JP2018101641A5 - - Google Patents
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- JP2018101641A5 JP2018101641A5 JP2018050524A JP2018050524A JP2018101641A5 JP 2018101641 A5 JP2018101641 A5 JP 2018101641A5 JP 2018050524 A JP2018050524 A JP 2018050524A JP 2018050524 A JP2018050524 A JP 2018050524A JP 2018101641 A5 JP2018101641 A5 JP 2018101641A5
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- 239000007784 solid electrolyte Substances 0.000 claims description 96
- 239000000758 substrate Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 27
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive Effects 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 210000002356 Skeleton Anatomy 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000011810 insulating material Substances 0.000 claims description 2
- 239000011800 void material Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 3
- 238000005259 measurement Methods 0.000 claims 2
- 238000000691 measurement method Methods 0.000 claims 1
- 239000002203 sulfidic glass Substances 0.000 claims 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
Description
すなわち、本発明によれば、
シート状の多孔性基材と、
上記多孔性基材の空隙の内部に充填されている無機固体電解質材料と、
を備える固体電解質シートであって、
上記多孔性基材は不織布であり、
当該固体電解質シート中の、上記無機固体電解質材料同士を結着させるためのバインダーの含有量が、上記固体電解質シートの全体を１００質量％としたとき、０．５質量％以下である固体電解質シートが提供される。
That is, according to the present invention,
A sheet-like porous substrate;
An inorganic solid electrolyte material filled in the voids of the porous substrate;
A solid electrolyte sheet comprising :
The porous substrate is a nonwoven fabric,
The solid electrolyte sheet in which the content of the binder for binding the inorganic solid electrolyte materials in the solid electrolyte sheet is 0.5% by mass or less when the entire solid electrolyte sheet is 100% by mass. Is provided.
以上、本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することもできる。
なお、本発明は前述の実施形態に限定されるものではなく、本発明の目的を達成できる範囲での変形、改良等は本発明に含まれるものである。
以下、参考形態の例を付記する。
＜付記＞
（付記１）
シート状の多孔性基材と、
前記多孔性基材の空隙の内部に充填されている無機固体電解質材料と、
を備える固体電解質シート。
（付記２）
付記１に記載の固体電解質シートにおいて、
少なくとも前記多孔性基材の空隙を囲む骨格部表面に付着した粘着剤をさらに備え、
前記無機固体電解質材料の少なくとも一部が前記粘着剤に付着している固体電解質シート。
（付記３）
付記１または２に記載の固体電解質シートにおいて、
当該固体電解質シートの厚みが３００μｍ以下である固体電解質シート。
（付記４）
付記１乃至３いずれか一つに記載の固体電解質シートにおいて、
前記無機固体電解質材料の充填量が、当該固体電解質シートの全体を１００質量％としたとき、１５質量％以上８５質量％以下である固体電解質シート。
（付記５）
付記１乃至４いずれか一つに記載の固体電解質シートにおいて、
当該固体電解質シート中のバインダーの含有量が、前記固体電解質シートの全体を１００質量％としたとき、０．５質量％未満である固体電解質シート。
（付記６）
付記１乃至５いずれか一つに記載の固体電解質シートにおいて、
全固体型リチウムイオン電池を構成する固体電解質層に用いられるものである固体電解質シート。
（付記７）
付記１乃至６いずれか一つに記載の固体電解質シートにおいて、
前記多孔性基材は不織布である固体電解質シート。
（付記８）
付記１乃至７いずれか一つに記載の固体電解質シートにおいて、
前記多孔性基材は絶縁性材料により構成されている固体電解質シート。
（付記９）
付記１乃至８いずれか一つに記載の固体電解質シートにおいて、
前記多孔性基材の空隙率が５０％以上９５％以下である固体電解質シート。
（付記１０）
正極層と、固体電解質層と、負極層とがこの順番に積層された全固体型リチウムイオン電池であって、
前記固体電解質層が、付記１乃至９いずれか一つに記載の固体電解質シートにより構成されたものである全固体型リチウムイオン電池。
（付記１１）
付記２に記載の固体電解質シートを製造するための製造方法であって、
シート状の多孔性基材の少なくとも一方の面に、粘着剤層を形成する工程と、
前記粘着剤層上に無機固体電解質材料を付着させることにより無機固体電解質材料層を形成し、前記多孔性基材、前記粘着剤層、および前記無機固体電解質材料層がこの順番に積層された積層体を得る工程と、
得られた前記積層体を加圧することにより、前記粘着剤層を構成する粘着剤を前記多孔性基材の空隙を囲む骨格部表面に付着させるとともに、前記多孔性基材の前記空隙内に前記無機固体電解質材料層を構成する前記無機固体電解質材料を充填する工程と、
を含む固体電解質シートの製造方法。
（付記１２）
付記２に記載の固体電解質シートを製造するための製造方法であって、
シート状の多孔性基材と、粘着剤を準備する工程と、
前記多孔性基材の空隙を囲む骨格部表面に、前記粘着剤をコーティングする工程と、
前記多孔性基材の前記空隙内に無機固体電解質材料を充填する工程と、
を含む固体電解質シートの製造方法。
（付記１３）
付記１１または１２に記載の固体電解質シートの製造方法であって、
前記多孔性基材の空隙体積をＡとし、前記粘着剤の体積をＢとしたとき、
［（Ａ−Ｂ）／Ａ］×１００で定義される残空隙率が１０％以上９０％以下である固体電解質シートの製造方法。
As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
Hereinafter, examples of the reference form will be added.
<Appendix>
(Appendix 1)
A sheet-like porous substrate;
An inorganic solid electrolyte material filled in the voids of the porous substrate; and
A solid electrolyte sheet comprising:
(Appendix 2)
In the solid electrolyte sheet according to appendix 1,
Further comprising an adhesive attached to the surface of the skeleton part surrounding at least the voids of the porous substrate;
A solid electrolyte sheet in which at least a part of the inorganic solid electrolyte material is attached to the pressure-sensitive adhesive.
(Appendix 3)
In the solid electrolyte sheet according to appendix 1 or 2,
A solid electrolyte sheet having a thickness of 300 μm or less.
(Appendix 4)
In the solid electrolyte sheet according to any one of appendices 1 to 3,
A solid electrolyte sheet in which the filling amount of the inorganic solid electrolyte material is 15% by mass or more and 85% by mass or less when the total amount of the solid electrolyte sheet is 100% by mass.
(Appendix 5)
In the solid electrolyte sheet according to any one of appendices 1 to 4,
The solid electrolyte sheet whose content of the binder in the said solid electrolyte sheet is less than 0.5 mass% when the whole said solid electrolyte sheet is 100 mass%.
(Appendix 6)
In the solid electrolyte sheet according to any one of appendices 1 to 5,
A solid electrolyte sheet used for a solid electrolyte layer constituting an all solid-state lithium ion battery.
(Appendix 7)
In the solid electrolyte sheet according to any one of appendices 1 to 6,
A solid electrolyte sheet in which the porous substrate is a nonwoven fabric.
(Appendix 8)
In the solid electrolyte sheet according to any one of appendices 1 to 7,
The porous substrate is a solid electrolyte sheet made of an insulating material.
(Appendix 9)
In the solid electrolyte sheet according to any one of appendices 1 to 8,
A solid electrolyte sheet in which the porosity of the porous substrate is 50% or more and 95% or less.
(Appendix 10)
An all-solid-state lithium ion battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated in this order,
An all-solid-state lithium ion battery in which the solid electrolyte layer is constituted by the solid electrolyte sheet according to any one of appendices 1 to 9.
(Appendix 11)
A manufacturing method for manufacturing the solid electrolyte sheet according to appendix 2,
Forming an adhesive layer on at least one surface of the sheet-like porous substrate; and
An inorganic solid electrolyte material layer is formed by attaching an inorganic solid electrolyte material on the pressure-sensitive adhesive layer, and the porous base material, the pressure-sensitive adhesive layer, and the inorganic solid electrolyte material layer are laminated in this order. Obtaining a body;
By pressurizing the obtained laminate, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is attached to the surface of the skeleton surrounding the voids of the porous substrate, and the voids in the porous substrate are Filling the inorganic solid electrolyte material constituting the inorganic solid electrolyte material layer;
The manufacturing method of the solid electrolyte sheet containing this.
(Appendix 12)
A manufacturing method for manufacturing the solid electrolyte sheet according to appendix 2,
A step of preparing a sheet-like porous substrate and an adhesive;
Coating the pressure-sensitive adhesive on the surface of the skeleton surrounding the voids of the porous substrate;
Filling an inorganic solid electrolyte material in the voids of the porous substrate;
The manufacturing method of the solid electrolyte sheet containing this.
(Appendix 13)
A method for producing a solid electrolyte sheet according to appendix 11 or 12,
When the void volume of the porous substrate is A and the volume of the adhesive is B,
The manufacturing method of the solid electrolyte sheet whose remaining porosity defined by [(A-B) / A] x100 is 10% or more and 90% or less.
Claims (15)
前記多孔性基材の空隙の内部に充填されている無機固体電解質材料と、
を備える固体電解質シートであって、
前記多孔性基材は不織布であり、
当該固体電解質シート中の、前記無機固体電解質材料同士を結着させるためのバインダーの含有量が、前記固体電解質シートの全体を１００質量％としたとき、０．５質量％以下である固体電解質シート。 A sheet-like porous substrate;
An inorganic solid electrolyte material filled in the voids of the porous substrate; and
A solid electrolyte sheet comprising :
The porous substrate is a nonwoven fabric,
The solid electrolyte sheet in which the content of the binder for binding the inorganic solid electrolyte materials in the solid electrolyte sheet is 0.5% by mass or less when the entire solid electrolyte sheet is 100% by mass. .
少なくとも前記多孔性基材の空隙を囲む骨格部表面に付着した粘着剤をさらに備え、
前記無機固体電解質材料の少なくとも一部が前記粘着剤に付着している固体電解質シート。 In the solid electrolyte sheet according to claim 1,
Further comprising an adhesive attached to the surface of the skeleton part surrounding at least the voids of the porous substrate;
A solid electrolyte sheet in which at least a part of the inorganic solid electrolyte material is attached to the pressure-sensitive adhesive.
当該固体電解質シートの厚みが３００μｍ以下である固体電解質シート。 The solid electrolyte sheet according to claim 1 or 2,
A solid electrolyte sheet having a thickness of 300 μm or less.
前記無機固体電解質材料の充填量が、当該固体電解質シートの全体を１００質量％としたとき、１５質量％以上８５質量％以下である固体電解質シート。 In the solid electrolyte sheet according to any one of claims 1 to 3,
A solid electrolyte sheet in which the filling amount of the inorganic solid electrolyte material is 15% by mass or more and 85% by mass or less when the total amount of the solid electrolyte sheet is 100% by mass.
当該固体電解質シート中のバインダーの含有量が、前記固体電解質シートの全体を１００質量％としたとき、０．５質量％未満である固体電解質シート。 In the solid electrolyte sheet according to any one of claims 1 to 4,
The solid electrolyte sheet whose content of the binder in the said solid electrolyte sheet is less than 0.5 mass% when the whole said solid electrolyte sheet is 100 mass%.
全固体型リチウムイオン電池を構成する固体電解質層に用いられるものである固体電解質シート。 In the solid electrolyte sheet according to any one of claims 1 to 5,
A solid electrolyte sheet used for a solid electrolyte layer constituting an all solid-state lithium ion battery.
２７．０℃、印加電圧１０ｍＶ、測定周波数域０．１Ｈｚ〜７ＭＨｚの測定条件における交流インピーダンス法による、前記固体電解質シートのリチウムイオン伝導度が０．２×１０ −４ Ｓ・ｃｍ −１ 以上である固体電解質シート。 In the solid electrolyte sheet according to any one of claims 1 to 6,
When the lithium ion conductivity of the solid electrolyte sheet is 0.2 × 10 −4 S · cm −1 or more by an AC impedance method under measurement conditions of 27.0 ° C., applied voltage 10 mV, and measurement frequency range 0.1 Hz to 7 MHz A solid electrolyte sheet.
前記多孔性基材は絶縁性材料により構成されている固体電解質シート。 In the solid electrolyte sheet according to any one of claims 1 to 7,
The porous substrate is a solid electrolyte sheet made of an insulating material.
前記多孔性基材の空隙率が５０％以上９５％以下である固体電解質シート。 In the solid electrolyte sheet according to any one of claims 1 to 8,
A solid electrolyte sheet in which the porosity of the porous substrate is 50% or more and 95% or less.
前記無機固体電解質材料が硫化物固体電解質材料および酸化物固体電解質材料から選択される少なくとも一種を含む固体電解質シート。 A solid electrolyte sheet, wherein the inorganic solid electrolyte material includes at least one selected from sulfide solid electrolyte materials and oxide solid electrolyte materials.
レーザー回折散乱式粒度分布測定法による重量基準粒度分布における、前記無機固体電解質材料の平均粒子径ｄ Average particle diameter d of the inorganic solid electrolyte material in a weight-based particle size distribution measured by a laser diffraction / scattering particle size distribution measurement method ５０50 が１μｍ以上２０μｍ以下である固体電解質シート。Is a solid electrolyte sheet having a thickness of 1 μm or more and 20 μm or less.
前記固体電解質層が、請求項１乃至１１いずれか一項に記載の固体電解質シートにより構成されたものである全固体型リチウムイオン電池。 An all-solid-state lithium ion battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated in this order,
The all-solid-state lithium ion battery in which the said solid electrolyte layer is comprised with the solid electrolyte sheet as described in any one of Claims 1 thru | or 11 .
シート状の多孔性基材の少なくとも一方の面に、粘着剤層を形成する工程と、
前記粘着剤層上に無機固体電解質材料を付着させることにより無機固体電解質材料層を形成し、前記多孔性基材、前記粘着剤層、および前記無機固体電解質材料層がこの順番に積層された積層体を得る工程と、
得られた前記積層体を加圧することにより、前記粘着剤層を構成する粘着剤を前記多孔性基材の空隙を囲む骨格部表面に付着させるとともに、前記多孔性基材の前記空隙内に前記無機固体電解質材料層を構成する前記無機固体電解質材料を充填する工程と、
を含む固体電解質シートの製造方法。 A manufacturing method for manufacturing the solid electrolyte sheet according to claim 2,
Forming an adhesive layer on at least one surface of the sheet-like porous substrate; and
An inorganic solid electrolyte material layer is formed by attaching an inorganic solid electrolyte material on the pressure-sensitive adhesive layer, and the porous base material, the pressure-sensitive adhesive layer, and the inorganic solid electrolyte material layer are laminated in this order. Obtaining a body;
By pressurizing the obtained laminate, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is attached to the surface of the skeleton surrounding the voids of the porous substrate, and the voids in the porous substrate are Filling the inorganic solid electrolyte material constituting the inorganic solid electrolyte material layer;
The manufacturing method of the solid electrolyte sheet containing this.
シート状の多孔性基材と、粘着剤を準備する工程と、
前記多孔性基材の空隙を囲む骨格部表面に、前記粘着剤をコーティングする工程と、
前記多孔性基材の前記空隙内に無機固体電解質材料を充填する工程と、
を含む固体電解質シートの製造方法。 A manufacturing method for manufacturing the solid electrolyte sheet according to claim 2,
A step of preparing a sheet-like porous substrate and an adhesive;
Coating the pressure-sensitive adhesive on the surface of the skeleton surrounding the voids of the porous substrate;
Filling an inorganic solid electrolyte material in the voids of the porous substrate;
The manufacturing method of the solid electrolyte sheet containing this.
前記多孔性基材の空隙体積をＡとし、前記粘着剤の体積をＢとしたとき、
［（Ａ−Ｂ）／Ａ］×１００で定義される残空隙率が１０％以上９０％以下である固体電解質シートの製造方法。 A method for producing a solid electrolyte sheet according to claim 13 or 14 ,
When the void volume of the porous substrate is A and the volume of the adhesive is B,
The manufacturing method of the solid electrolyte sheet whose remaining porosity defined by [(A-B) / A] x100 is 10% or more and 90% or less.
Priority Applications (1)
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| JP2018050524A JP6498335B2 (en) | 2018-03-19 | 2018-03-19 | Solid electrolyte sheet, all solid-state lithium ion battery, and method for producing solid electrolyte sheet |
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| JP2018050524A JP6498335B2 (en) | 2018-03-19 | 2018-03-19 | Solid electrolyte sheet, all solid-state lithium ion battery, and method for producing solid electrolyte sheet |
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| JP2014023429A Division JP6310716B2 (en) | 2014-02-10 | 2014-02-10 | Solid electrolyte sheet, all solid-state lithium ion battery, and method for producing solid electrolyte sheet |
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| JP2018101641A JP2018101641A (en) | 2018-06-28 |
| JP2018101641A5 true JP2018101641A5 (en) | 2018-08-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6992710B2 (en) * | 2018-09-03 | 2022-01-13 | トヨタ自動車株式会社 | A composite solid electrolyte layer, a method for manufacturing the same, and a method for manufacturing an all-solid-state battery. |
| WO2020054081A1 (en) * | 2018-09-11 | 2020-03-19 | マクセルホールディングス株式会社 | Solid electrolyte sheet and all-solid-state lithium secondary battery |
| KR102171532B1 (en) * | 2018-10-12 | 2020-10-29 | 한국과학기술연구원 | Eutectic liquid metal-air batteries comprising liquid metal electrode and method of preparation thereof |
| WO2020137912A1 (en) * | 2018-12-28 | 2020-07-02 | 株式会社パワーフォー | Secondary battery |
| JP6836281B2 (en) * | 2018-12-28 | 2021-02-24 | 株式会社パワーフォー | Rechargeable battery |
| JP7090808B2 (en) * | 2019-03-19 | 2022-06-24 | エルジー エナジー ソリューション リミテッド | Solid electrolyte membrane, its manufacturing method and method for selecting a solid electrolyte membrane |
| KR102605224B1 (en) * | 2019-03-19 | 2023-11-23 | 주식회사 엘지에너지솔루션 | A solid electrolyte membrane, a method for manufacturing the same and a method for selecting a solid electrolyte membrane |
| JP7390635B2 (en) * | 2019-04-26 | 2023-12-04 | 株式会社日本製鋼所 | Solid electrolyte membrane manufacturing method, all-solid-state battery manufacturing method, solid-state electrolyte membrane manufacturing device, and all-solid-state battery manufacturing device |
| US20210328260A1 (en) * | 2019-05-03 | 2021-10-21 | Lg Chem, Ltd. | Solid electrolyte membrane, method for manufacturing same and solid-state battery including same |
| EP4130370A4 (en) * | 2020-03-31 | 2024-04-17 | Mitsubishi Paper Mills Ltd | Non-woven fabric for supporting solid electrolyte, and solid electrolyte sheet |
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| JP4359077B2 (en) * | 2003-06-10 | 2009-11-04 | Ｎｂｃ株式会社 | Woven fabric for solid electrolyte support and solid electrolyte sheet for lithium battery |
| JP2008103258A (en) * | 2006-10-20 | 2008-05-01 | Idemitsu Kosan Co Ltd | Solid electrolyte sheet, electrode sheet, and all-solid secondary battery using it |
| JP5456954B2 (en) * | 2006-11-30 | 2014-04-02 | 日産自動車株式会社 | Bipolar type secondary battery module structure |
| US20130040225A1 (en) * | 2010-03-08 | 2013-02-14 | Nippon Sheet Glass Company, Limited | Reinforcing sheet for solid electrolyte membrane |
| JP2013062038A (en) * | 2011-09-12 | 2013-04-04 | Hitachi Maxell Energy Ltd | Lithium ion secondary battery |
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