厚み１００μｍ）であって、Ｑ５１の奥行きが正極集電箔の奥行よりも大きく、両面テープＮｏ．５６０５の奥行きが正極集電箔の奥行きよりも小さい絶縁層を準備した。絶縁層の厚み（１００μｍ）は積層体の厚み（１３０μｍ）よりも小さい。
絶縁層を３ｍｍ幅に裁断し、当該絶縁層を、両面テープＮｏ．５６０５が第２集電体としての正極集電箔と接するように正極集電箔の面上の積層体を配置する予定の領域に隣接する領域（負極端子側から面方向に７０～７２ｍｍの位置）に貼合わせ、正極集電箔と絶縁層の接合体を形成した。
(3) Joined Body Forming Step FIG. 4 is a diagram schematically showing (3) joined body forming step and (4) bonding step of the first embodiment. 20 is a positive current collector foil, 21 is a double-sided tape No. 5605, 22 are Q51, 30 is a positive electrode layer, 40 is a laminate of solid electrolyte layer - negative electrode layer - negative electrode current collector + negative electrode terminal - negative electrode layer - solid electrolyte layer, 41 is a negative electrode terminal, 50 is, A laminate of positive electrode layer-solid electrolyte layer-negative electrode layer-negative electrode current collector+negative electrode terminal-negative electrode layer-solid electrolyte layer-positive electrode layer is shown.
Polyethylene naphthalate film Q51 (thickness: 50 µm) manufactured by Teijin Dipon and double-sided tape No. 1 manufactured by Nitto Denko. 5605 (thickness: 50 μm) and two layers (thickness: 100 μm), the depth of Q51 is greater than the depth of the positive electrode current collector foil, and the double-sided tape No. 5605 (thickness: 50 μm). An insulating layer 5605 having a depth smaller than the depth of the positive electrode current collector foil was prepared. The thickness of the insulating layer (100 μm) is smaller than the thickness of the laminate (130 μm).
The insulating layer was cut to a width of 3 mm, and the insulating layer was attached to a double-sided tape No. 1. 5605 is in contact with the positive electrode current collector foil as the second current collector, the area adjacent to the area where the laminate is to be arranged on the surface of the positive electrode current collector foil (position 70 to 72 mm in the planar direction from the negative electrode terminal side) ) to form a bonded body of the positive current collector foil and the insulating layer.
（４）接着工程
正極集電箔上にホットメルト材を塗布した。その後、正極集電箔の面上において、絶縁層（テープ）を積層体の配置の位置決めの基準として、正極集電箔の面上の積層体を配置する予定の領域に第２電極層が正極集電箔と接するように積層体を配置し、且つ、絶縁層に積層体の面一である側面を接触させ、絶縁層と積層体の面一である側面と、を接着し、且つ、これらを１４０℃で加熱し、正極集電箔と積層体をホットメルト材により接着して固定した。
その後、積層体の正極集電箔側とは積層方向の反対側に別の正極集電箔をホットメルト材を介して配置し、これらを１４０℃、５ＭＰａの条件でプレスして貼り合わせ、正極端子を溶接し、その後、これらを真空シールし、全固体電池を得た。
その後、全固体電池の抵抗を測定し、短絡しているか否かを確認した。
(4) Adhesion process A hot-melt material was applied onto the positive electrode current collector foil. After that, on the surface of the positive electrode current collector foil, the insulating layer (tape) is used as a reference for positioning the laminate, and the second electrode layer is placed on the area where the laminate is to be arranged on the surface of the positive electrode current collector foil. Disposing the laminate so as to be in contact with the current collector foil, bringing the flush side surface of the laminate into contact with the insulating layer, bonding the insulating layer and the flush side surface of the laminate, and was heated at 140° C., and the positive current collector foil and the laminate were adhered and fixed with a hot-melt material.
After that, another positive electrode current collector foil is placed on the opposite side of the laminate from the positive electrode current collector foil side in the stacking direction via a hot-melt material, and these are pressed under conditions of 140° C. and 5 MPa to bond them together, forming a positive electrode. The terminals were welded and then vacuum-sealed to obtain an all solid state battery.
After that, the resistance of the all-solid-state battery was measured to confirm whether or not it was short-circuited.
（実施例２）
図５は、実施例２の（３）接合体形成工程、（４）接着工程の概略を示す図である。図５に示す数字の意味は図４と同じである。
上記（３）接合体形成工程において、日東電工社製両面テープＮｏ．５６０５（厚み５０μｍ）と帝人ディポン社製ポリエチレンナフタレートフィルムＱ５１（厚み５０μｍ）と日東電工社製両面テープＮｏ．５６０５（厚み５０μｍ）との３層の積層体（厚み１５０μｍ）であって、Ｑ５１の奥行きが正極集電箔の奥行よりも大きく、両面テープＮｏ．５６０５の奥行きが正極集電箔の奥行きよりも小さい絶縁層を準備した。絶縁層の厚み（１５０μｍ）は積層体の厚み（１３０μｍ）よりも大きい。
絶縁層を３ｍｍ幅に裁断し、当該絶縁層を、一方の両面テープＮｏ．５６０５が第２集電体としての正極集電箔と接するように正極集電箔の面上の積層体を配置する予定の領域に隣接する領域に貼合わせ、正極集電箔と絶縁層の接合体を形成したこと以外は実施例１と同様の方法で全固体電池を得た。
(Example 2)
FIG. 5 is a diagram schematically showing (3) bonded body forming step and (4) bonding step in Example 2. As shown in FIG. The meanings of numbers shown in FIG. 5 are the same as in FIG.
In the above (3) bonding body forming step, double-sided tape No. 5605 (thickness: 50 μm), polyethylene naphthalate film Q51 (thickness: 50 μm) manufactured by Teijin Dipon, and double-sided tape No. 5605 (thickness: 50 μm) manufactured by Nitto Denko. 5605 (
The insulating layer was cut to a width of 3 mm, and the insulating layer was attached to one of the double-sided tape No. 5605 is in contact with the positive electrode current collector foil as the second current collector, and the positive electrode current collector foil and the insulating layer are bonded to the area adjacent to the area where the laminate on the surface of the positive electrode current collector foil is to be arranged. An all-solid battery was obtained in the same manner as in Example 1, except that the body was formed.
（実施例３）
図６は、実施例３の（３）接合体形成工程、（４）接着工程の概略を示す図である。２３は、ハイボンＺＨ２３４－１を示し、それ以外の図６に示す数字の意味は図４と同じである。
上記（３）接合体形成工程において、絶縁層として、日立化成社製ハイボンＺＨ２３４－１を厚み１４０μｍのスペーサーと一緒に１２０℃の条件でプレスして得たものを準備した。絶縁層の厚み（１４０μｍ）は積層体の厚み（１３０μｍ）よりも大きい。
絶縁層を３ｍｍ幅に裁断し、当該絶縁層を結着剤としてのＰＶＤＦを含む酪酸ブチル溶液を用いて、正極集電箔の面上の積層体を配置する予定の領域に隣接する領域に貼合わせ、正極集電箔と絶縁層の接合体を形成した。これら以外は実施例１と同様の方法で全固体電池を得た。
(Example 3)
FIG. 6 is a diagram schematically showing (3) bonded body forming step and (4) bonding step of Example 3. In FIG. 23 indicates Hibon ZH234-1, and the meanings of other numbers shown in FIG. 6 are the same as in FIG.
In the step (3) of forming the joined body, an insulating layer was prepared by pressing Hybon ZH234-1 manufactured by Hitachi Chemical Co., Ltd. together with a spacer having a thickness of 140 μm at a temperature of 120°C. The thickness of the insulating layer (140 μm) is greater than the thickness of the laminate (130 μm).
The insulating layer was cut to a width of 3 mm, and a butyl butyrate solution containing PVDF as a binder was used to attach the insulating layer to a region adjacent to the region where the laminate was to be placed on the surface of the positive electrode current collector foil. Together, a bonded body of the positive electrode current collector foil and the insulating layer was formed. An all-solid battery was obtained in the same manner as in Example 1 except for these.
（比較例１）
図７は、比較例１の（３）接合体形成工程、（４）接着工程の概略を示す図である。図７に示す数字の意味は図４と同じである。
上記（４）接着工程において、積層体の負極端子側側面の正極層端部から面方向中心部に向かって１ｍｍの位置を正極集電体と張り合わせる基準位置として設定し、積層体の負極端子側側面の正極層端部から面方向中心部に向かって１ｍｍまでの領域が正極集電箔と対向しないように、正極集電箔上に積層体を配置し、正極集電箔と積層体を固定した。すなわち、上記（３）接合体形成工程において、絶縁層の一部（幅１ｍｍ）を正極集電箔の面上の積層体を配置する予定の領域（負極端子側から面方向に７０～７２ｍｍの位置ではなく６９～７１ｍｍの位置）に配置した。これ以外は実施例１と同様の方法で全固体電池を得た。
(Comparative example 1)
FIG. 7 is a diagram schematically showing (3) bonded body forming step and (4) bonding step of Comparative Example 1. As shown in FIG. The meanings of numbers shown in FIG. 7 are the same as in FIG.
In the above (4) bonding step, a position 1 mm from the positive electrode layer end on the side surface of the laminate on the negative terminal side toward the center in the plane direction is set as a reference position for bonding with the positive electrode current collector. The laminate was placed on the positive electrode current collector foil so that the positive electrode current collector foil did not face the positive electrode current collector foil in a region extending from the end of the positive electrode layer on the side surface to the center in the plane direction, and the positive electrode current collector foil and the laminate were separated. Fixed. That is, in the above (3) joined body forming step, part of the insulating layer (width 1 mm) is placed on the surface of the positive electrode current collector foil (70 to 72 mm in the planar direction from the negative electrode terminal side). 69-71 mm position). An all-solid battery was obtained in the same manner as in Example 1 except for this.
（比較例２）
図８は、比較例２の（３）接合体形成工程、（４）接着工程の概略を示す図である。図８に示す数字の意味は図４と同じである。
上記（４）接着工程において、積層体の負極端子側側面の正極層端部から面方向中心部に向かって２ｍｍの位置を正極集電体と張り合わせる基準位置として設定し、積層体の負極端子側側面の正極層端部から面方向中心部に向かって２ｍｍまでの領域が正極集電箔と対向しないように、正極集電箔上に積層体を配置し、正極集電箔と積層体を固定した。すなわち、上記（３）接合体形成工程において、絶縁層の一部（幅２ｍｍ）を正極集電箔の面上の積層体を配置する予定の領域（負極端子側から面方向に７０～７２ｍｍの位置ではなく６８～７０ｍｍの位置）に配置した。これ以外は実施例１と同様の方法で全固体電池を得た。
(Comparative example 2)
FIG. 8 is a diagram schematically showing (3) bonded body forming step and (4) bonding step of Comparative Example 2. As shown in FIG. The meanings of numbers shown in FIG. 8 are the same as in FIG.
In the bonding step (4), a position 2 mm from the positive electrode layer end on the side surface of the laminate on the negative terminal side toward the center in the plane direction is set as a reference position for bonding with the positive electrode current collector, and the negative electrode terminal of the laminate is set. The laminate was placed on the positive electrode current collector foil so that the positive electrode current collector foil did not face the positive electrode current collector foil in a region extending from the end of the positive electrode layer on the side surface to the center in the plane direction, and the positive electrode current collector foil and the laminate were separated. Fixed. That is, in the above (3) bonded body forming step, a part of the insulating layer (width 2 mm) is placed on the surface of the positive electrode current collector foil (70 to 72 mm in the planar direction from the negative electrode terminal side). 68-70 mm position). An all-solid battery was obtained in the same manner as in Example 1 except for this.
［評価方法］
実施例１～３、比較例１～２の全固体電池のサンプルをそれぞれ１０個作製し、それぞれ抵抗を測定し、短絡の発生したサンプルの個数及び、正極層と絶縁層との重なりが発生したサンプルの個数を確認した。これらの結果を表１に示す。
[Evaluation method]
Ten samples of the all-solid-state batteries of Examples 1 to 3 and Comparative Examples 1 and 2 were prepared, and the resistance was measured. Check the number of samples. These results are shown in Table 1.
［評価結果］
表１に示すように、実施例１～３の全固体電池は、短絡が発生せず、正極層と絶縁層の重なりも発生しないことがわかる。したがって、本開示の製造方法によれば、全固体電池のエネルギー密度を向上させることできる。
[Evaluation results]
As shown in Table 1, in the all-solid-state batteries of Examples 1 to 3, no short circuit occurred, and no overlap between the positive electrode layer and the insulating layer occurred. Therefore, according to the manufacturing method of the present disclosure, it is possible to improve the energy density of the all-solid-state battery.
１１ 第１集電体
１２ 第１電極層
１３ 固体電解質層
１４ 第２電極層
１５ 第２集電体
１６ 絶縁層
２０ 正極集電箔
２１ 両面テープＮｏ．５６０５
２２ Ｑ５１
２３ ハイボンＺＨ２３４－１
３０ 正極層
４０ 固体電解質層－負極層－負極集電体＋負極端子－負極層－固体電解質層の積層体
４１ 負極端子
５０ 正極層－固体電解質層－負極層－負極集電体＋負極端子－負極層－固体電解質層－正極層の積層体
11 First current collector 12
22 Q51
23 Hibon ZH234-1
30
Claims (1)
前記第１集電体の両面に、前記第１電極層、前記固体電解質層、前記第２電極層をこの順で積層した積層体を得る工程と、
前記積層体の積層方向の少なくとも１つの側面を裁断により面一とする工程と、
前記第２集電体の面上の前記積層体を配置する予定の領域に隣接する領域に絶縁層を配置し、当該第２集電体と当該絶縁層の接合体を形成する工程と、
前記第２集電体の面上の前記積層体を配置する予定の領域に前記第２電極層が当該第２集電体と接するように前記積層体を配置し、且つ、前記絶縁層と前記積層体の面一である側面と、を接着する工程と、を備えることを特徴とする全固体電池の製造方法。 A method for manufacturing an all-solid-state battery having a first electrode layer, a solid electrolyte layer, a second electrode layer, and a second current collector in this order on both sides of a first current collector,
obtaining a laminate in which the first electrode layer, the solid electrolyte layer, and the second electrode layer are laminated in this order on both sides of the first current collector;
a step of cutting at least one side surface of the laminate in the stacking direction to make it flush;
disposing an insulating layer in a region adjacent to a region where the laminate is to be disposed on the surface of the second current collector, and forming a bonded body of the second current collector and the insulating layer;
The laminate is arranged so that the second electrode layer is in contact with the second current collector in a region where the laminate is to be arranged on the surface of the second current collector, and the insulating layer and the A method for manufacturing an all-solid-state battery, comprising a step of adhering a side surface of the laminate that is flush with the laminate.
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