JP2020098745A - Electrode plate for all-solid battery - Google Patents
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Abstract
Description
本開示は、全固体電池用電極板に関する。 The present disclosure relates to an electrode plate for all-solid-state batteries.
リチウムイオン電池等の電池の分野において、電解液の代わりに固体電解質を使用する全固体電池の開発が行われている。全固体電池は、電池内に可燃性の有機溶媒を用いないので、安全装置の簡素化が図れ、製造コストや生産性に優れると考えられている。全固体電池では、各層間の物理的な接触により導通をとっているため、各層が互いに接触するように配置される。
一方、電池の高電圧化及び高容量化等の要求に対し、多数の電池ユニットを積層した積層型電池の開発が行われている。積層型電池においては、積層された電池ユニット間の配置がずれると、電池性能が変動してしまうため、振動や衝撃等により各電池ユニットがずれないように固定されることが望ましい。
BACKGROUND ART In the field of batteries such as lithium-ion batteries, development of all-solid-state batteries that use a solid electrolyte instead of an electrolytic solution is underway. Since the all-solid-state battery does not use a flammable organic solvent in the battery, it is considered that the safety device can be simplified and the manufacturing cost and the productivity are excellent. In an all-solid-state battery, the layers are arranged so that they are in contact with each other because they are electrically connected by physical contact between the layers.
On the other hand, in order to meet the demands for higher voltage and higher capacity of batteries, a stacked battery in which a large number of battery units are stacked is being developed. In the stack type battery, if the arrangement of the stacked battery units shifts, the battery performance fluctuates. Therefore, it is desirable that the battery units be fixed so as not to shift due to vibration or shock.
例えば、本出願人は、特許文献１に、２個以上の電池ユニットが積層されてなる全固体電池において、隣接して積層された２個の電池ユニット間を固定するために、一方の電池ユニットの表面にある集電体と、もう一方の電池ユニットの表面にある集電体又は活物質層とを、熱可塑性樹脂を用いて四隅で接着する接着手段を開示している。 For example, in the all-solid-state battery in which two or more battery units are stacked, the present applicant discloses in Patent Document 1 one battery unit in order to fix between two battery units that are adjacently stacked. There is disclosed an adhesion means for adhering the current collector on the surface of the battery and the current collector or active material layer on the surface of the other battery unit at four corners by using a thermoplastic resin.
一方、電解液を用いた非水電解液電池の分野では、例えば特許文献２に、集電体の少なくとも一方の面に、カーボンを含有したポリアミドイミド樹脂からなる接着層と、活物質層とを順に積層した電池用電極板が開示されている。特許文献３には、正極集電体上に直接正極合剤を塗布、乾燥することにより正極活物質層を設けた正極板、及び負極集電体上に直接負極合剤を塗布、乾燥することにより負極活物質層を設けた負極板が開示されている。 On the other hand, in the field of non-aqueous electrolyte batteries using an electrolytic solution, for example, in Patent Document 2, an adhesive layer made of a polyamide-imide resin containing carbon and an active material layer are provided on at least one surface of a current collector. An electrode plate for a battery, which is sequentially stacked, is disclosed. In Patent Document 3, a positive electrode mixture is directly coated on a positive electrode current collector and dried to form a positive electrode plate provided with a positive electrode active material layer, and a negative electrode mixture is directly coated on a negative electrode current collector and dried. Discloses a negative electrode plate provided with a negative electrode active material layer.
しかしながら、従来の全固体電池においては、電池製造中や電池使用中に発生する異物が、集電体と電極活物質層との間に混入する恐れがある。異物が混入すると、異物除去工程や異物検査工程が必要となり、生産コスト増につながったり、工程内不良発生により歩留まりが悪化したりする場合がある。
本開示は、上記実情に鑑み、集電体と電極活物質層との間に異物が混入することを抑制できる全固体電池用電極板を提供することを目的とする。
However, in the conventional all-solid-state battery, foreign matter generated during battery production or during battery use may be mixed between the current collector and the electrode active material layer. When foreign matter is mixed in, a foreign matter removing step and a foreign matter inspecting step are required, which may lead to an increase in production cost and may deteriorate the yield due to the occurrence of in-process defects.
In view of the above situation, an object of the present disclosure is to provide an electrode plate for an all-solid-state battery that can prevent foreign matter from entering between the current collector and the electrode active material layer.
本開示の全固体電池用電極板は、集電体と、電極活物質層と、前記集電体と前記電極活物質層とを接着する接着剤部とを有し、
前記接着剤部が、互いに接着する前記集電体と前記電極活物質層との重複領域の外周全体に沿った前記重複領域の端部に少なくとも存在することを特徴とする。
The electrode plate for an all-solid-state battery of the present disclosure has a current collector, an electrode active material layer, and an adhesive part that bonds the current collector and the electrode active material layer,
It is characterized in that the adhesive portion is present at least at an end portion of the overlapping region along the entire outer periphery of the overlapping region of the current collector and the electrode active material layer which are bonded to each other.
本開示によれば、互いに接着する集電体と電極活物質層との重複領域の外周全体に沿った前記重複領域の端部が、接着剤部により接着されていることにより、集電体と電極活物質層との間に異物が混入することを抑制することができる。 According to the present disclosure, the end portion of the overlapping region along the entire outer periphery of the overlapping region of the current collector and the electrode active material layer that are bonded to each other is bonded by the adhesive portion, and thus It is possible to prevent foreign matter from mixing with the electrode active material layer.
本開示の全固体電池用電極板は、集電体と、電極活物質層と、前記集電体と前記電極活物質層とを接着する接着剤部とを有し、
前記接着剤部が、互いに接着する前記集電体と前記電極活物質層との重複領域の外周全体に沿った前記重複領域の端部に少なくとも存在することを特徴とする。
The electrode plate for an all-solid-state battery of the present disclosure has a current collector, an electrode active material layer, and an adhesive part that bonds the current collector and the electrode active material layer,
It is characterized in that the adhesive portion is present at least at an end portion of the overlapping region along the entire outer periphery of the overlapping region of the current collector and the electrode active material layer which are bonded to each other.
特許文献１の全固体電池は、集電体と電極活物質層とが四隅で接着されており、部分的な接着のため、接着されていない集電体と電極活物質層との間に隙間が生じやすく、電池製造中や電池使用中に生じる電極粉や、集電体に用いられる金属箔のバリが脱落して生じる金属片等の異物が、集電体と電極活物質層との間に生じた隙間に混入する恐れがある。
それに対し、本開示の全固体電池用電極板は、接着剤部により、集電体と電極活物質層との重複領域の外周全体に沿った前記重複領域の端部が少なくとも接着されているため、互いに接着する集電体と電極活物質層との間に隙間が生じ難く、集電体と電極活物質層との間に異物が混入することが抑制される。
In the all-solid-state battery of Patent Document 1, the current collector and the electrode active material layer are bonded at the four corners, and due to partial bonding, there is a gap between the unbonded current collector and the electrode active material layer. Between the current collector and the electrode active material layer is likely to occur due to electrode powder generated during battery manufacturing or during battery use, or metal pieces such as metal flakes resulting from the burrs of the metal foil used for the current collector falling off. There is a risk that it will be mixed in the gap created in.
On the other hand, the electrode plate for all-solid-state batteries of the present disclosure, at least the end portion of the overlapping region along the entire outer periphery of the overlapping region of the current collector and the electrode active material layer is adhered by the adhesive portion. A gap is unlikely to be formed between the current collector and the electrode active material layer that are adhered to each other, and entry of foreign matter between the current collector and the electrode active material layer is suppressed.
本開示の全固体電池用電極板において、前記接着剤部により互いに接着する集電体と電極活物質層との組み合わせとしては、正極集電体と正極活物質層との組み合わせ、及び負極集電体と負極活物質層との組み合わせが挙げられる。
本開示の全固体電池用電極板の実施形態としては、例えば、
（ｉ）正極集電体と、正極活物質層と、前記正極集電体と前記正極活物質層とを接着する接着剤部とを有し、
前記接着剤部が、互いに接着する前記正極集電体と前記正極活物質層との重複領域の外周全体に沿った前記重複領域の端部に少なくとも存在する、全固体電池用電極板、
（ｉｉ）負極集電体と、負極活物質層と、前記負極集電体と前記負極活物質層とを接着する接着剤部とを有し、
前記接着剤部が、互いに接着する前記負極集電体と前記負極活物質層との重複領域の外周全体に沿った前記重複領域の端部に少なくとも存在する、全固体電池用電極板、及び、
（ｉｉｉ）正極集電体と、正極活物質層と、前記正極集電体と前記正極活物質層とを接着する接着剤部と、負極集電体と、負極活物質層と、前記負極集電体と前記負極活物質層とを接着する接着剤部とを有し、
前記正極集電体と前記正極活物質層とを接着する接着剤部が、互いに接着する前記正極集電体と前記正極活物質層との重複領域の外周全体に沿った前記重複領域の端部に少なくとも存在し、
前記負極集電体と前記負極活物質層とを接着する接着剤部が、互いに接着する前記負極集電体と前記負極活物質層との重複領域の外周全体に沿った前記重複領域の端部に少なくとも存在する、全固体電池用電極板を挙げることができる。
In the electrode plate for an all-solid-state battery of the present disclosure, as the combination of the current collector and the electrode active material layer that are bonded to each other by the adhesive part, a combination of a positive electrode current collector and a positive electrode active material layer, and a negative electrode current collector A combination of the body and the negative electrode active material layer may be mentioned.
Examples of the embodiment of the electrode plate for an all-solid battery of the present disclosure include, for example,
(I) a positive electrode current collector, a positive electrode active material layer, and an adhesive portion for bonding the positive electrode current collector and the positive electrode active material layer,
The adhesive portion, at least at the end of the overlapping region along the entire outer periphery of the overlapping region of the positive electrode current collector and the positive electrode active material layer to be bonded to each other, all-solid-state battery electrode plate,
(Ii) a negative electrode current collector, a negative electrode active material layer, and an adhesive part for bonding the negative electrode current collector and the negative electrode active material layer,
The adhesive portion, at least at the end of the overlapping region along the entire outer periphery of the overlapping region of the negative electrode current collector and the negative electrode active material layer to be bonded to each other, all-solid battery electrode plate, and,
(Iii) A positive electrode current collector, a positive electrode active material layer, an adhesive part for adhering the positive electrode current collector and the positive electrode active material layer, a negative electrode current collector, a negative electrode active material layer, and the negative electrode current collector. An adhesive part for adhering the electric body and the negative electrode active material layer,
An adhesive part for adhering the positive electrode current collector and the positive electrode active material layer is an end part of the overlapping region along the entire outer circumference of the overlapping region of the positive electrode current collector and the positive electrode active material layer adhering to each other. Exists at least in
An adhesive portion for adhering the negative electrode current collector and the negative electrode active material layer, an end portion of the overlapping region along the entire outer circumference of the overlapping region of the negative electrode current collector and the negative electrode active material layer adhering to each other. The electrode plate for all-solid-state batteries, which exists at least in the above, can be mentioned.
１．集電体
本開示の全固体電池用電極板が有する集電体は、後述する電極活物質層の集電を行う機能を有するものであり、正極活物質層に対しては正極集電体を用い、負極活物質層に対しては負極集電体を用いる。
1. Current collector The current collector included in the electrode plate for an all-solid battery of the present disclosure has a function of collecting current in the electrode active material layer described below, and a positive electrode current collector is provided for the positive electrode active material layer. A negative electrode current collector is used for the negative electrode active material layer.
（１−１）正極集電体
正極集電体は、後述する正極活物質層の集電を行う機能を有するものであり、全固体電池の正極集電体として使用可能な公知のものを適宜選択して用いることができ、特に限定はされない。
前記正極集電体の材料としては、例えば、ＳＵＳ、Ｎｉ、Ｃｒ、Ａｕ、Ｐｔ、Ａｌ、Ｆｅ、Ｔｉ、Ｚｎ等の金属を挙げることができる。
(1-1) Positive Electrode Current Collector The positive electrode current collector has a function of collecting current in the positive electrode active material layer described later, and may be any known material that can be used as a positive electrode current collector for all-solid-state batteries. It can be selected and used without any particular limitation.
Examples of the material of the positive electrode current collector include metals such as SUS, Ni, Cr, Au, Pt, Al, Fe, Ti and Zn.
前記正極集電体は、前記金属を含有する金属箔の表面の少なくとも一部に、Ｎｉ、Ｃｒ、Ｃ（カーボン）等の導電助剤を含有するコート層を有するものであっても良い。前記コート層を有することにより、正極集電体の表面に不動態被膜が形成されて内部抵抗が増大することを抑制できる。
前記コート層は、少なくとも前記導電助剤を含有し、必要に応じて、結着剤等のその他の成分を更に含有していても良い。前記コート層が含有していても良い結着剤としては、例えば、後述する正極活物質層が含有していても良い結着剤と同様のものを挙げることができる。また、前記コート層は、前記導電助剤からなるめっき層又は蒸着層であっても良い。
前記コート層の具体例としては、例えば、導電助剤としてのＣ（カーボン）を１５質量％含有し、更に結着剤としてのポリフッ化ビニリデン（ＰＶＤＦ）を８５質量％含有し、体積抵抗率が５×１０３Ωｃｍのカーボンコート層を挙げることができる。
前記コート層の厚みは特に限定はされないが、内部抵抗の増大を抑制する点から、好ましくは１μｍ以上５０μｍ以下であり、例えば１０μｍ程度とすることができる。
前記コート層は、前記正極集電体の表面において、互いに接着する正極集電体と正極活物質層との重複領域内に配置されていることが、内部抵抗の増大を抑制しやすい点から好ましい。中でも、互いに接着する正極集電体と正極活物質層とが、後述する接着剤部を介さずに直接接触する部分を有する場合に、正極活物質層と直接接触する前記正極集電体の表面の少なくとも一部に、前記コート層を有することが好ましい。
The positive electrode current collector may have a coating layer containing a conductive additive such as Ni, Cr or C (carbon) on at least a part of the surface of the metal foil containing the metal. By having the coating layer, it is possible to suppress an increase in internal resistance due to formation of a passivation film on the surface of the positive electrode current collector.
The coat layer contains at least the conductive additive, and may further contain other components such as a binder, if necessary. Examples of the binder that the coat layer may contain include the same binders that the positive electrode active material layer described later may contain. Further, the coat layer may be a plating layer or a vapor deposition layer made of the conductive additive.
Specific examples of the coating layer include, for example, 15% by mass of C (carbon) as a conductive additive, 85% by mass of polyvinylidene fluoride (PVDF) as a binder, and a volume resistivity of An example is a carbon coating layer of 5×10 3 Ωcm.
The thickness of the coat layer is not particularly limited, but is preferably 1 μm or more and 50 μm or less, for example, about 10 μm, from the viewpoint of suppressing an increase in internal resistance.
It is preferable that the coat layer is arranged in the overlapping region of the positive electrode current collector and the positive electrode active material layer, which are bonded to each other, on the surface of the positive electrode current collector, from the viewpoint of easily suppressing an increase in internal resistance. .. Among them, in the case where the positive electrode current collector and the positive electrode active material layer which are adhered to each other have a portion which is in direct contact without an adhesive part described later, the surface of the positive electrode current collector which is in direct contact with the positive electrode active material layer. It is preferable to have the coat layer on at least a part of the above.
（１−２）負極集電体
負極集電体は、後述する負極活物質層の集電を行う機能を有するものであり、全固体電池の負極集電体として使用可能な公知のものを適宜選択して用いることができ、特に限定はされない。
前記負極集電体の材料としては、例えば、ＳＵＳ、Ｃｕ、Ｎｉ、Ｆｅ、Ｔｉ、Ｃｏ、Ｚｎ等の金属を挙げることができる。
(1-2) Negative Electrode Current Collector The negative electrode current collector has a function of collecting current from the negative electrode active material layer described later, and may be any known material that can be used as a negative electrode current collector for all-solid-state batteries. It can be selected and used without any particular limitation.
Examples of the material of the negative electrode current collector include metals such as SUS, Cu, Ni, Fe, Ti, Co and Zn.
２．電極活物質層
本開示の全固体電池用電極板が有する電極活物質層は、正極活物質層及び負極活物質層から選ばれる少なくとも１種である。
（２−１）正極活物質層
正極活物質層は、少なくとも正極活物質を含有し、必要に応じ、固体電解質、結着剤及び導電材等を更に含有していても良い。
前記正極活物質としては、コバルト酸リチウム等に代表される公知の正極活物質を適宜選択して用いることができる。
2. Electrode Active Material Layer The electrode active material layer included in the electrode plate for an all-solid battery of the present disclosure is at least one selected from a positive electrode active material layer and a negative electrode active material layer.
(2-1) Positive Electrode Active Material Layer The positive electrode active material layer contains at least a positive electrode active material, and may further contain a solid electrolyte, a binder, a conductive material and the like, if necessary.
As the positive electrode active material, a known positive electrode active material typified by lithium cobalt oxide can be appropriately selected and used.
前記正極活物質層が含有していても良い固体電解質としては、例えば、Ｌｉ２Ｓを含む原料組成物を用いてなる硫化物系固体電解質等の公知の固体電解質を適宜選択して用いることができる。Ｌｉ２Ｓを含む硫化物系固体電解質としては、例えば、Ｌｉ２ＳとＰ２Ｓ５との質量比（Ｌｉ２Ｓ／Ｐ２Ｓ５）が０．５以上となるように、Ｌｉ２Ｓ及びＰ２Ｓ５を混合して作製される硫化物系固体電解質を挙げることができる。具体的には例えば、質量比でＬｉ２Ｓ：Ｐ２Ｓ５が７０：３０となるようにＬｉ２Ｓ及びＰ２Ｓ５を混合して作製される硫化物系固体電解質が、イオン伝導性の点から好ましく用いられる。 As the solid electrolyte that may be contained in the positive electrode active material layer, for example, a known solid electrolyte such as a sulfide-based solid electrolyte obtained by using a raw material composition containing Li 2 S may be appropriately selected and used. it can. The sulfide-based solid electrolyte containing Li 2 S, for example, as the mass ratio of Li 2 S and P 2 S 5 (Li 2 S / P 2 S 5) is 0.5 or more, Li 2 S And a sulfide-based solid electrolyte produced by mixing P 2 S 5 with each other. Specifically, for example, a sulfide-based solid electrolyte prepared by mixing Li 2 S and P 2 S 5 such that Li 2 S:P 2 S 5 has a mass ratio of 70:30 is ion-conductive. It is preferably used from the viewpoint of.
前記正極活物質層が含有していても良い結着剤としては、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）等のフッ素含有樹脂等の公知の結着剤を適宜選択して用いることができる。
前記正極活物質層が含有していても良い導電材としては、例えば、ＶＧＣＦ（気相法炭素繊維）及びアセチレンブラック等の公知の導電材を適宜選択して用いることができる。
As the binder that may be contained in the positive electrode active material layer, for example, a known binder such as a fluorine-containing resin such as polyvinylidene fluoride (PVDF) can be appropriately selected and used.
As the conductive material that may be contained in the positive electrode active material layer, for example, a known conductive material such as VGCF (vapor grown carbon fiber) and acetylene black can be appropriately selected and used.
前記正極活物質層の厚みは、特に限定されないが、例えば、０．１μｍ以上１０００μｍ以下とすることができる。 The thickness of the positive electrode active material layer is not particularly limited, but may be, for example, 0.1 μm or more and 1000 μm or less.
（２−２）負極活物質層
負極活物質層は、少なくとも負極活物質を含有し、必要に応じ、固体電解質、結着剤及び導電材等を更に含有していても良い。
前記負極活物質としては、グラファイト等の公知の炭素系負極活物質、及びその他の公知の負極活物質の中から適宜選択して用いることができる。
前記負極活物質層が含有していても良い固体電解質、結着剤及び導電材としては、例えば、前記正極活物質層が含有していても良い固体電解質、結着剤及び導電材と同様のものを挙げることができる。
前記負極活物質層の厚みは、特に限定されないが、例えば、０．１μｍ以上１０００μｍ以下とすることができる。
(2-2) Negative Electrode Active Material Layer The negative electrode active material layer contains at least a negative electrode active material, and may further contain a solid electrolyte, a binder, a conductive material and the like, if necessary.
The negative electrode active material can be appropriately selected from known carbon-based negative electrode active materials such as graphite and other known negative electrode active materials.
Examples of the solid electrolyte that the negative electrode active material layer may contain, the binder and the conductive material include, for example, the same solid electrolyte, binder and conductive material that the positive electrode active material layer may contain. I can list things.
The thickness of the negative electrode active material layer is not particularly limited, but can be, for example, 0.1 μm or more and 1000 μm or less.
３．電極体
前記集電体及び前記電極活物質層は、各々電極体の表面に形成されたものであっても良い。
前記正極活物質層を表面に有する電極体としては、例えば、前記正極活物質層と、固体電解質層と、前記負極活物質層と、前記負極集電体とがこの順に積層された層構成を有する電極体を挙げることができる。
前記正極集電体を表面に有する電極体としては、例えば、前記正極活物質層を表面に有する電極体の当該正極活物質層上に、後述する接着剤部を介して、前記正極集電体が積層された電極体を挙げることができる。
前記負極活物質層を表面に有する電極体としては、例えば、前記負極活物質層と、固体電解質層と、前記正極活物質層と、前記正極集電体がこの順に積層された層構成を有する電極体を挙げることができる。
前記負極集電体を表面に有する電極体としては、例えば、前記負極活物質層を表面に有する電極体の当該負極活物質層上に、後述する接着剤部を介して、前記負極集電体が積層された電極体を挙げることができる。
3. Electrode Body Each of the current collector and the electrode active material layer may be formed on the surface of an electrode body.
The electrode body having the positive electrode active material layer on the surface has, for example, a layer structure in which the positive electrode active material layer, a solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector are laminated in this order. The electrode body which it has can be mentioned.
Examples of the electrode body having the positive electrode current collector on the surface include, for example, the positive electrode current collector on the positive electrode active material layer of the electrode body having the positive electrode active material layer on the surface via an adhesive part described later. An electrode body in which is laminated can be given.
The electrode body having the negative electrode active material layer on its surface has, for example, a layer structure in which the negative electrode active material layer, a solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector are laminated in this order. An electrode body can be mentioned.
Examples of the electrode body having the negative electrode current collector on the surface include, for example, the negative electrode current collector on the negative electrode active material layer of the electrode body having the negative electrode active material layer on the surface via an adhesive part described later. An electrode body in which is laminated can be given.
前記電極体が有する固体電解質層は、少なくとも固体電解質を含有する層であり、全固体電池に使用可能な公知の固体電解質層を適宜選択して用いることができる。前記固体電解質層が含有する固体電解質としては、例えば、前記正極活物質層が含有していても良い固体電解質と同様のものを挙げることができる。前記固体電解質層は、必要に応じて、結着剤等を更に含有していても良い。前記固体電解質層が含有していても良い結着剤としては、例えば、ブタジエンゴム（ＢＲ）等を挙げることができる。
前記固体電解質層の厚さは、固体電解質層が含有する固体電解質の種類や、電極体の構成等に応じて調整されるものであり、特に限定はされないが、例えば０．１μｍ以上１０００μｍ以下の範囲内とすることができ、０．１μｍ以上３００μｍ以下の範囲内であっても良い。
The solid electrolyte layer included in the electrode body is a layer containing at least a solid electrolyte, and a known solid electrolyte layer that can be used in an all-solid battery can be appropriately selected and used. Examples of the solid electrolyte contained in the solid electrolyte layer include the same solid electrolytes that may be contained in the positive electrode active material layer. The solid electrolyte layer may further contain a binder and the like, if necessary. Examples of the binder that the solid electrolyte layer may contain include butadiene rubber (BR).
The thickness of the solid electrolyte layer is adjusted according to the type of solid electrolyte contained in the solid electrolyte layer, the configuration of the electrode body, and the like, and is not particularly limited, but is, for example, 0.1 μm or more and 1000 μm or less. It can be within the range, and may be within the range of 0.1 μm or more and 300 μm or less.
前記電極体の製造方法は、公知の方法を採用することができ、特に限定はされない。例えば、各層の原料となるスラリー又はペーストを塗布、乾燥した後、必要に応じてプレスすることにより各層を形成する塗工法、各層の原料となる粉末又はペレットをプレスすることにより各層を形成するプレス法、及びこれらを組み合わせた方法等を挙げることができる。 A known method can be adopted as a method for producing the electrode body, and is not particularly limited. For example, a coating method of forming each layer by applying a slurry or paste that is a raw material of each layer and drying, and then pressing if necessary, a press that forms each layer by pressing a powder or pellet that is a raw material of each layer The method, the method which combined these, etc. can be mentioned.
前記電極体の製造方法の一例として、両表面に正極活物質層を有する電極体の製造方法を以下に説明する。まず、少なくとも固体電解質を含有する固体電解質層用スラリーを、剥離シートの片面に塗布、乾燥することにより、剥離シートの片面に固体電解質層を有する固体電解質シートを作製する。一方、負極集電体の両面に、少なくとも負極活物質を含有する負極活物質層用スラリーを塗布、乾燥することにより、負極集電体の両面に負極活物質層を有する負極シートを作製する。次いで、固体電解質層と負極活物質層とが接触するように、前記負極シートの両面に前記固体電解質シートを積層し、例えば１０ＭＰａ以上５００ＭＰａ以下の範囲内の圧力、より具体的には例えば１００ＭＰａ程度の圧力でプレスすることにより、前記負極シートの両面に固体電解質層が転写された中間積層体１を得る。一方、少なくとも正極活物質を含有する正極活物質層用スラリーを、剥離シートの片面に塗布、乾燥することにより、剥離シートの片面に正極活物質層を有する正極シートを作製する。前記中間積層体１の両面にある剥離シートを剥離した後、固体電解質層と正極活物質層とが接触するように、前記中間積層体１の両面に前記正極シートを積層し、例えば１０ＭＰａ以上１００００ＭＰａ以下の範囲内の圧力、より具体的には例えば６００ＭＰａ程度の圧力でプレスし、両面の剥離シートを剥離することにより、後述する図２に示す電極体２０のような、両表面に正極活物質層を有する電極体を得ることができる。 As an example of the method of manufacturing the electrode body, a method of manufacturing the electrode body having positive electrode active material layers on both surfaces will be described below. First, a solid electrolyte layer slurry containing at least a solid electrolyte is applied to one surface of a release sheet and dried to produce a solid electrolyte sheet having a solid electrolyte layer on one surface of the release sheet. On the other hand, a negative electrode sheet having negative electrode active material layers on both surfaces of the negative electrode current collector is prepared by applying a slurry for negative electrode active material layer containing at least a negative electrode active material on both surfaces of the negative electrode current collector and drying. Then, the solid electrolyte sheet is laminated on both surfaces of the negative electrode sheet so that the solid electrolyte layer and the negative electrode active material layer are in contact with each other, and the pressure is in the range of 10 MPa or more and 500 MPa or less, more specifically, for example, about 100 MPa. By pressing at a pressure of 1, the intermediate laminate 1 in which the solid electrolyte layer is transferred to both surfaces of the negative electrode sheet is obtained. On the other hand, a positive electrode active material layer slurry containing at least a positive electrode active material is applied to one surface of a release sheet and dried to prepare a positive electrode sheet having a positive electrode active material layer on one surface of the release sheet. After peeling off the release sheets on both sides of the intermediate laminate 1, the positive electrode sheets are laminated on both sides of the intermediate laminate 1 so that the solid electrolyte layer and the positive electrode active material layer are in contact with each other, for example, 10 MPa or more and 10000 MPa. By pressing at a pressure within the following range, more specifically, at a pressure of, for example, about 600 MPa, the release sheets on both sides are peeled off, so that the positive electrode active material on both surfaces, such as the electrode body 20 shown in FIG. An electrode body having layers can be obtained.
前記電極体の製造方法の別の一例として、両表面に負極活物質層を有する電極体の製造方法としては、例えば、前記と同様に、剥離シートの片面に固体電解質層を有する固体電解質シートを作製し、一方、正極集電体の両面に、少なくとも正極活物質を含有する正極活物質層用スラリーを塗布、乾燥することにより、正極集電体の両面に正極活物質層を有する正極シートを作製する。次いで、固体電解質層と正極活物質層とが接触するように、前記正極シートの両面に前記固体電解質シートを積層し、例えば１０ＭＰａ以上５００ＭＰａ以下の範囲内の圧力、より具体的には例えば１００ＭＰａ程度の圧力でプレスすることにより、前記正極シートの両面に固体電解質層が転写された中間積層体２を得る。一方、少なくとも負極活物質を含有する負極活物質層用スラリーを、剥離シートの片面に塗布、乾燥することにより、剥離シートの片面に負極活物質層を有する負極シートを作製する。前記中間積層体２の両面にある剥離シートを剥離した後、固体電解質層と負極活物質層とが接触するように、前記中間積層体２の両面に前記負極シートを積層し、例えば１０ＭＰａ以上１００００ＭＰａ以下の範囲内の圧力、より具体的には例えば６００ＭＰａ程度の圧力でプレスし、両面の剥離シートを剥離することにより、両表面に負極活物質層を有する電極体を得ることができる。 As another example of the manufacturing method of the electrode body, as a manufacturing method of the electrode body having a negative electrode active material layer on both surfaces, for example, similar to the above, a solid electrolyte sheet having a solid electrolyte layer on one surface of the release sheet, On the other hand, a positive electrode sheet having a positive electrode active material layer on both surfaces of the positive electrode current collector is prepared by applying a slurry for a positive electrode active material layer containing at least a positive electrode active material on both surfaces of the positive electrode current collector, and drying. Create. Then, the solid electrolyte sheets are laminated on both surfaces of the positive electrode sheet so that the solid electrolyte layer and the positive electrode active material layer are in contact with each other, and the pressure is in the range of 10 MPa or more and 500 MPa or less, more specifically, for example, about 100 MPa. By pressing with the pressure of, the intermediate laminate 2 having the solid electrolyte layer transferred to both surfaces of the positive electrode sheet is obtained. On the other hand, a negative electrode active material layer slurry containing at least a negative electrode active material is applied to one surface of a release sheet and dried to prepare a negative electrode sheet having a negative electrode active material layer on one surface of the release sheet. After peeling off the release sheets on both sides of the intermediate laminate 2, the negative electrode sheets are laminated on both sides of the intermediate laminate 2 so that the solid electrolyte layer and the negative electrode active material layer are in contact with each other, for example, 10 MPa or more and 10000 MPa. An electrode body having a negative electrode active material layer on both surfaces can be obtained by pressing at a pressure within the following range, more specifically, a pressure of, for example, about 600 MPa, and peeling the release sheets on both sides.
前記電極体の製造に用いる負極シート及び正極シートにおいて、集電体上に電極活物質層を有するシートの場合は、剥離シート上に電極活物質層用スラリーを塗布、乾燥することにより形成した電極活物質層を、接着剤を配置した集電体上に積層した後、前記接着剤の種類に応じた手段で、前記集電体と前記電極活物質層とを接着させることにより、前記集電体と前記電極活物質層との間に後述する接着剤部を設けたものであっても良い。 In the negative electrode sheet and the positive electrode sheet used in the production of the electrode body, in the case of a sheet having an electrode active material layer on a current collector, an electrode formed by applying a slurry for an electrode active material layer on a release sheet and drying. After the active material layer is laminated on the current collector on which the adhesive is arranged, the current collector and the electrode active material layer are adhered by a means according to the type of the adhesive to obtain the current collector. An adhesive agent portion described below may be provided between the body and the electrode active material layer.
４．接着剤部
本開示の全固体電池用電極板が有する接着剤部は、前記集電体と前記電極活物質層とを接着する部位であり、例えば接着剤の固化物からなる。
前記接着剤部は、互いに接着される前記集電体と前記電極活物質層との重複領域の外周全体に沿った前記重複領域の端部に少なくとも存在する。ここで、前記集電体と前記電極活物質層との重複領域とは、本開示の全固体電池用電極板を厚み方向に平面視したときに、互いに接着する前記集電体と前記電極活物質層とが重なり合う領域のことをいう。前記集電体と前記電極活物質層との重複領域の外周全体に沿った前記重複領域の端部は、特に限定はされないが、例えば、前記集電体と前記電極活物質層との重複領域の輪郭から、前記重複領域の中心に向かう一定の距離までの領域とすることができる。前記重複領域の端部は、例えば、前記重複領域の輪郭と、前記重複領域の輪郭を縮小した相似形とに囲まれる領域であっても良い。
また、前記接着剤部は、前記集電体と前記電極活物質層との重複領域の外周全体に沿った前記重複領域の端部にのみ存在していても良いし、前記重複領域の端部と、当該端部に囲まれた内部の少なくとも一部とに存在していても良いし、前記集電体と前記電極活物質層との重複領域全体に存在していても良い。中でも、内部抵抗の増大を抑制する点から、前記接着剤部は、前記集電体と前記電極活物質層との重複領域の外周全体に沿った前記重複領域の端部にのみ存在していることが好ましい。
4. Adhesive Part The adhesive part of the electrode plate for an all-solid battery of the present disclosure is a part for adhering the current collector and the electrode active material layer, and is made of, for example, a solidified adhesive.
The adhesive portion is present at least at an end portion of the overlapping region along the entire outer periphery of the overlapping region of the current collector and the electrode active material layer that are bonded to each other. Here, the overlapping region of the current collector and the electrode active material layer is the current collector and the electrode active material that adhere to each other when the electrode plate for an all-solid-state battery of the present disclosure is viewed in a plan view in the thickness direction. The area where the material layer overlaps. The end of the overlapping region along the entire outer periphery of the overlapping region of the current collector and the electrode active material layer is not particularly limited, for example, the overlapping region of the current collector and the electrode active material layer From the contour of the above, it is possible to set it as an area up to a certain distance toward the center of the overlapping area. The end portion of the overlapping region may be, for example, a region surrounded by the outline of the overlapping region and a similar shape obtained by reducing the outline of the overlapping region.
Further, the adhesive portion may be present only at an end portion of the overlapping area along the entire outer periphery of the overlapping area of the current collector and the electrode active material layer, or an end portion of the overlapping area. And may exist in at least a part of the inside surrounded by the end portion, or may exist in the entire overlapping region of the current collector and the electrode active material layer. Among them, from the viewpoint of suppressing an increase in internal resistance, the adhesive portion is present only at the end portion of the overlapping region along the entire outer periphery of the overlapping region of the current collector and the electrode active material layer. It is preferable.
前記接着剤部に用いられる接着剤としては、例えば、少なくとも接着性樹脂を含有し、必要に応じて導電性物質等を更に含有していても良い接着剤を挙げることができる。
前記接着剤としては、中でも、電池材料の劣化を抑制しながら接着する観点から、前記接着性樹脂として熱可塑性樹脂を含有する熱可塑性接着剤が好ましく、更に、電池材料の劣化温度未満に融点を有する熱可塑性樹脂を含有する熱可塑性接着剤が、接着時における電池材料の劣化を抑制しやすい点からより好ましい。
前記接着性樹脂は、公知のものを適宜選択して用いることができ、特に限定はされない。前記接着性樹脂に用いられる熱可塑性樹脂としては、例えば、エチレン酢酸ビニル共重合体（ＥＶＡ）及び低密度ポリエチレン（ＬＤＰＥ）等のポリオレフィン系樹脂等を挙げることができる。前記接着性樹脂としては、中でも、接着力に優れ、適度な融点を有する点から、エチレン酢酸ビニル共重合体（ＥＶＡ）を好ましく用いることができる。
Examples of the adhesive used for the adhesive part include an adhesive containing at least an adhesive resin and optionally a conductive substance or the like.
As the adhesive, among others, from the viewpoint of adhering while suppressing deterioration of the battery material, a thermoplastic adhesive containing a thermoplastic resin as the adhesive resin is preferable, and further, has a melting point below the deterioration temperature of the battery material. The thermoplastic adhesive containing the thermoplastic resin is more preferable because it is easy to suppress deterioration of the battery material at the time of adhesion.
As the adhesive resin, a publicly known adhesive resin can be appropriately selected and used without any particular limitation. Examples of the thermoplastic resin used as the adhesive resin include polyolefin-based resins such as ethylene vinyl acetate copolymer (EVA) and low density polyethylene (LDPE). Among them, ethylene vinyl acetate copolymer (EVA) can be preferably used as the adhesive resin because of its excellent adhesive strength and proper melting point.
前記接着剤が含有していても良い導電性物質としては、例えば、カーボン粉末、及びアルミニウム粉末等の金属粉末等を挙げることができる。互いに接着する前記正極集電体と前記正極活物質層との重複領域全体に前記接着剤部が存在する場合は、前記接着剤部は、導電性物質を含有する接着剤の固化物であることが、前記正極集電体と前記正極活物質層との導通が良好になる点から好ましい。
前記導電性物質を含有する接着剤において、前記導電性物質の含有量は、特に限定はされないが、前記正極集電体と前記正極活物質層との導通を良好にする点及び電池抵抗の増加を抑制する点から、体積抵抗率が１０×１０３Ωｃｍ以下となるように調整されることが好ましく、中でも、前記カーボンコート層と同等の体積抵抗率となるように調整されることが好ましい。
前記接着剤としては、市販品を用いても良く、例えば、接着剤又は粘着剤として市販されているものを適宜選択して用いても良い。
Examples of the conductive substance that the adhesive may contain include metal powder such as carbon powder and aluminum powder. When the adhesive part exists in the entire overlapping region of the positive electrode current collector and the positive electrode active material layer that are adhered to each other, the adhesive part is a solidified product of an adhesive containing a conductive substance. However, it is preferable from the viewpoint that the conduction between the positive electrode current collector and the positive electrode active material layer is good.
In the adhesive containing the conductive substance, the content of the conductive substance is not particularly limited, but the point of improving the conduction between the positive electrode current collector and the positive electrode active material layer and the increase of the battery resistance. From the viewpoint of suppressing the above, the volume resistivity is preferably adjusted to 10×10 3 Ωcm or less, and particularly, the volume resistivity is preferably adjusted to be equivalent to that of the carbon coat layer.
As the adhesive, a commercially available product may be used, for example, a commercially available adhesive or pressure-sensitive adhesive may be appropriately selected and used.
５．全固体電池用電極板の構成
本開示の全固体電池用電極板は、少なくとも前記集電体と、前記電極活物質層と、前記集電体と前記電極活物質層とを接着する前記接着剤部とを有するものであれば良い。本開示の全固体電池用電極板は、例えば、前記正極集電体と、前記正極活物質層と、前記正極集電体と前記正極活物質層とを接着する前記接着剤部とからなる電極板であっても良いし、前記負極集電体と、前記負極活物質層と、前記負極集電体と前記負極活物質層とを接着する前記接着剤部とからなる電極板であっても良い。或いは、本開示の全固体電池用電極板は、前記集電体又は前記集電体を表面に有する電極体と、前記電極活物質層を表面に有する電極体とを、前記接着剤部を介して接着したものであっても良い。ここで、前記集電体又は前記電極活物質層を表面に有する電極体が、前記集電体と、前記電極活物質層と、前記集電体と前記電極活物質層とを接着する前記接着剤部とを有するもの、すなわち、本開示の全固体電池用電極板を含む電極体であっても良い。
5. Configuration of electrode plate for all-solid-state battery The electrode plate for all-solid-state battery of the present disclosure includes at least the current collector, the electrode active material layer, and the adhesive that bonds the current collector and the electrode active material layer. It is sufficient if it has a part. The electrode plate for an all-solid-state battery of the present disclosure is, for example, an electrode including the positive electrode current collector, the positive electrode active material layer, and the adhesive part that bonds the positive electrode current collector and the positive electrode active material layer. It may be a plate, or an electrode plate including the negative electrode current collector, the negative electrode active material layer, and the adhesive portion that bonds the negative electrode current collector and the negative electrode active material layer. good. Alternatively, the electrode plate for an all-solid-state battery of the present disclosure, the electrode body having the current collector or the current collector on the surface, and the electrode body having the electrode active material layer on the surface, via the adhesive portion. It may be glued together. Here, the electrode body having the current collector or the electrode active material layer on the surface is the adhesive that bonds the current collector, the electrode active material layer, and the current collector and the electrode active material layer. It may have an agent part, that is, an electrode body including the electrode plate for an all-solid-state battery of the present disclosure.
また、本開示の全固体電池用電極板は、電池ユニットを１つのみ有する全固体電池用であっても良いし、複数の電池ユニットを積層した積層型全固体電池用であっても良い。積層型全固体電池用である本開示の全固体電池用電極板は、集電体と、電極活物質層と、前記集電体と前記電極活物質層とを接着する接着剤部とを有する層構成を、１つのみ含むものであっても、複数含むものであっても良い。 Moreover, the electrode plate for all-solid-state batteries of the present disclosure may be for all-solid-state batteries having only one battery unit, or may be for laminated all-solid-state batteries in which a plurality of battery units are stacked. An electrode plate for an all-solid-state battery of the present disclosure, which is for a laminated all-solid-state battery, has a current collector, an electrode active material layer, and an adhesive portion that bonds the current collector and the electrode active material layer. The layer structure may include only one or a plurality of layers.
６．全固体電池用電極板の製造方法
本開示の全固体電池用電極板の製造方法は、前述した本開示の全固体電池用電極板を得ることができる方法であれば特に限定はされないが、例えば、
前記接着剤を前記集電体の少なくとも一方の面に配置する工程と、
前記集電体上に、前記電極活物質層を表面に有する前記電極体を積層する工程と、
前記接着剤の種類に応じた手段で、前記集電体と前記電極活物質層とを接着させることにより、前記接着剤を、前記集電体と前記電極活物質層とを接着する前記接着剤部とする工程と、を有する製造方法を挙げることができる。
6. Method for producing electrode plate for all-solid-state battery The method for producing electrode plate for all-solid-state battery of the present disclosure is not particularly limited as long as it is a method capable of obtaining the electrode plate for all-solid-state battery of the present disclosure, for example, ,
Disposing the adhesive on at least one surface of the current collector;
A step of stacking the electrode body having the electrode active material layer on the surface of the current collector;
The adhesive for adhering the current collector and the electrode active material layer to each other by adhering the current collector and the electrode active material layer by a means according to the type of the adhesive. And a step of forming a part.
本開示の全固体電池用電極板の製造方法の一例として、前記（ｉ）の実施形態に係る本開示の全固体電池用電極板の製造方法の一例を、図１を参照して説明する。
図１に示す例においては、まず、正極集電体１０の少なくとも一方の面に接着剤３１を配置する。図１に示す正極集電体１０は、金属箔１１と、カーボンコート層１２とを有する。正極集電体１０において、点線で囲まれた領域は、正極集電体１０上に、正極活物質層２１を有する電極体２０を積層したときに、正極集電体１０と正極活物質層２１とが重複する重複領域Ａである。接着剤３１は、正極集電体１０の表面において、前記重複領域Ａの外周全体に沿った前記重複領域Ａの端部が少なくとも接着されるように配置される。次いで、予め準備しておいた少なくとも正極活物質層２１を表面に有する電極体２０の正極活物質層２１が、正極集電体１０の接着剤３１が配置された側の面と接するように、正極集電体１０上に電極体２０を積層する。その後、接着剤３１の種類に応じた手段で、正極集電体１０と正極活物質層２１とを接着させることにより、前記接着剤３１が、正極集電体１０と正極活物質層２１とを接着する接着剤部３０になり、正極集電体１０と、正極活物質層２１を有する電極体２０と、前記正極集電体１０と前記正極活物質層２１とを接着する接着剤部３０とを有する本開示の全固体電池用電極板４０を製造することができる。全固体電池用電極板４０が有する接着剤部３０は、互いに接着する正極集電体１０と正極活物質層２１との重複領域Ａの外周全体に沿った前記重複領域Ａの端部に少なくとも存在している。
なお、図示はしないが、正極活物質層の表面に接着剤を配置して、正極活物質層の前記接着剤が配置された側の面に正極集電体を積層し、正極集電体１０と正極活物質層２１とを接着させることにより、本開示の全固体電池用電極板を製造しても良い。
As an example of the method for manufacturing the electrode plate for an all-solid battery of the present disclosure, an example of the method for manufacturing the electrode plate for an all-solid-state battery of the present disclosure according to the embodiment (i) will be described with reference to FIG. 1.
In the example shown in FIG. 1, first, the adhesive 31 is arranged on at least one surface of the positive electrode current collector 10. The positive electrode current collector 10 shown in FIG. 1 has a metal foil 11 and a carbon coat layer 12. In the positive electrode current collector 10, a region surrounded by a dotted line is formed when the electrode body 20 having the positive electrode active material layer 21 is laminated on the positive electrode current collector 10 and the positive electrode current collector 10 and the positive electrode active material layer 21. Is an overlapping area A where and overlap. The adhesive 31 is arranged on the surface of the positive electrode current collector 10 so that at least the ends of the overlapping region A along the entire outer periphery of the overlapping region A are bonded. Next, so that the positive electrode active material layer 21 of the electrode body 20 having at least the positive electrode active material layer 21 on the surface prepared in advance contacts the surface of the positive electrode current collector 10 on the side where the adhesive 31 is arranged, The electrode body 20 is laminated on the positive electrode current collector 10. After that, the positive electrode current collector 10 and the positive electrode active material layer 21 are adhered to each other by a means depending on the type of the adhesive agent 31, so that the adhesive agent 31 bonds the positive electrode current collector 10 and the positive electrode active material layer 21. The positive electrode current collector 10, the electrode body 20 having the positive electrode active material layer 21, and the adhesive agent portion 30 that adheres the positive electrode current collector 10 and the positive electrode active material layer 21. It is possible to manufacture the electrode plate 40 for an all-solid battery of the present disclosure having the above. The adhesive portion 30 of the electrode plate 40 for all-solid-state batteries is present at least at the end portion of the overlapping area A along the entire outer periphery of the overlapping area A of the positive electrode current collector 10 and the positive electrode active material layer 21 that are bonded to each other. doing.
Although not shown, an adhesive is arranged on the surface of the positive electrode active material layer, and the positive electrode current collector is laminated on the surface of the positive electrode active material layer on the side where the adhesive is arranged. The electrode plate for an all-solid-state battery of the present disclosure may be manufactured by adhering the positive electrode active material layer 21 to the positive electrode active material layer 21.
前記接着剤を前記集電体の少なくとも一方の面に配置する方法は、例えば、ペースト状の接着剤を塗布する方法、及び、フィルム乃至シート状の接着剤を貼り付ける方法等が挙げられる。フィルム乃至シート状の接着剤としては、具体的には例えば、両面テープ等が挙げられる。中でも、接着剤部の厚みを低減しやすく、プレスした際の圧力が均等にかかりやすい点から、ペースト状の接着剤を塗布する方法が好ましい。前記接着剤が、ペレットタイプ等の固体の熱可塑性接着剤の場合は、例えば、ホットメルト塗布機を用いて、加熱溶融させながら塗布することができる。溶剤を含有するペーストタイプの熱可塑性接着剤は、室温で塗布することが可能であり、塗布後、溶剤を乾燥することにより、固化させることができる。
前記接着剤を前記集電体上に配置する際は、前記集電体と前記電極活物質層との重複領域の外周全体に沿った前記重複領域の端部が少なくとも接着されるように配置する。
Examples of the method of disposing the adhesive on at least one surface of the current collector include a method of applying a paste adhesive and a method of attaching a film or sheet adhesive. Specific examples of the film or sheet adhesive include double-sided tape. Above all, the method of applying the paste-like adhesive is preferable because the thickness of the adhesive portion can be easily reduced and the pressure when pressed can be applied uniformly. When the adhesive is a solid thermoplastic adhesive such as a pellet type, it can be applied while being heated and melted by using a hot melt applicator, for example. The paste-type thermoplastic adhesive containing a solvent can be applied at room temperature, and can be solidified by drying the solvent after application.
When arranging the adhesive on the current collector, it is arranged so that at least an end portion of the overlapping region along the entire outer periphery of the overlapping region of the current collector and the electrode active material layer is bonded. ..
前記集電体上に、前記電極活物質層を表面に有する前記電極体を積層する工程においては、前記電極体の前記電極活物質層が、前記集電体の前記接着剤が配置された側の面と接するように、前記集電体上に前記電極体を積層する。 In the step of laminating the electrode body having the electrode active material layer on the surface of the current collector, the electrode active material layer of the electrode body is a side where the adhesive of the current collector is arranged. The electrode body is laminated on the current collector so as to be in contact with the surface.
前記集電体と前記電極活物質層とは、前記接着剤の種類に応じた手段で接着される。前記接着剤が熱可塑性接着剤の場合は、例えば、前記集電体上に、前記電極活物質層を表面に有する前記電極体乃至前記電極活物質層を積層した接着前積層体を、加熱しながら積層方向にプレスした後、冷却することにより、前記集電体と前記電極活物質層とを接着することができる。熱可塑性接着剤が、加熱により溶融した後、冷却により固化するため、前記集電体と前記電極活物質層とは、接着剤の固化物からなる接着剤部により接着される。
前記接着前積層体を加熱しながら積層方向にプレスする際の加熱温度は、電池材料の劣化温度未満且つ前記接着剤中の熱可塑性樹脂の融点以上の温度となるように適宜調整され、特に限定はされない。前記接着剤がＥＶＡを含有する場合は、例えば、１４０℃程度とすることができる。
前記接着前積層体をプレスする際の圧力は、例えば０．１ＭＰａ以上１０ＭＰａ以下とすることができ、より具体的には例えば１ＭＰａ程度とすることができる。
前記接着前積層体をプレスする際の加圧の方法としては、例えば、機械加圧、及びガス加圧等が挙げられる。
機械加圧としては、例えば、モーターを駆動し、ボールネジを介して前記集電体と前記電極活物質層との積層方向に加圧する方法、及びモーターを駆動して油圧を介して前記集電体と前記電極活物質層との積層方向に加圧する方法等が挙げられる。機械加圧では、所定圧力まで加圧若しくは降圧した後、メカニカルストッパーで稼動部を固定することにより、モーターの駆動に伴うエネルギー消費を必要最低限に抑制することができる。
ガス加圧としては、例えば、予め搭載したガスボンベから加圧ガスを介して加圧する方法が考えられる。
なお、前記加圧方法は当然に上記に限定されるものではない。
前記接着前積層体を加熱しながら積層方向にプレスした後に行う冷却は、前記接着剤が固化する温度まで冷却すれば良いため、前記接着剤中の熱可塑性樹脂の融点未満の温度まで冷却すれば良く、特に限定はされないが、例えば、室温まで冷却することにより行うことができる。
The current collector and the electrode active material layer are adhered by a means suitable for the type of the adhesive. When the adhesive is a thermoplastic adhesive, for example, a pre-adhesion laminate in which the electrode body or the electrode active material layer having the electrode active material layer on the surface thereof is laminated on the current collector is heated. While pressing in the stacking direction while cooling, the current collector and the electrode active material layer can be bonded to each other. Since the thermoplastic adhesive is melted by heating and then solidified by cooling, the current collector and the electrode active material layer are bonded to each other by the adhesive portion made of a solidified material of the adhesive.
The heating temperature during pressing in the stacking direction while heating the pre-adhesion laminate is appropriately adjusted so as to be lower than the deterioration temperature of the battery material and not lower than the melting point of the thermoplastic resin in the adhesive, and is particularly limited. It is not done. When the adhesive contains EVA, the temperature may be about 140° C., for example.
The pressure for pressing the pre-bonding laminate can be, for example, 0.1 MPa or more and 10 MPa or less, and more specifically, can be, for example, about 1 MPa.
Examples of the pressing method when pressing the pre-bonding laminate include mechanical pressing and gas pressing.
As the mechanical pressurization, for example, a method of driving a motor to pressurize in the stacking direction of the current collector and the electrode active material layer via a ball screw, and a method of driving the motor to hydraulically press the current collector And a method of applying pressure in the stacking direction of the electrode active material layer. In the mechanical pressurization, after the pressurization or depressurization to a predetermined pressure is performed, the operating portion is fixed by the mechanical stopper, so that the energy consumption accompanying the driving of the motor can be suppressed to the necessary minimum.
As the gas pressurization, for example, a method of pressurizing via a pressurized gas from a gas cylinder installed in advance can be considered.
The pressing method is not limited to the above, of course.
Cooling performed after pressing the pre-adhesion laminate in the laminating direction while heating is performed by cooling the adhesive to a temperature at which it solidifies, so that it may be cooled to a temperature lower than the melting point of the thermoplastic resin in the adhesive. Although there is no particular limitation, it can be performed, for example, by cooling to room temperature.
７．全固体電池用電極板が用いられる全固体電池
本開示の全固体電池用電極板は、全固体電池に用いられるものであり、中でも、複数の電池ユニットを積層した積層型全固体電池に好適に用いることができる。積層型全固体電池は、本開示の全固体電池用電極板の層構成を複数含むことができるため、本開示の全固体電池用電極板を用いることによる異物の混入を抑制する効果が発揮されやすい。
7. All-solid-state battery in which the electrode plate for all-solid-state battery is used The electrode plate for all-solid-state battery of the present disclosure is used for all-solid-state batteries, and among them, is suitable for a stacked-type all-solid-state battery in which a plurality of battery units are stacked. Can be used. Since the laminated all-solid-state battery can include a plurality of layer configurations of the electrode plate for all-solid-state battery of the present disclosure, the effect of suppressing the mixing of foreign matter by using the electrode plate for all-solid-state battery of the present disclosure is exhibited. Cheap.
図２は、本開示の全固体電池用電極板を用いた全固体電池の製造方法の一例を説明する概略図であり、積層型全固体電池の製造方法の一例を説明する概略図である。図２に示す製造方法においては、まず、正極活物質層２１と、固体電解質層２２と、負極活物質層２３と、負極集電体２４と、負極活物質層２３と、固体電解質層２２と、正極活物質層２１とがこの順に積層された電極体２０を複数準備し、更に、正極集電体１０の両面に接着剤３１を配置した接着剤付正極集電体１０Ａと、正極集電体１０の片面に接着剤３１を配置した接着剤付正極集電体１０Ｂを準備する。ここで、接着剤３１は、正極集電体１０と正極活物質層２１とを接着させた際の正極集電体１０と正極活物質層２１との重複領域の外周全体に沿った前記重複領域の端部が少なくとも接着されるように配置する。次いで、電極体２０同士を、前記接着剤付正極集電体１０Ａを介して積層し、最も表面側に位置する電極体２０の正極活物質層２１上には、前記接着剤付正極集電体１０Ｂを積層する。その後、接着剤３１の種類に応じた方法で、前記正極活物質層２１と前記正極集電体１０とを接着させ、接着剤３１を接着剤部３０とすることにより、正極集電体１０と、正極活物質層２１と、前記正極集電体１０と前記正極活物質層２１とを接着する接着剤部３０とを有し、前記接着剤部３０が、前記正極集電体１０と前記正極活物質層２１との重複領域の外周全体に沿った前記重複領域の端部に少なくとも存在する本開示の全固体電池用電極板４０を備える全固体電池５０を得ることができる。
なお、図２に示す全固体電池５０は、電池ユニット数が３個の積層型全固体電池であるが、積層型全固体電池が有する電池ユニット数は、特に限定はされず、例えば、２個以上５０以下とすることができる。
また、本開示の全固体電池用電極板が用いられる全固体電池が備える正極集電体及び負極集電体は、集電用リードにより外部に通じる正極端子又は負極端子と接続されていても良い。
FIG. 2 is a schematic diagram illustrating an example of a method of manufacturing an all-solid-state battery using the electrode plate for an all-solid-state battery of the present disclosure, and a schematic diagram illustrating an example of a method of manufacturing a stacked all-solid-state battery. In the manufacturing method shown in FIG. 2, first, the positive electrode active material layer 21, the solid electrolyte layer 22, the negative electrode active material layer 23, the negative electrode current collector 24, the negative electrode active material layer 23, and the solid electrolyte layer 22. , A plurality of electrode bodies 20 in which a positive electrode active material layer 21 is laminated in this order, and further, a positive electrode current collector 10A with an adhesive in which an adhesive 31 is arranged on both surfaces of the positive electrode current collector 10, and a positive electrode current collector An adhesive-attached positive electrode current collector 10B in which an adhesive 31 is arranged on one surface of the body 10 is prepared. Here, the adhesive 31 is the overlapping region along the entire outer periphery of the overlapping region of the positive electrode current collector 10 and the positive electrode active material layer 21 when the positive electrode current collector 10 and the positive electrode active material layer 21 are bonded together. Are arranged so that at least the ends thereof are bonded. Next, the electrode bodies 20 are laminated via the positive electrode current collector with adhesive 10A, and the positive electrode current collector with adhesive is placed on the positive electrode active material layer 21 of the electrode body 20 located on the most front surface side. Stack 10B. After that, the positive electrode active material layer 21 and the positive electrode current collector 10 are adhered by a method depending on the type of the adhesive agent 31, and the adhesive agent 31 is used as the adhesive agent portion 30. A positive electrode active material layer 21, and an adhesive part 30 for adhering the positive electrode current collector 10 and the positive electrode active material layer 21, the adhesive part 30 including the positive electrode current collector 10 and the positive electrode. It is possible to obtain the all-solid-state battery 50 including the electrode plate 40 for the all-solid-state battery of the present disclosure which is present at least at the end portion of the overlapping region along the entire outer periphery of the overlapping region with the active material layer 21.
Note that the all-solid-state battery 50 shown in FIG. 2 is a stacked all-solid-state battery having three battery units, but the number of battery units included in the all-solid-state battery is not particularly limited, and for example, two batteries are provided. It can be 50 or less.
Further, the positive electrode current collector and the negative electrode current collector included in the all-solid-state battery using the all-solid-state battery electrode plate of the present disclosure may be connected to a positive electrode terminal or a negative electrode terminal that communicates with the outside by a current collection lead. ..
本開示の全固体電池用電極板が用いられる全固体電池において、使用時に前記全固体電池に付与される圧力は、例えば１ＭＰａ以上４５ＭＰａ以下とすることができ、非使用時に前記全固体電池に付与される圧力は、例えば０ＭＰａ以上１ＭＰａ以下とすることができる。 In the all-solid-state battery using the electrode plate for all-solid-state battery of the present disclosure, the pressure applied to the all-solid-state battery during use can be, for example, 1 MPa or more and 45 MPa or less, and the pressure applied to the all-solid-state battery when not in use. The applied pressure can be, for example, 0 MPa or more and 1 MPa or less.
本開示の全固体電池用電極板が用いられる全固体電池は、例えば、車両が搭載する電源、又は、携帯用電子機器等の駆動用電源等として用いられるが、これらの用途に限定されるものではない。本開示の全固体電池用電極板が用いられる全固体電池が適用される車両は、電池を搭載しエンジンを搭載しない電気自動車に限定されず、電池とエンジンの双方を搭載するハイブリッド車等も包含する。 The all-solid-state battery using the electrode plate for all-solid-state battery of the present disclosure is used, for example, as a power source mounted on a vehicle or as a driving power source for portable electronic devices, but is limited to these applications. is not. The vehicle to which the all-solid-state battery using the electrode plate for all-solid-state battery of the present disclosure is applied is not limited to an electric vehicle that has a battery and does not have an engine, and includes a hybrid vehicle that has both a battery and an engine. To do.
１０ 正極集電体
１１ 金属箔
１２ カーボンコート層
２０ 電極体
２１ 正極活物質層
２２ 固体電解質層
２３ 負極活物質層
２４ 負極集電体
３０ 接着剤部
３１ 接着剤
４０ 全固体電池用電極板
５０ 全固体電池
10 Positive Electrode Current Collector 11 Metal Foil 12 Carbon Coat Layer 20 Electrode Body 21 Positive Electrode Active Material Layer 22 Solid Electrolyte Layer 23 Negative Electrode Active Material Layer 24 Negative Current Collector 30 Adhesive Part 31 Adhesive 40 All Solid Battery Electrode Plate 50 All Solid battery
Claims (1)
前記接着剤部が、互いに接着する前記集電体と前記電極活物質層との重複領域の外周全体に沿った前記重複領域の端部に少なくとも存在することを特徴とする、全固体電池用電極板。 A current collector, an electrode active material layer, and an adhesive part that bonds the current collector and the electrode active material layer,
An electrode for an all-solid-state battery, wherein the adhesive portion is present at least at an end portion of the overlapping region along the entire outer periphery of the overlapping region of the current collector and the electrode active material layer that are bonded to each other. Board.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010257893A (en) * | 2009-04-28 | 2010-11-11 | Nissan Motor Co Ltd | Bipolar type electrode and bipolar type secondary battery using this |
| JP2013125707A (en) * | 2011-12-15 | 2013-06-24 | Samsung Yokohama Research Institute Co Ltd | Solid-state battery electrode, solid-state battery, adhesive film for solid-state battery, and method for manufacturing solid-state battery electrode |
| WO2013146916A1 (en) * | 2012-03-28 | 2013-10-03 | 日本ゼオン株式会社 | Electrode for all-solid-state secondary batteries and method for producing same |
| JP2014093156A (en) * | 2012-11-01 | 2014-05-19 | Furukawa Co Ltd | Electrode for all-solid-state lithium ion battery, all-solid-state lithium ion battery, and method of manufacturing all-solid-state lithium ion battery |
| JP2014096281A (en) * | 2012-11-09 | 2014-05-22 | National Institute Of Advanced Industrial & Technology | Lithium ion secondary battery positive electrode and lithium ion secondary battery using the same |
| JP2016071955A (en) * | 2014-09-26 | 2016-05-09 | トヨタ自動車株式会社 | Method for manufacturing electrode for lithium ion secondary battery |
-
2018
- 2018-12-19 JP JP2018237158A patent/JP7099302B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010257893A (en) * | 2009-04-28 | 2010-11-11 | Nissan Motor Co Ltd | Bipolar type electrode and bipolar type secondary battery using this |
| JP2013125707A (en) * | 2011-12-15 | 2013-06-24 | Samsung Yokohama Research Institute Co Ltd | Solid-state battery electrode, solid-state battery, adhesive film for solid-state battery, and method for manufacturing solid-state battery electrode |
| WO2013146916A1 (en) * | 2012-03-28 | 2013-10-03 | 日本ゼオン株式会社 | Electrode for all-solid-state secondary batteries and method for producing same |
| JP2014093156A (en) * | 2012-11-01 | 2014-05-19 | Furukawa Co Ltd | Electrode for all-solid-state lithium ion battery, all-solid-state lithium ion battery, and method of manufacturing all-solid-state lithium ion battery |
| JP2014096281A (en) * | 2012-11-09 | 2014-05-22 | National Institute Of Advanced Industrial & Technology | Lithium ion secondary battery positive electrode and lithium ion secondary battery using the same |
| JP2016071955A (en) * | 2014-09-26 | 2016-05-09 | トヨタ自動車株式会社 | Method for manufacturing electrode for lithium ion secondary battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4057372A1 (en) | 2021-03-08 | 2022-09-14 | Prime Planet Energy & Solutions, Inc. | Method for producing secondary battery electrode and method for producing secondary battery |
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