JP7400729B2 - Electrodes for inorganic solid electrolyte secondary batteries, and inorganic solid electrolyte secondary batteries - Google Patents
Electrodes for inorganic solid electrolyte secondary batteries, and inorganic solid electrolyte secondary batteries Download PDFInfo
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- JP7400729B2 JP7400729B2 JP2020557702A JP2020557702A JP7400729B2 JP 7400729 B2 JP7400729 B2 JP 7400729B2 JP 2020557702 A JP2020557702 A JP 2020557702A JP 2020557702 A JP2020557702 A JP 2020557702A JP 7400729 B2 JP7400729 B2 JP 7400729B2
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- solid electrolyte
- electrode
- inorganic solid
- electrolyte secondary
- secondary battery
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- 229910003480 inorganic solid Inorganic materials 0.000 title claims description 88
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- 150000002500 ions Chemical class 0.000 claims description 63
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- 239000011149 active material Substances 0.000 claims description 33
- 229910003002 lithium salt Inorganic materials 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 30
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- 238000000034 method Methods 0.000 claims description 15
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- 239000000463 material Substances 0.000 claims description 9
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- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000002322 conducting polymer Substances 0.000 claims description 7
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- 238000010438 heat treatment Methods 0.000 claims description 6
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- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- LLEVMYXEJUDBTA-UHFFFAOYSA-N heptanedinitrile Chemical compound N#CCCCCCC#N LLEVMYXEJUDBTA-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
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- 229910052745 lead Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
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- 229920000609 methyl cellulose Polymers 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QXOYPGTWWXJFDI-UHFFFAOYSA-N nonanedinitrile Chemical compound N#CCCCCCCCC#N QXOYPGTWWXJFDI-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- AVNANMSIFNUHNY-MQQKCMAXSA-N oxiran-2-ylmethyl (2e,4e)-hexa-2,4-dienoate Chemical compound C\C=C\C=C\C(=O)OCC1CO1 AVNANMSIFNUHNY-MQQKCMAXSA-N 0.000 description 1
- JUVGLPRIQOJMIR-UHFFFAOYSA-N oxiran-2-ylmethyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OCC1CO1 JUVGLPRIQOJMIR-UHFFFAOYSA-N 0.000 description 1
- NZSXYXVUIOHHSF-UHFFFAOYSA-N oxiran-2-ylmethyl hex-4-enoate Chemical compound CC=CCCC(=O)OCC1CO1 NZSXYXVUIOHHSF-UHFFFAOYSA-N 0.000 description 1
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- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002226 superionic conductor Substances 0.000 description 1
- GJSGYPDDPQRWPK-UHFFFAOYSA-N tetrapentylammonium Chemical compound CCCCC[N+](CCCCC)(CCCCC)CCCCC GJSGYPDDPQRWPK-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Description
本発明は、無機固体電解質二次電池用電極、その製造方法、及び無機固体電解質二次電池に関する。 The present invention relates to an electrode for an inorganic solid electrolyte secondary battery, a method for manufacturing the same, and an inorganic solid electrolyte secondary battery.
従来、リチウムイオン電池に代表される非水電解質二次電池は、電解質にイオン伝導性の点から溶液またはペースト状のものが用いられている。しかし、液漏れによる機器の損傷の恐れがあることから、種々の安全対策が必要であり、大型電池開発の障壁になっている。 Conventionally, non-aqueous electrolyte secondary batteries, typified by lithium ion batteries, have used solution or paste electrolytes from the viewpoint of ionic conductivity. However, since there is a risk of damage to equipment due to liquid leakage, various safety measures are required, which is an obstacle to the development of large batteries.
これに対し高分子固体電解質、無機固体電解質などの電解質が固体化された固体電解質が提案されている。高分子固体電解質は、一般に柔軟性、曲げ加工性、および成形性に優れ、応用されるデバイスの設計の自由度が高くなるなどの利点があるが、負荷特性や低温特性が悪いために、高温作動の電池用途に限られるという欠点がある。一方、無機固体電解質は、高分子固体電解質と比べて、イオン伝導性が高いものの、電解質が結晶質あるいは非晶質からなり、充放電時の正負極活物質による体積変化の緩和が難しく、更に、電極と電解質の界面抵抗が高いため、充放電特性が不十分という問題がある。 In contrast, solid electrolytes in which electrolytes are solidified, such as polymer solid electrolytes and inorganic solid electrolytes, have been proposed. Polymer solid electrolytes generally have excellent flexibility, bending workability, and formability, and have the advantage of increasing the degree of freedom in designing the devices to which they are applied. However, due to poor load characteristics and low-temperature characteristics, The disadvantage is that it is limited to battery-operated applications. On the other hand, although inorganic solid electrolytes have higher ionic conductivity than solid polymer electrolytes, the electrolytes are crystalline or amorphous, making it difficult to alleviate volume changes caused by positive and negative electrode active materials during charging and discharging. However, due to the high interfacial resistance between the electrode and the electrolyte, there is a problem in that the charging and discharging characteristics are insufficient.
無機固体電解質と電極の界面の抵抗を下げる方法として、例えば、特許文献１においては、リチウムイオン伝導性バインダーを含む溶媒中に活物質を分散させ、硫化物系固体電解質を添加し、加熱乾燥後、活物質シートを形成させている。しかしながら、活物質とリチウムイオン伝導性バインダーを分散させて、電極を作製すると、電極内に空隙ができる。電解液系では、電極内の空隙は、有機電解液で満たされており、電極内のイオン伝導性に寄与されるが、硫化物系固体電解質を含む電極には、空隙が存在するので、特に、体積エネルギー密度に不利な要素となる。また、硫化物系固体電解質の添加量は活物質１００質量部に対して、２５～１００質量部が必要であり、電極の活物質量が少なく、高エネルギー密度の電池には不向きである。 As a method of lowering the resistance at the interface between an inorganic solid electrolyte and an electrode, for example, in Patent Document 1, an active material is dispersed in a solvent containing a lithium ion conductive binder, a sulfide-based solid electrolyte is added, and after heating and drying. , forming an active material sheet. However, when an electrode is prepared by dispersing an active material and a lithium ion conductive binder, voids are created within the electrode. In an electrolyte system, the voids within the electrode are filled with an organic electrolyte, which contributes to ionic conductivity within the electrode, but electrodes containing sulfide-based solid electrolytes have voids, so , which is a disadvantageous factor for volumetric energy density. Further, the amount of the sulfide-based solid electrolyte added is required to be 25 to 100 parts by mass per 100 parts by mass of the active material, and the amount of active material in the electrode is small, making it unsuitable for high energy density batteries.
また、例えば特許文献２においては、高分子化合物と電解質塩と電極活物質を希釈剤に入れ、加熱攪拌後、被覆された電極活物質を得ている。この方法では、活物質同士の結着性に対して効果があるが、特許文献１と同様、電極内に空隙ができる。 Furthermore, for example, in Patent Document 2, a polymer compound, an electrolyte salt, and an electrode active material are placed in a diluent, and after heating and stirring, a coated electrode active material is obtained. Although this method is effective in improving the binding properties between active materials, voids are created in the electrode as in Patent Document 1.
さらに、電極内に高分子固体電解質を含浸する方法として、例えば特許文献３の実施例には、モノマー状にあるポリエチレンオキシドとＬｉＢＦ4を含浸させて重合の記載があるが、ポリエチレンオキシドを更に重合できる方法は知られていない。また、ポリエチレンオキシドは過酸化物などの重合開始剤を用いても、架橋することはできない。ポリエチレンオキシドは、結晶性が高く、融点（６０℃）以下になると、結晶化に伴い、柔軟性がなくなり、結着性が弱くなる。また、融点以上になると、ポリエチレンオキシドが溶融するため形状維持ができなくなり、結着性が弱くなるという問題がある。ポリエチレンオキシドでは無機固体電解質の界面の抵抗を下げることは困難である。Furthermore, as a method of impregnating a polymer solid electrolyte into an electrode, for example, in the example of Patent Document 3, there is a description of polymerization by impregnating polyethylene oxide and LiBF 4 in monomer form, but polyethylene oxide is further polymerized. There is no known way to do this. Moreover, polyethylene oxide cannot be crosslinked even if a polymerization initiator such as peroxide is used. Polyethylene oxide has high crystallinity, and when the temperature falls below its melting point (60° C.), it loses flexibility as it crystallizes and its binding properties become weak. Moreover, when the temperature exceeds the melting point, polyethylene oxide melts, making it impossible to maintain its shape, resulting in a problem of weakened binding. With polyethylene oxide, it is difficult to lower the resistance at the interface of the inorganic solid electrolyte.
本発明は、無機固体電解質二次電池に優れた充放電特性を発揮させる新規な無機固体電解質二次電池用電極を提供することを主な目的とする。さらに、本発明は、当該無機固体電解質二次電池用電極の製造方法、及び当該無機固体電解質二次電池用電極を利用した無機固体電解質二次電池を提供することも目的とする。 The main object of the present invention is to provide a novel electrode for an inorganic solid electrolyte secondary battery that allows the inorganic solid electrolyte secondary battery to exhibit excellent charge and discharge characteristics. Furthermore, another object of the present invention is to provide a method for manufacturing the electrode for an inorganic solid electrolyte secondary battery, and an inorganic solid electrolyte secondary battery using the electrode for an inorganic solid electrolyte secondary battery.
本発明者は、上記の課題を解決すべく鋭意検討を行った。その結果、側鎖にエチレンオキシド単位を有するイオン伝導性ポリマー及びリチウム塩化合物を含むイオン伝導性ポリマー材料と、活物質とを含有する電極材料層を備える固体電解質二次電池用電極は、固体電解質二次電池に優れた充放電特性を発揮させることを見出した。本発明は、このような知見に基づいて、さらに検討を重ねることにより完成したものである。 The present inventor conducted extensive studies to solve the above problems. As a result, an electrode for a solid electrolyte secondary battery comprising an electrode material layer containing an ion conductive polymer material having an ethylene oxide unit in a side chain and an ion conductive polymer material containing a lithium salt compound, and an active material is obtained. It has been discovered that the new battery exhibits excellent charging and discharging characteristics. The present invention was completed through further studies based on such knowledge.
即ち、本発明は、下記に掲げる態様の発明を提供する。
項１． 側鎖にエチレンオキシド単位を有するイオン伝導性ポリマー及びリチウム塩化合物を含むイオン伝導性ポリマー材料と、活物質とを含有する電極材料層を備える、無機固体電解質二次電池用電極。
項２． 前記活物質が、ＬｉＭＯ2、ＬｉＭ2Ｏ4、Ｌｉ2ＭＯ3、ＬｉＭＥＯ4（式中のＭは、遷移金属からなり、Ｃｏ、Ｍｎ、Ｎｉ、Ｃｒ、Ｆｅ、Ｔｉの少なくとも一種を含んでいる。ＥはＰ、Ｓｉの少なくとも１種を含んでいる。）からなる群より選択される少なくとも１種である、項１に記載の無機固体電解質二次電池用電極。
項３． 前記活物質が、炭素材料、シリコン系化合物、及びスズ系化合物からなる群より選択される少なくとも１種である、項１に記載の無機固体電解質二次電池用電極。
項４． 前記イオン伝導性ポリマーは、側鎖にエチレンオキシド単位を有するポリエーテルである、項１～３のいずれか１項に記載の無機固体電解質二次電池用電極。
項５． 無機固体電解質と共に、固体電解質二次電池に用いられる、項１～４のいずれか１項に記載の無機固体電解質二次電池用電極。
項６． 前記無機固体電解質は、酸化物系固体電解質又は硫化物系固体電解質である、項５に記載の無機固体電解質二次電池用電極。
項７． 活物質を含む層に、側鎖にエチレンオキシド単位を有するイオン伝導性ポリマー及びリチウム塩化合物を含むイオン伝導性ポリマー材料を含浸させる工程を含む、無機固体電解質二次電池用電極の製造方法。
項８． 前記イオン伝導性ポリマー材料を含浸させた層を、加熱又は活性エネルギー線照射によって架橋させる工程を含む、項７に記載の無機固体電解質二次電池用電極の製造方法。
項９． 項１～６のいずれかに記載の無機固体電解質二次電池用電極を含む、無機固体電解質二次電池。That is, the present invention provides the inventions of the following aspects.
Item 1. An electrode for an inorganic solid electrolyte secondary battery, comprising an electrode material layer containing an ion conductive polymer material having an ion conductive polymer having an ethylene oxide unit in a side chain and a lithium salt compound, and an active material.
Item 2. The active material is LiMO 2 , LiM 2 O 4 , Li 2 MO 3 , LiMEO 4 (M in the formula is a transition metal and contains at least one of Co, Mn, Ni, Cr, Fe, and Ti). Item 2. The electrode for an inorganic solid electrolyte secondary battery according to item 1, wherein E is at least one selected from the group consisting of P and Si.
Item 3. Item 2. The electrode for an inorganic solid electrolyte secondary battery according to Item 1, wherein the active material is at least one selected from the group consisting of a carbon material, a silicon-based compound, and a tin-based compound.
Item 4. Item 4. The electrode for an inorganic solid electrolyte secondary battery according to any one of Items 1 to 3, wherein the ion-conductive polymer is a polyether having an ethylene oxide unit in a side chain.
Item 5. The electrode for an inorganic solid electrolyte secondary battery according to any one of Items 1 to 4, which is used in a solid electrolyte secondary battery together with an inorganic solid electrolyte.
Item 6. 6. The inorganic solid electrolyte secondary battery electrode according to item 5, wherein the inorganic solid electrolyte is an oxide solid electrolyte or a sulfide solid electrolyte.
Section 7. A method for producing an electrode for an inorganic solid electrolyte secondary battery, the method comprising the step of impregnating a layer containing an active material with an ion conductive polymer material containing an ion conductive polymer having an ethylene oxide unit in a side chain and a lithium salt compound.
Section 8. Item 8. The method for producing an electrode for an inorganic solid electrolyte secondary battery according to item 7, which includes a step of crosslinking the layer impregnated with the ion-conductive polymer material by heating or irradiating with active energy rays.
Item 9. Item 7. An inorganic solid electrolyte secondary battery comprising the inorganic solid electrolyte secondary battery electrode according to any one of Items 1 to 6.
本発明によれば、無機固体電解質二次電池に優れた充放電特性を発揮させる新規な無機固体電解質二次電池用電極を提供することができる。さらに、本発明によれば、当該無機固体電解質二次電池用電極の製造方法、及び当該無機固体電解質二次電池用電極を利用した無機固体電解質二次電池を提供することもできる。 According to the present invention, it is possible to provide a novel electrode for an inorganic solid electrolyte secondary battery that allows an inorganic solid electrolyte secondary battery to exhibit excellent charge and discharge characteristics. Furthermore, according to the present invention, it is also possible to provide a method for manufacturing the electrode for an inorganic solid electrolyte secondary battery, and an inorganic solid electrolyte secondary battery using the electrode for an inorganic solid electrolyte secondary battery.
本発明の無機固体電解質二次電池用電極は、側鎖にエチレンオキシド単位を有するイオン伝導性ポリマー及びリチウム塩化合物を含むイオン伝導性ポリマー材料と、活物質とを含有する電極材料層を備えることを特徴としている。本発明の無機固体電解質二次電池用電極は、このような構成を備えていることにより、無機固体電解質二次電池に優れた充放電特性を発揮させることができる。 The electrode for an inorganic solid electrolyte secondary battery of the present invention includes an electrode material layer containing an ion conductive polymer material containing an ion conductive polymer having an ethylene oxide unit in a side chain and a lithium salt compound, and an active material. It is a feature. The inorganic solid electrolyte secondary battery electrode of the present invention having such a configuration allows the inorganic solid electrolyte secondary battery to exhibit excellent charge/discharge characteristics.
より具体的には、本発明の無機固体電解質二次電池用電極（以下、「本発明の電極」と表記することがある）においては、活物質に加えて、さらに、前記のイオン伝導性ポリマー材料が、電極材料層に含まれていることにより、電極材料層に含まれる活物質などの電極材料（具体的には、活物質粒子、バインダー、導電助剤、増粘剤、無機固体電解質など）の空隙がイオン伝導性ポリマー材料によって埋められ、電極材料層の内部の界面抵抗が効果的に低下し、結果として、優れた充放電特性が発揮されるものと考えられる。また、無機固体電解質二次電池は、高温環境（例えば１００℃以上の高温環境）で使用されることもあるが、本発明の電極を用いることにより、高温環境において優れた充放電特性が発揮される。以下、本発明の無機固体電解質二次電池用電極、その製造方法、及び本発明の無機固体電解質二次電池用電極を利用した無機固体電解質二次電池について詳述する。 More specifically, in the inorganic solid electrolyte secondary battery electrode of the present invention (hereinafter sometimes referred to as "the electrode of the present invention"), in addition to the active material, the above-mentioned ion conductive polymer is further added. By the material being included in the electrode material layer, electrode materials such as active materials contained in the electrode material layer (specifically, active material particles, binders, conductive aids, thickeners, inorganic solid electrolytes, etc.) ) is filled with the ion-conductive polymer material, the interfacial resistance inside the electrode material layer is effectively reduced, and as a result, it is thought that excellent charge-discharge characteristics are exhibited. In addition, inorganic solid electrolyte secondary batteries are sometimes used in high-temperature environments (for example, high-temperature environments of 100°C or higher), and by using the electrode of the present invention, excellent charge-discharge characteristics can be exhibited in high-temperature environments. Ru. Hereinafter, the inorganic solid electrolyte secondary battery electrode of the present invention, its manufacturing method, and the inorganic solid electrolyte secondary battery using the inorganic solid electrolyte secondary battery electrode of the present invention will be described in detail.
なお、本明細書において、「～」で結ばれた数値は、「～」の前後の数値を下限値及び上限値として含む数値範囲を意味する。複数の下限値と複数の上限値が別個に記載されている場合、任意の下限値と上限値を選択し、「～」で結ぶことができるものとする。 In this specification, numerical values connected by "-" mean a numerical range that includes the numerical values before and after "-" as lower and upper limits. If multiple lower limit values and multiple upper limit values are listed separately, it is possible to select any lower limit value and upper limit value and connect them with "~".
本発明の電極は、側鎖にエチレンオキシド単位を有するイオン伝導性ポリマー及びリチウム塩化合物を含むイオン伝導性ポリマー材料と、活物質とを含有する電極材料層を備える。より具体的には、本発明の電極は、当該電極材料層に加えて、集電体を備えており、電極材料層は集電体の上に形成されている。イオン伝導性ポリマー材料の詳細については後述する。 The electrode of the present invention includes an electrode material layer containing an ion-conductive polymer material containing an ion-conductive polymer having an ethylene oxide unit in a side chain and a lithium salt compound, and an active material. More specifically, the electrode of the present invention includes a current collector in addition to the electrode material layer, and the electrode material layer is formed on the current collector. Details of the ion-conductive polymer material will be described later.
本発明の電極は、無機固体電解質二次電池において、正極及び負極のいずれとすることもできる。正極においては、集電体に正極材料層を形成し、負極においては、集電体に負極材料層を形成する。本発明の電極が正極である場合には、正極材料層が前記のイオン伝導性ポリマー材料と正極活物質とを含有する。また、本発明の電極が負極である場合には、負極材料層が前記のイオン伝導性ポリマー材料と負極活物質とを含有する。 The electrode of the present invention can be used as either a positive electrode or a negative electrode in an inorganic solid electrolyte secondary battery. In the positive electrode, a positive electrode material layer is formed on the current collector, and in the negative electrode, a negative electrode material layer is formed on the current collector. When the electrode of the present invention is a positive electrode, the positive electrode material layer contains the above-described ion-conductive polymer material and a positive electrode active material. Further, when the electrode of the present invention is a negative electrode, the negative electrode material layer contains the above-mentioned ion-conductive polymer material and negative electrode active material.
正極、負極には、公知の集電体を用いることができる。具体的には、正極には、集電体として、アルミニウム、ニッケル、ステンレス、金、白金、チタン等の金属が使用される。負極には、集電体として、銅、ニッケル、ステンレス、金、白金、チタン等の金属が使用される。 A known current collector can be used for the positive electrode and the negative electrode. Specifically, metals such as aluminum, nickel, stainless steel, gold, platinum, and titanium are used as current collectors in the positive electrode. For the negative electrode, a metal such as copper, nickel, stainless steel, gold, platinum, titanium, etc. is used as a current collector.
また、正極材料層、負極材料層は、それぞれ、前記のイオン伝導性ポリマー材料に加えて、少なくとも正極活物質、負極活物質を含有し、更に導電助剤、バインダー、増粘剤を含有していてもよく、必要に応じて、後述の無機固体電解質を含有させてもよい。 Further, the positive electrode material layer and the negative electrode material layer each contain at least a positive electrode active material and a negative electrode active material in addition to the above-mentioned ion-conductive polymer material, and further contain a conductive aid, a binder, and a thickener. If necessary, an inorganic solid electrolyte described below may be included.
本発明で使用される正極活物質は、ＬｉＭＯ2、ＬｉＭ2Ｏ4、Ｌｉ2ＭＯ3、ＬｉＭＥＯ4のいずれかの組成からなるリチウム金属含有複合酸化物粉末である。ここで式中のＭは主として遷移金属からなり、Ｃｏ、Ｍｎ、Ｎｉ、Ｃｒ、Ｆｅ、Ｔｉの少なくとも一種を含んでいる。Ｍは遷移金属からなるが、遷移金属以外にもＡｌ、Ｇａ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉ、Ｓｉ、Ｐ、Ｂなどが添加されていてもよい。ＥはＰ、Ｓｉの少なくとも１種を含んでいる。正極活物質の粒子径には５０μｍ以下が好ましく、更に好ましくは２０μｍ以下のものを用いる。これらの活物質は、３Ｖ（ｖｓ．Ｌｉ／Ｌｉ＋）以上の起電力を有するものである。The positive electrode active material used in the present invention is a lithium metal-containing composite oxide powder having a composition of LiMO 2 , LiM 2 O 4 , Li 2 MO 3 , and LiMEO 4 . Here, M in the formula mainly consists of a transition metal and contains at least one of Co, Mn, Ni, Cr, Fe, and Ti. M is made of a transition metal, but other than the transition metal, Al, Ga, Ge, Sn, Pb, Sb, Bi, Si, P, B, etc. may be added. E contains at least one of P and Si. The particle size of the positive electrode active material is preferably 50 μm or less, more preferably 20 μm or less. These active materials have an electromotive force of 3V (vs. Li/Li+) or more.
正極活物質の具体例としては、コバルト酸リチウム、ニッケル酸リチウム、ニッケル／コバルト／マンガン酸リチウム（３元系）、スピネル型マンガン酸リチウム、リン酸鉄リチウムなどが挙げられる。 Specific examples of the positive electrode active material include lithium cobalt oxide, lithium nickel oxide, nickel/cobalt/lithium manganate (ternary system), spinel-type lithium manganate, lithium iron phosphate, and the like.
本発明で使用される負極活物質は、リチウムイオンなどのアルカリ金属イオンを吸蔵・放出可能な構造（層間化合物）を有する炭素材料（天然黒鉛、人造黒鉛、非晶質炭素等）か、リチウムイオンなどのアルカリ金属イオンを吸蔵・放出可能なリチウム、アルミニウム系化合物、スズ系化合物、シリコン系化合物、チタン系化合物等の金属である。粉末の場合、粒子径は１０ｎｍ以上１００μｍ以下が好ましく、更に好ましくは２０ｎｍ以上２０μｍ以下である。また、金属と炭素材料との混合活物質として用いてもよい。 The negative electrode active material used in the present invention is a carbon material (natural graphite, artificial graphite, amorphous carbon, etc.) that has a structure (intercalation compound) that can absorb and release alkali metal ions such as lithium ions, or lithium ions. These are metals such as lithium, aluminum compounds, tin compounds, silicon compounds, and titanium compounds that can absorb and release alkali metal ions such as ions. In the case of powder, the particle size is preferably 10 nm or more and 100 μm or less, more preferably 20 nm or more and 20 μm or less. Further, it may be used as a mixed active material of metal and carbon material.
導電助剤を用いる場合には、公知の導電助剤を用いることができ、黒鉛、ファーネスブラック、アセチレンブラック、ケッチェンブラックなどの導電性カーボンブラック、カーボンナノチューブなどの炭素繊維、または金属粉末等が挙げられる。これら導電助剤は１種または２種以上用いてもよい。 When using a conductive aid, a known conductive aid may be used, such as conductive carbon black such as graphite, furnace black, acetylene black, or Ketjen black, carbon fiber such as carbon nanotube, or metal powder. Can be mentioned. One or more types of these conductive aids may be used.
バインダーとしては、例えばＰＶｄＦ等のフッ素樹脂、フッ素ゴムやアクリルゴム、変性アクリルゴム、スチレン－ブタジエンゴム、アクリル系重合体、ビニル系重合体、前記記載のイオン伝導性ポリマーから選ばれる１種以上の化合物を用いることができる。これらバインダーは活物質を１００質量部として、好ましくは５質量部以下、より好ましくは３質量部以下、例えば０．０１～２質量部添加する。 The binder may be one or more selected from fluororesins such as PVdF, fluororubbers, acrylic rubbers, modified acrylic rubbers, styrene-butadiene rubbers, acrylic polymers, vinyl polymers, and the ion-conductive polymers described above. Compounds can be used. These binders are preferably added in an amount of 5 parts by weight or less, more preferably 3 parts by weight or less, for example 0.01 to 2 parts by weight, based on 100 parts by weight of the active material.
増粘剤の具体例としては、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、エチルセルロースおよびこれらの塩（ナトリウム塩等のアルカリ金属塩、アンモニウム塩）、ポリビニルアルコール、ポリアクリル酸塩、ポリエチレンオキサイド等が挙げられるこれら増粘剤は１種または２種以上用いてもよい。これら増粘剤は活物質を１００質量部として、好ましくは５質量部以下、より好ましくは３質量部以下、例えば０．０１～２質量部添加する。また、塗工液の粘度が低い場合には増粘剤を併用することができる。 Specific examples of thickeners include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, salts thereof (alkali metal salts such as sodium salts, ammonium salts), polyvinyl alcohol, polyacrylates, polyethylene oxide, etc. One or more types of thickeners may be used. These thickeners are preferably added in an amount of 5 parts by mass or less, more preferably 3 parts by mass or less, for example 0.01 to 2 parts by mass, based on 100 parts by mass of the active material. Further, when the viscosity of the coating liquid is low, a thickener can be used in combination.
集電体と電極材料層を備える電極の作製方法は特に限定されず一般的な方法を利用することができる。例えば、正極活物質あるいは負極活物質、導電助剤、バインダー、水またはＮ-メチル-２-ピロリドン（ＮＭＰ）等の溶媒、必要に応じて増粘剤などからなる電極材料のペースト（塗工液）をドクターブレード法やシルクスクリーン法などにより集電体表面上に適切な厚さに均一に塗布することより行われる。 The method for producing an electrode including a current collector and an electrode material layer is not particularly limited, and a general method can be used. For example, an electrode material paste (coating liquid ) is applied uniformly to an appropriate thickness on the surface of the current collector using a doctor blade method, silk screen method, etc.
例えばドクターブレード法では、負極活物質粉末や正極活物質粉末、導電助剤、バインダー等を水に分散してスラリー状にし、金属電極基板に塗布した後、所定のスリット幅を有するブレードにより適切な厚さに均一化する。電極は活物質塗布後、余分な有機溶剤を除去するため、例えば、１００℃の熱風や８０℃減圧状態で乾燥する。乾燥後の電極はプレス装置によってプレス成型することで、集電体の上に電極材料層を積層した電極前駆体を形成する。 For example, in the doctor blade method, negative electrode active material powder, positive electrode active material powder, conductive additive, binder, etc. are dispersed in water to form a slurry, and after being applied to a metal electrode substrate, a blade having a predetermined slit width is used to form a slurry. Make the thickness uniform. After coating the active material, the electrode is dried, for example, with hot air at 100° C. or under reduced pressure at 80° C. in order to remove excess organic solvent. The dried electrode is press-molded using a press device to form an electrode precursor in which an electrode material layer is laminated on a current collector.
本発明の電極においては、このように形成された電極前駆体の電極材料層に、イオン伝導性ポリマー材料を含浸させることにより、イオン伝導性ポリマー材料と活物質とを含む電極を好適に製造することができる。すなわち、前述した従来の電極材料層の製造方法を利用して、電極材料層を形成すると、電極材料層を構成している電極材料間には活物質粒子などの空隙が形成される。本発明の電極においては、電極材料の空隙をイオン伝導性ポリマー材料が埋めるため、電極材料層の内部の界面抵抗を効率的に低下させることができる。 In the electrode of the present invention, an electrode containing an ion-conducting polymer material and an active material is suitably manufactured by impregnating the electrode material layer of the electrode precursor formed in this way with an ion-conducting polymer material. be able to. That is, when an electrode material layer is formed using the conventional electrode material layer manufacturing method described above, voids such as active material particles are formed between the electrode materials forming the electrode material layer. In the electrode of the present invention, since the ion conductive polymer material fills the voids in the electrode material, it is possible to efficiently reduce the interfacial resistance inside the electrode material layer.
イオン伝導性ポリマー材料は、側鎖にエチレンオキシド単位を有するイオン伝導性ポリマー及びリチウム塩化合物を含む。具体的には、本発明のイオン伝導性ポリマー材料は、側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーと、リチウム塩化合物との混合物である。 The ionically conductive polymer material includes an ionically conductive polymer having ethylene oxide units in the side chain and a lithium salt compound. Specifically, the ion-conducting polymer material of the present invention is a mixture of an ion-conducting polymer having ethylene oxide units in its side chain and a lithium salt compound.
本発明の電極において、電極材料層に含まれるイオン伝導性ポリマー材料の含有量としては、特に制限されないが、充放電特性を好適に向上させる観点から、活物質１００質量部に対して、好ましくは５～５０質量部、より好ましくは１５～３０質量部である。 In the electrode of the present invention, the content of the ion-conductive polymer material contained in the electrode material layer is not particularly limited, but from the viewpoint of suitably improving charge/discharge characteristics, it is preferably based on 100 parts by mass of the active material. The amount is 5 to 50 parts by weight, more preferably 15 to 30 parts by weight.
側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーとしては、例えば、側鎖にエチレンオキシド単位を有するポリエーテル、側鎖にエチレンオキシド単位を有するホウ酸エステル、側鎖にエチレンオキシド単位を有するポリオレフィン等があり、好ましくは側鎖にエチレンオキシド単位を有するポリエーテルである。 Examples of ion conductive polymers having ethylene oxide units in side chains include polyethers having ethylene oxide units in side chains, borate esters having ethylene oxide units in side chains, polyolefins having ethylene oxide units in side chains, etc. is a polyether having ethylene oxide units in its side chains.
側鎖にエチレンオキシド単位を有するポリエーテルは、側鎖にエチレンオキシド単位を有するエポキシ化合物から形成された構成単位を含むことが好ましい。すなわち、イオン伝導性ポリマーは、側鎖にエチレンオキシド単位を有するエポキシ化合物を少なくとも単量体としたポリマーであることが好ましい。 The polyether having ethylene oxide units in its side chains preferably includes a structural unit formed from an epoxy compound having ethylene oxide units in its side chains. That is, the ion conductive polymer is preferably a polymer containing at least a monomer of an epoxy compound having an ethylene oxide unit in its side chain.
側鎖にエチレンオキシド単位を有するエポキシ化合物としては、例えば、下記式（２）で表される単量体が挙げられ、下記式（２）、必要により下記式（１）、下記式（３）で表される単量体を用いた分岐型ポリエーテルは、側鎖にエチレンオキシド単位を有するポリエーテル（ｉ）となる。式（１）～（３）で表される単量体は、１種類のみを用いてもよいし、２種類以上を混合して用いてもよい。 Examples of the epoxy compound having an ethylene oxide unit in the side chain include a monomer represented by the following formula (2), and if necessary, the following formula (1) or the following formula (3). A branched polyether using the monomer shown is polyether (i) having an ethylene oxide unit in the side chain. The monomers represented by formulas (1) to (3) may be used alone or in combination of two or more.
［式（２）中、Ｒは－ＣＨ2Ｏ（ＣＨ2ＣＨ2Ｏ）nＲ4であり、Ｒ4は炭素数１～６のアルキル基であり、ｎは０～１２の数である。］[In formula (2), R is -CH 2 O(CH 2 CH 2 O) n R 4 , R 4 is an alkyl group having 1 to 6 carbon atoms, and n is a number from 0 to 12. ]
［式（３）中、Ｒ5は、エチレン性不飽和基を含有する基を表す。］[In formula (3), R 5 represents a group containing an ethylenically unsaturated group. ]
式（３）の単量体としては、アリルグリシジルエーテル、４－ビニルシクロヘキシルグリシジルエーテル、α－テルピニルグリシジルエーテル、シクロヘキセニルメチルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、アリルフェニルグリシジルエーテル、ビニルグリシジルエーテル、３，４－エポキシ－１－ブテン、３，４－エポキシ－１－ペンテン、４，５－エポキシ－２－ペンテン、１，２－エポキシ－５，９－シクロドデカンジエン、３，４－エポキシ－１－ビニルシクロヘキセン、１，２－エポキシ－５－シクロオクテン、アクリル酸グリシジル、メタクリル酸グリシジル、ソルビン酸グリシジル、ケイ皮酸グリシジル、クロトン酸グリシジル、グリシジル－４－ヘキセノエートが用いられる。好ましくは、アリルグリシジルエーテル、アクリル酸グリシジル、メタクリル酸グリシジルである。 Examples of the monomer of formula (3) include allyl glycidyl ether, 4-vinylcyclohexyl glycidyl ether, α-terpinyl glycidyl ether, cyclohexenylmethyl glycidyl ether, p-vinylbenzyl glycidyl ether, allyl phenyl glycidyl ether, and vinyl glycidyl ether. Ether, 3,4-epoxy-1-butene, 3,4-epoxy-1-pentene, 4,5-epoxy-2-pentene, 1,2-epoxy-5,9-cyclododecanediene, 3,4- Epoxy-1-vinylcyclohexene, 1,2-epoxy-5-cyclooctene, glycidyl acrylate, glycidyl methacrylate, glycidyl sorbate, glycidyl cinnamate, glycidyl crotonate, and glycidyl-4-hexenoate are used. Preferred are allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate.
側鎖にエチレンオキシド単位を有するポリエーテル（ｉ）の合成は、例えば、次のようにして行うことができる。開環重合触媒として有機アルミニウムを主体とする触媒系、有機亜鉛を主体とする触媒系、有機錫－リン酸エステル縮合物触媒系などの配位アニオン開始剤、または対イオンにＫ+を含むカリウムアルコキシド、ジフェニルメチルカリウム、水酸化カリウムなどのアニオン開始剤を用いて、各単量体を溶媒の存在下又は不存在下、反応温度１０～１２０℃、撹拌下で反応させることによってポリエーテル（ｉ）が得られる。重合度、あるいは得られる共重合体の性質などの点から、配位アニオン開始剤が好ましく、なかでも有機錫－リン酸エステル縮合物触媒系が取り扱い易く特に好ましい。The polyether (i) having an ethylene oxide unit in its side chain can be synthesized, for example, as follows. As a ring-opening polymerization catalyst, a coordination anion initiator such as a catalyst system mainly composed of organoaluminum, a catalyst system mainly composed of organozinc, an organotin-phosphoric acid ester condensate catalyst system, or potassium containing K + as a counter ion. Polyether (i ) is obtained. From the viewpoint of the degree of polymerization or the properties of the resulting copolymer, coordinating anion initiators are preferred, and among them, organotin-phosphoric acid ester condensate catalyst systems are particularly preferred because they are easy to handle.
側鎖にエチレンオキシド単位を有するポリエーテル（ｉ）において、式（１）の単量体に由来する繰り返し単位（Ａ）と、式（２）の単量体に由来する繰り返し単位（Ｂ）と、式（３）の単量体に由来する繰り返し単位（Ｃ）とのモル比は、（Ａ）９５～５モル％、（Ｂ）５～９５モル％、および（Ｃ）０～２０モル％が適当であり、好ましくは（Ａ）９２～９モル％、（Ｂ）７～９０モル％、および（Ｃ）１～１５モル％、更に好ましくは（Ａ）８８～１８モル％、（Ｂ）１０～８０モル％、および（Ｃ）２～１５モル％である。繰り返し単位（Ａ）が９５モル％以下であるとガラス転移温度の上昇とオキシエチレン鎖の結晶化を招かず、結果的にイオン伝導性の点で好ましい。 In the polyether (i) having an ethylene oxide unit in the side chain, a repeating unit (A) derived from the monomer of formula (1), a repeating unit (B) derived from the monomer of formula (2), The molar ratio with the repeating unit (C) derived from the monomer of formula (3) is (A) 95 to 5 mol%, (B) 5 to 95 mol%, and (C) 0 to 20 mol%. suitable, preferably (A) 92-9 mol%, (B) 7-90 mol%, and (C) 1-15 mol%, more preferably (A) 88-18 mol%, (B) 10 ~80 mol%, and (C) 2~15 mol%. When the content of the repeating unit (A) is 95 mol % or less, an increase in the glass transition temperature and crystallization of oxyethylene chains are not caused, which is preferable in terms of ionic conductivity.
側鎖にエチレンオキシド単位を有するポリエーテル（ｉ）の具体例としては、エチレンオキシド／ジエチレングリコールメチルグリシジルエーテル／アリルグリシジルエーテル三元共重合体、エチレンオキシド／ジエチレングリコールメチルグリシジルエーテル／メタクリル酸グリシジル三元共重合体、エチレンオキシド／ジエチレングリコールメチルグリシジルエーテル／アクリル酸グリシジル三元共重合体等が挙げられる。 Specific examples of the polyether (i) having an ethylene oxide unit in the side chain include ethylene oxide/diethylene glycol methyl glycidyl ether/allyl glycidyl ether terpolymer, ethylene oxide/diethylene glycol methyl glycidyl ether/glycidyl methacrylate terpolymer, Examples include ethylene oxide/diethylene glycol methyl glycidyl ether/glycidyl acrylate terpolymer.
側鎖にエチレンオキシド単位を有するポリエーテル（ｉ）の重量平均分子量は特に限定されないが、１万～３００万であってよく、５万～２５０万であることがより好ましく、１０万～２００万であることが特に好ましい。重量平均分子量はゲルパーミエーションクロマトグラフィー（ＧＰＣ）で、溶媒としてジメチルホルムアミド（ＤＭＦ）を使用して、標準ポリスチレン換算により算出する。 The weight average molecular weight of the polyether (i) having ethylene oxide units in the side chain is not particularly limited, but may be from 10,000 to 3 million, more preferably from 50,000 to 2,500,000, and from 100,000 to 2,000,000. It is particularly preferable that there be. The weight average molecular weight is calculated by gel permeation chromatography (GPC) using dimethylformamide (DMF) as a solvent in terms of standard polystyrene.
イオン伝導性ポリマー材料に含まれるイオン伝導性ポリマーの含有量としては、導電性ポリマー材料全体を１００質量部として、好ましくは５～９５質量部、より好ましくは１０～９０質量部である。 The content of the ion conductive polymer contained in the ion conductive polymer material is preferably 5 to 95 parts by mass, more preferably 10 to 90 parts by mass, based on 100 parts by mass of the entire conductive polymer material.
イオン伝導性ポリマーは、架橋体を含んでいてもよい。 The ion conductive polymer may include a crosslinked material.
リチウム塩化合物としては、リチウムイオン電池に一般的に利用されているような、広い電位窓を有するリチウム塩化合物が好適である。リチウム塩化合物としては、例えば、ＬｉＢＦ4、ＬｉＰＦ6、ＬｉＣｌＯ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2（ＬｉＴＦＳＩ），ＬｉＮ（ＳＦＯ2）2（ＬｉＦＳＩ）、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、ＬｉＮ［ＣＦ3ＳＣ（Ｃ2Ｆ5ＳＯ2）3］2などを挙げられるが、これらに限定されない。これらは、単独で用いても、２種類以上を混合して用いても良い。As the lithium salt compound, a lithium salt compound having a wide potential window, such as those commonly used in lithium ion batteries, is suitable. Examples of lithium salt compounds include LiBF 4 , LiPF 6 , LiClO 4 , LiCF 3 SO 3 , LiN(CF 3 SO 2 ) 2 (LiTFSI), LiN(SFO 2 ) 2 (LiFSI), LiN(C 2 F 5 Examples include, but are not limited to, SO 2 ) 2 , LiN[CF 3 SC(C 2 F 5 SO 2 ) 3 ] 2 . These may be used alone or in combination of two or more.
イオン伝導性ポリマー材料に含まれるリチウム塩化物の含有量としては、リチウム塩化合物のモル数／イオン伝導性ポリマーのエーテル酸素原子の総モル数の値が０．０００１～５が好ましく、更に好ましくは０．００１～０．５の範囲がよい。 The content of lithium chloride contained in the ion conductive polymer material is preferably such that the value of the number of moles of the lithium salt compound/the total number of moles of ether oxygen atoms in the ion conductive polymer is 0.0001 to 5, more preferably A range of 0.001 to 0.5 is preferable.
また、イオン伝導性ポリマー材料には、常温溶融塩が含まれていてもよい。常温溶融塩は、常温において少なくとも一部が液状を呈する塩をいい、常温とは電源が通常作動すると想定される温度範囲をいう。電源が通常作動すると想定される温度範囲とは、上限が１２０℃程度、場合によっては６０℃程度であり、下限は－４０℃程度、場合によっては－２０℃程度である。 The ion-conductive polymer material may also contain a room temperature molten salt. Room temperature molten salt refers to salt that is at least partially liquid at room temperature, and room temperature refers to the temperature range in which the power source is expected to normally operate. The temperature range in which the power supply is expected to normally operate has an upper limit of about 120°C, in some cases about 60°C, and a lower limit of about -40°C, in some cases about -20°C.
常温溶融塩はイオン液体とも呼ばれており、ピリジン系、脂肪族アミン系、脂環族アミン系の４級アンモニウム有機物カチオンが知られている。４級アンモニウム有機物カチオンとしては、ジアルキルイミダゾリウム、トリアルキルイミダゾリウム、などのイミダゾリウムイオン、テトラアルキルアンモニウムイオン、アルキルピリジニウムイオン、ピラゾリウムイオン、ピロリジニウムイオン、ピペリジニウムイオンなどが挙げられる。特に、イミダゾリウムカチオンが好ましい。 Room temperature molten salts are also called ionic liquids, and pyridine-based, aliphatic amine-based, and alicyclic amine-based quaternary ammonium organic cations are known. Examples of the quaternary ammonium organic cation include imidazolium ions such as dialkylimidazolium and trialkylimidazolium, tetraalkylammonium ions, alkylpyridinium ions, pyrazolium ions, pyrrolidinium ions, and piperidinium ions. In particular, imidazolium cations are preferred.
なお、テトラアルキルアンモニウムイオンとしては、トリメチルエチルアンモニウムイオン、トリメチルエチルアンモニウムイオン、トリメチルプロピルアンモニウムイオン、トリメチルヘキシルアンモニウムイオン、テトラペンチルアンモニウムイオン、トリエチルメチルアンモニウムイオンなどが挙げられるが、これらに限定されるものではない。 Examples of the tetraalkylammonium ion include, but are not limited to, trimethylethylammonium ion, trimethylethylammonium ion, trimethylpropylammonium ion, trimethylhexylammonium ion, tetrapentylammonium ion, triethylmethylammonium ion, etc. isn't it.
また、アルキルピリジウムイオンとしては、Ｎ－メチルピリジウムイオン、Ｎ－エチルピリジニウムイオン、Ｎ－プロピルピリジニウムイオン、Ｎ－ブチルピリジニウムイオン、１－エチル－２メチルピリジニウムイオン、１－ブチル－４－メチルピリジニウムイオン、１－ブチル－２，４ジメチルピリジニウムイオンなどが挙げられるが、これらに限定されるものではない。 In addition, as the alkylpyridium ion, N-methylpyridium ion, N-ethylpyridinium ion, N-propylpyridinium ion, N-butylpyridinium ion, 1-ethyl-2methylpyridinium ion, 1-butyl-4-methyl Examples include, but are not limited to, pyridinium ion, 1-butyl-2,4 dimethylpyridinium ion, and the like.
イミダゾリウムカチオンとしては、１，３－ジメチルイミダゾリウムイオン、１－エチル－３－メチルイミダゾリウムイオン、１－メチル－３－エチルイミダゾリウムイオン、１－メチル－３－ブチルイミダゾリウムイオン、１－ブチル－３－メチルイミダゾリウムイオン、１，２，３－トリメチルイミダゾリウムイオン、１，２－ジメチル－３－エチルイミダゾリウムイオン、１，２－ジメチル－３－プロピルイミダゾリウムイオン、１－ブチル－２，３－ジメチルイミダゾリウムイオンなどが挙げられるが、これらに限定されるものではない。 Examples of imidazolium cations include 1,3-dimethylimidazolium ion, 1-ethyl-3-methylimidazolium ion, 1-methyl-3-ethylimidazolium ion, 1-methyl-3-butylimidazolium ion, 1- Butyl-3-methylimidazolium ion, 1,2,3-trimethylimidazolium ion, 1,2-dimethyl-3-ethylimidazolium ion, 1,2-dimethyl-3-propylimidazolium ion, 1-butyl- Examples include, but are not limited to, 2,3-dimethylimidazolium ion.
なお、これらのカチオンを有する常温溶融塩は、単独で用いてもよく、または２種以上を混合して用いても良い。 Note that the room temperature molten salts having these cations may be used alone or in combination of two or more.
イオン伝導性ポリマー材料に常温溶融塩が含まれる場合、その含有量としては、イオン伝導性ポリマー１００質量部に対して、好ましくは１０～１０００質量部、より好ましくは２０～５００質量部である。 When the ion conductive polymer material contains a room temperature molten salt, its content is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, based on 100 parts by mass of the ion conductive polymer.
イオン伝導性ポリマー材料は、可塑剤などを含んでいてもよい。可塑剤としては、特に限定されないが、ジシアノ化合物、分岐型エーテル化合物が好ましい。可塑剤を添加する場合は、イオン伝導性ポリマーを架橋することが好ましい。この架橋は、化学架橋であり、イオン伝導性ポリマー材料からの可塑剤の流出を抑制できる。 The ionically conductive polymeric material may also include plasticizers and the like. The plasticizer is not particularly limited, but dicyano compounds and branched ether compounds are preferred. When adding a plasticizer, it is preferable to crosslink the ion conductive polymer. This crosslinking is a chemical crosslinking and can suppress the outflow of the plasticizer from the ion conductive polymer material.
ジシアノ化合物としてはスクシノニトリル、グルタロニトリル、アジポニトリル、１，５－ジシアノペンタン、１，６－ジシアノヘキサン、１，７－ジシアノヘプタン、１，８－ジシアノオクタン等が挙げられる。分岐型エーテル化合物の例として、下記の多分岐型エーテル化合物などが挙げられる。 Examples of the dicyano compound include succinonitrile, glutaronitrile, adiponitrile, 1,5-dicyanopentane, 1,6-dicyanohexane, 1,7-dicyanoheptane, and 1,8-dicyanooctane. Examples of branched ether compounds include the following hyperbranched ether compounds.
イオン伝導性ポリマー材料に可塑剤が含まれる場合、可塑剤の含有量としては、イオン伝導性ポリマー１００質量部に対して、好ましくは１０～１０００質量部、より好ましくは２０～５００質量部である。 When the ion conductive polymer material contains a plasticizer, the content of the plasticizer is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, based on 100 parts by mass of the ion conductive polymer. .
イオン伝導性ポリマー材料の形成には、熱反応開始剤、光反応開始剤、架橋助剤を用いてもよい。 Thermal initiators, photoinitiators, and crosslinking coagents may be used to form the ionically conductive polymeric material.
熱反応開始剤としては、有機過酸化物、アゾ化合物等から選ばれるラジカル開始剤が用いられる。有機過酸化物としては、ケトンパーオキシド、パーオキシケタール、ハイドロパーオキシド、ジアルキルパーオキシド、ジアシルパーオキシド、パーオキシエステル等、通常架橋用途に使用されているものが用いられ、アゾ化合物としてはアゾニトリル化合物、アゾアミド化合物、アゾアミジン化合物等、通常架橋用途に使用されているものが用いられる。ラジカル開始剤の添加量は種類により異なるが、通常、イオン伝導性ポリマーを１００質量部として０．１～１０質量部の範囲内である。 As the thermal reaction initiator, a radical initiator selected from organic peroxides, azo compounds, etc. is used. As organic peroxides, those commonly used for crosslinking purposes are used, such as ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, and peroxy ester, and as an azo compound, azonitrile is used. Compounds, azoamide compounds, azoamidine compounds, etc., which are commonly used for crosslinking purposes, are used. The amount of the radical initiator added varies depending on the type, but is usually within the range of 0.1 to 10 parts by weight based on 100 parts by weight of the ion-conductive polymer.
光反応開始剤としては、アルキルフェノン系、ベンゾフェノン系、アシルフォスフィンオキサイド系、チタノセン類、トリアジン類、ビスイミダゾール類、オキシムエステル類などラジカル開始剤が用いられる。これらのラジカル重合開始剤の添加量は種類により異なるが、通常、イオン伝導性ポリマーを１００質量部として０．０１～５．０質量部の範囲内である。 As the photoreaction initiator, radical initiators such as alkylphenones, benzophenones, acylphosphine oxides, titanocenes, triazines, bisimidazoles, and oxime esters are used. The amount of these radical polymerization initiators added varies depending on the type, but is usually within the range of 0.01 to 5.0 parts by weight, based on 100 parts by weight of the ion-conductive polymer.
架橋助剤としては、エチレングリコールジアクリレート、エチレングリコールジメタクリレート、オリゴエチレングリコールジアクリレート、オリゴエチレングリコールジメタクリレート、トリメチロールプロパントリアクリレート、アリルメタクリレート、アリルアクリレート、ジアリルマレート、トリアリルイソシアヌレート、マレイミド、フェニルマレイミド、無水マレイン酸等を任意に用いることができる。 Examples of crosslinking aids include ethylene glycol diacrylate, ethylene glycol dimethacrylate, oligoethylene glycol diacrylate, oligoethylene glycol dimethacrylate, trimethylolpropane triacrylate, allyl methacrylate, allyl acrylate, diallyl maleate, triallyl isocyanurate, and maleimide. , phenylmaleimide, maleic anhydride, etc. can be optionally used.
イオン伝導性ポリマー材料には、後述する方法のため、側鎖にエチレンオキシド単位を有するイオン伝導性ポリマー、リチウム塩化合物を溶解させる溶媒を含有してもよく、アセトニトリル、トルエン、テトラヒドロフラン（ＴＨＦ）、ジオキサン、ジメチルスルホキシド（ＤＭＳＯ）、水等の極性の高い溶媒を用いることができる。 For the method described below, the ion conductive polymer material may contain an ion conductive polymer having an ethylene oxide unit in its side chain and a solvent for dissolving the lithium salt compound, such as acetonitrile, toluene, tetrahydrofuran (THF), dioxane, etc. , dimethyl sulfoxide (DMSO), water, and other highly polar solvents can be used.
電極材料間の空隙にイオン伝導性ポリマー材料を含ませる方法としては、前述の通り、特に限定されないが、側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーおよびリチウム塩化合物が溶媒によって完全に溶解された溶液（組成物）を、活物質を含む層（より具体的には電極材料層前駆体を構成する電極材料の空隙）に含浸させることにより行うことができる。含浸する条件は、できる限り、低い温度（好ましくは、室温以下）で、溶媒をゆっくり蒸発させながら、空隙にイオン伝導性ポリマーおよびリチウム塩化合物を含有させる。また、電極材料層が厚膜の場合には、減圧下で行うこともできる。 As mentioned above, the method for including the ion-conductive polymer material in the gap between the electrode materials is not particularly limited, but the ion-conductive polymer having an ethylene oxide unit in the side chain and the lithium salt compound are completely dissolved in a solvent. This can be carried out by impregnating the layer containing the active material (more specifically, the voids of the electrode material constituting the electrode material layer precursor) with a solution (composition). The impregnation conditions are such that the ion conductive polymer and the lithium salt compound are contained in the voids while slowly evaporating the solvent at a temperature as low as possible (preferably below room temperature). In addition, when the electrode material layer is a thick film, it can also be carried out under reduced pressure.
側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーを架橋する場合には、イオン伝導性ポリマー材料を含浸させた層を、加熱又は活性エネルギー線照射（紫外線照射など）によって架橋させることができる。 When crosslinking an ion conductive polymer having ethylene oxide units in its side chains, the layer impregnated with the ion conductive polymer material can be crosslinked by heating or irradiation with active energy rays (such as ultraviolet irradiation).
無機固体電解質二次電池
本発明の無機固体電解質二次電池は、本発明の無機固体電解質二次電池用電極を含む。より具体的には、正極及び負極（少なくとも一方は、本発明の電極によって構成されている）と、正極と負極の間に配置された無機固体電解質とを備える。なお、正極及び負極のうち、本発明の電極を用いなかった電極には、固体電解質二次電池に用いられる公知の電極を用いることができる。本発明の無機固体電解質二次電池用電極については、前述の通りである。 Inorganic Solid Electrolyte Secondary Battery The inorganic solid electrolyte secondary battery of the present invention includes the electrode for an inorganic solid electrolyte secondary battery of the present invention. More specifically, it includes a positive electrode and a negative electrode (at least one of which is constituted by the electrode of the present invention), and an inorganic solid electrolyte disposed between the positive electrode and the negative electrode. Note that among the positive electrode and the negative electrode, a known electrode used in solid electrolyte secondary batteries can be used as the electrode that does not use the electrode of the present invention. The electrode for an inorganic solid electrolyte secondary battery of the present invention is as described above.
本発明の無機固体電解質二次電池に用いられる本発明の電極は、活物質に加えて、さらに、前記のイオン伝導性ポリマー材料が、電極材料層に含まれていることにより、電極材料層に含まれる活物質などの電極材料（具体的には、活物質粒子、バインダー、導電助剤、増粘剤、無機固体電解質など）の空隙がイオン伝導性ポリマー材料によって埋められ、電極材料層の内部の界面抵抗が効果的に低下し、結果として、優れた充放電特性が発揮されるものと考えられる。また、本発明の固体電解質二次電池は、高温環境（例えば１００℃以上の高温環境）で使用されることもあるが、本発明の電極を用いることにより、高温環境において優れた充放電特性が発揮される。 In the electrode of the present invention used in the inorganic solid electrolyte secondary battery of the present invention, in addition to the active material, the ion-conductive polymer material is further included in the electrode material layer. The voids in the electrode material such as the active material (specifically, active material particles, binder, conductive aid, thickener, inorganic solid electrolyte, etc.) are filled with the ion conductive polymer material, and the inside of the electrode material layer It is thought that the interfacial resistance of the battery is effectively reduced, and as a result, excellent charge-discharge characteristics are exhibited. Furthermore, the solid electrolyte secondary battery of the present invention may be used in a high-temperature environment (for example, a high-temperature environment of 100°C or higher), and by using the electrode of the present invention, excellent charge-discharge characteristics can be achieved in a high-temperature environment. Demonstrated.
無機固体電解質としては、酸化物系固体電解質、及び硫化物系固体電解質を例示することができる。無機固体電解質は、一般に、電解質を構成する無機固体粒子の集合体である。 Examples of the inorganic solid electrolyte include oxide-based solid electrolytes and sulfide-based solid electrolytes. An inorganic solid electrolyte is generally an aggregate of inorganic solid particles that constitute the electrolyte.
酸化物系固体電解質は、酸素を含有し、かつ、周期律表第１族または第２族に属する金属のイオン伝導性を有し、かつ、電子絶縁性を有するものであれば特に限定されるものではない。 The oxide-based solid electrolyte is particularly limited as long as it contains oxygen, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and has electronic insulating properties. It's not a thing.
酸化物系固体電解質を構成する具体的な化合物としては、ＬｉxＬａyＴｉＯ3〔ｘ＝０．３～０．７、ｙ＝０．３～０．７〕（ＬＬＴ）、ＬｉxＬａyＺｒzＭmＯn（ＭはＡｌ，Ｍｇ，Ｃａ，Ｓｒ，Ｖ，Ｎｂ，Ｔａ，Ｔｉ，Ｇｅ，Ｉｎ，Ｓｎの少なくとも１種以上の元素でありｘは５≦ｘ≦１０を満たし、ｙは１≦ｙ≦４を満たし、ｚは１≦ｚ≦４を満たし、ｍは０≦ｍ≦２を満たし、ｎは５≦ｎ≦２０を満たす。）ＬｉxＢyＭzＯn（式中ＭはＣ，Ｓ，Ａｌ，Ｓｉ，Ｇａ，Ｇｅ，Ｉｎ，Ｓｎの少なくとも１種以上の元素でありｘは０≦ｘ≦５を満たし、ｙは０≦ｙ≦１を満たし、ｚは０≦ｚ≦１を満たし、ｎは０≦ｎ≦６を満たす。）、Ｌｉx（Ａｌ，Ｇａ）y（Ｔｉ，Ｇｅ）zＳｉaＰmＯn（ただし、１≦ｘ≦３、０≦ｙ≦１、０≦ｚ≦２、０≦ａ≦１、１≦ｍ≦７、３≦ｎ≦１３）、Ｌｉ(3-2x)ＭxＤＯ（ｘは０以上０．１以下の数を表し、Ｍは２価の金属原子を表す。Ｄはハロゲン原子または２種以上のハロゲン原子の組み合わせを表す。）、ＬｉxＳｉyＯz（１≦ｘ≦５、０＜ｙ≦３、１≦ｚ≦１０）、ＬｉxＳyＯz（１≦ｘ≦３、０＜ｙ≦２、１≦ｚ≦１０）、Ｌｉ3ＢＯ3－Ｌｉ2ＳＯ4、Ｌｉ2Ｏ－Ｂ2Ｏ3－Ｐ2Ｏ5、Ｌｉ2Ｏ－ＳｉＯ2、Ｌｉ6ＢａＬａ2Ｔａ2Ｏ12、Ｌｉ3ＰＯ(4-3/2w)Ｎw（ｗはｗ＜１）、ＬＩＳＩＣＯＮ（Ｌｉｔｈｉｕｍ ｓｕｐｅｒ ｉｏｎｉｃ ｃｏｎｄｕｃｔｏｒ）型結晶構造を有するＬｉ3.5Ｚｎ0.25ＧｅＯ4、ペロブスカイト型結晶構造を有するＬａ0.55Ｌｉ0.35ＴｉＯ3、ＮＡＳＩＣＯＮ（Ｎａｔｒｉｕｍ ｓｕｐｅｒ ｉｏｎｉｃ ｃｏｎｄｕｃｔｏｒ）型結晶構造を有するＬｉＴｉ2Ｐ3Ｏ12、Ｌｉ(1+x+y)（Ａｌ，Ｇａ）x（Ｔｉ，Ｇｅ）(2-x)ＳｉyＰ(3-y)Ｏ12（ただし、０≦ｘ≦１、０≦ｙ≦１）、ガーネット型結晶構造を有するＬｉ7Ｌａ3Ｚｒ2Ｏ１2等が挙げられる。またＬｉ、Ｐ及びＯを含むリン化合物も望ましい。例えばリン酸リチウム（Ｌｉ3ＰＯ4）、リン酸リチウムの酸素の一部を窒素で置換したＬｉＰＯＮ、ＬｉＰＯＤ（Ｄは、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｒ、Ｎｂ、Ｍｏ、Ｒｕ、Ａｇ、Ｔａ、Ｗ、Ｐｔ、Ａｕ等から選ばれた少なくとも１種）等が挙げられる。また、ＬｉＡＯＮ（Ａは、Ｓｉ、Ｂ、Ｇｅ、Ａｌ、Ｃ、Ｇａ等から選ばれた少なくとも１種）等も好ましく用いることができる。Specific compounds constituting the oxide solid electrolyte include Li x La y TiO 3 [x=0.3-0.7, y=0.3-0.7] (LLT), Li x La y Zr z M m O n (M is at least one element of Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, Sn, x satisfies 5≦x≦10, y satisfies 1≦y≦4, z satisfies 1≦z≦4, m satisfies 0≦m≦2, and n satisfies 5≦n≦20.) Li x B y M z O n (Formula Medium M is at least one element of C, S, Al, Si, Ga, Ge, In, Sn, x satisfies 0≦x≦5, y satisfies 0≦y≦1, and z is 0 ≦z≦1, and n satisfies 0≦n≦6.), Li x (Al, Ga) y (Ti, Ge) z Sia P m O n (However, 1≦x≦3, 0≦ y≦1, 0≦z≦2, 0≦a≦1, 1≦m≦7, 3≦n≦13), Li (3-2x) M x DO (x is a number between 0 and 0.1) (M represents a divalent metal atom. D represents a halogen atom or a combination of two or more halogen atoms.), Li x Si y O z (1≦x≦5, 0<y≦3, 1 ≦z≦10), Li x S y O z (1≦x≦3, 0<y≦2, 1≦z≦10), Li 3 BO 3 -Li 2 SO 4 , Li 2 O-B 2 O 3 -P 2 O 5 , Li 2 O-SiO 2 , Li 6 BaLa 2 Ta 2 O 12 , Li 3 PO (4-3/2w) N w (w<1), LISICON (Lithium super ionic conductor) type Li 3.5 Zn 0.25 GeO 4 with a crystal structure, La 0.55 Li 0.35 TiO 3 with a perovskite crystal structure, LiTi 2 P 3 O 12 with a NASICON (Natrium super ionic conductor) crystal structure, Li ( 1+x+y ) ( Al , Ga ) 7 La 3 Zr 2 O1 2 and the like. Also desirable are phosphorus compounds containing Li, P and O. For example, lithium phosphate (Li 3 PO 4 ), LiPON in which part of the oxygen in lithium phosphate is replaced with nitrogen, LiPOD (D is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb , Mo, Ru, Ag, Ta, W, Pt, Au, etc.). Furthermore, LiAON (A is at least one selected from Si, B, Ge, Al, C, Ga, etc.) can also be preferably used.
その中でも、ＬｉxＬａyＴｉＯ3〔ｘ＝０．３～０．７、ｙ＝０．３～０．７〕（ＬＬＴ）、ＬｉxＬａyＺｒzＭmＯn（ＭはＡｌ，Ｍｇ，Ｃａ，Ｓｒ，Ｖ，Ｎｂ，Ｔａ，Ｔｉ，Ｇｅ，Ｉｎ，Ｓｎの少なくとも１種以上の元素でありｘは５≦ｘ≦１０を満たし、ｙは１≦ｙ≦４を満たし、ｚは１≦ｚ≦４を満たし、ｍは０≦ｍ≦２を満たし、ｎは５≦ｎ≦２０を満たす。）、Ｌｉ7Ｌａ3Ｚｒ2Ｏ12（ＬＬＺ）、Ｌｉ3ＢＯ3、Ｌｉ3ＢＯ3－Ｌｉ2ＳＯ4、Ｌｉ3ＢＯ3－Ｌｉ2ＣＯ3、Ｌｉx（Ａｌ，Ｇａ）y（Ｔｉ，Ｇｅ）zＳｉaＰmＯn（ただし、１≦ｘ≦３、０≦ｙ≦１、０≦ｚ≦２、０≦ａ≦１、１≦ｍ≦７、３≦ｎ≦１３）が好ましい。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。Among them, Li x La y TiO 3 [x=0.3-0.7, y=0.3-0.7] (LLT), Li x La y Zr z M m O n (M is Al, Mg , Ca, Sr, V, Nb, Ta, Ti, Ge, In, and Sn, x satisfies 5≦x≦10, y satisfies 1≦y≦4, and z satisfies 1 ≦z≦4, m satisfies 0≦m≦2, and n satisfies 5≦n≦20.), Li 7 La 3 Zr 2 O 12 (LLZ), Li 3 BO 3 , Li 3 BO 3 -Li 2 SO 4 , Li 3 BO 3 -Li 2 CO 3 , Li x (Al, Ga) y (Ti, Ge) z Si a P m O n (1≦x≦3, 0≦y≦1 , 0≦z≦2, 0≦a≦1, 1≦m≦7, 3≦n≦13). These may be used alone or in combination of two or more.
硫化物系固体電解質は、硫黄を含有し、かつ、周期律表第１族または第２族に属する金属のイオン伝導性を有し、かつ、電子絶縁性を有するものであれば特に限定されるものではない。例えば下記式で示される組成を満たすリチウムイオン伝導性無機固体電解質が挙げられる。 The sulfide-based solid electrolyte is particularly limited as long as it contains sulfur, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and has electronic insulating properties. It's not a thing. For example, a lithium ion conductive inorganic solid electrolyte satisfying the composition shown by the following formula may be used.
ＬｉaＭbＰcＳdＡe Li a M b P c S d A e
式中、Ｍは、Ｂ、Ｚｎ、Ｓｎ、Ｓｉ、Ｃｕ、Ｇａ、Ｓｂ、Ａｌ及びＧｅから選択される元素を示す。なかでも、Ｂ、Ｓｎ、Ｓｉ、Ａｌ、Ｇｅが好ましく、Ｓｎ、Ａｌ、Ｇｅがより好ましい。Ａは、Ｉ、Ｂｒ、Ｃｌ、Ｆを示し、Ｉ、Ｂｒが好ましく、Ｉが特に好ましい。ａ～ｅは各元素の組成比を示し、ａ：ｂ：ｃ：ｄ：ｅは１～１２：０～１：１：２～１２：０～５を満たす。ａはさらに、１～９が好ましく、１．５～４がより好ましい。ｂは０～０．５が好ましい。ｄはさらに、３～７が好ましく、３．２５～４．５がより好ましい。ｅはさらに、０～３が好ましく、０～２がより好ましい。 In the formula, M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al and Ge. Among these, B, Sn, Si, Al, and Ge are preferred, and Sn, Al, and Ge are more preferred. A represents I, Br, Cl, or F, with I and Br being preferred, and I being particularly preferred. a to e indicate the composition ratio of each element, and a:b:c:d:e satisfies 1 to 12:0 to 1:1:2 to 12:0 to 5. Further, a is preferably 1 to 9, more preferably 1.5 to 4. b is preferably 0 to 0.5. d is further preferably 3 to 7, more preferably 3.25 to 4.5. Further, e is preferably 0 to 3, more preferably 0 to 2.
式において、Ｌｉ、Ｍ、Ｐ、Ｓ及びＡの組成比は、好ましくはｂ、ｅが０であり、より好ましくはｂ＝０、ｅ＝０で且つａ、ｃ及びｄの比（ａ：ｃ：ｄ）がａ：ｃ：ｄ＝１～９：１：３～７であり、さらに好ましくはｂ＝０、ｅ＝０で且つａ：ｃ：ｄ＝１．５～４：１：３．２５～４．５である。 In the formula, the composition ratio of Li, M, P, S and A is such that preferably b and e are 0, more preferably b=0 and e=0, and the ratio of a, c and d (a:c :d) is a:c:d=1 to 9:1:3 to 7, more preferably b=0, e=0 and a:c:d=1.5 to 4:1:3. It is 25 to 4.5.
無機固体電解質が粒子状である場合、その粒子径としては、例えば０．０１～１００μｍ、好ましくは０．１～２０μｍが挙げられる。 When the inorganic solid electrolyte is in the form of particles, the particle size is, for example, 0.01 to 100 μm, preferably 0.1 to 20 μm.
本発明の固体電解質二次電池においては、正極と無機固体電解質との間、及び負極と前記無機固体電解質との間の少なくとも一方に、リチウム塩化合物を含む側鎖にエチレンオキシド単位を有するイオン伝導性ポリマー材料の架橋フィルムを配置してもよい。イオン伝導性ポリマー材料の架橋フィルムは、リチウム塩化合物とイオン伝導性ポリマーを含む組成物の架橋フィルムである。当該架橋フィルムを配置することにより、電極や無機固体電解質の界面抵抗をより一層低下させることができる。 In the solid electrolyte secondary battery of the present invention, at least one of between the positive electrode and the inorganic solid electrolyte and between the negative electrode and the inorganic solid electrolyte has an ionic conductor having an ethylene oxide unit in a side chain containing a lithium salt compound. A crosslinked film of polymeric material may also be provided. A crosslinked film of ionically conductive polymeric material is a crosslinked film of a composition comprising a lithium salt compound and an ionically conductive polymer. By arranging the crosslinked film, the interfacial resistance of the electrode and the inorganic solid electrolyte can be further reduced.
架橋フィルムは、少なくとも、リチウム塩化合物と、側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーとを含む組成物を架橋することにより形成される。すなわち、架橋フィルムは、リチウム塩化合物とイオン伝導性ポリマーを含む組成物の架橋フィルムである。リチウム塩化合物及びイオン伝導性ポリマーについては、前述の通りである。 The crosslinked film is formed by crosslinking a composition containing at least a lithium salt compound and an ion conductive polymer having an ethylene oxide unit in a side chain. That is, the crosslinked film is a crosslinked film of a composition containing a lithium salt compound and an ion conductive polymer. The lithium salt compound and the ion conductive polymer are as described above.
架橋フィルムに含まれるイオン伝導性ポリマーの含有量としては、架橋フィルム全体を１００質量部として、好ましくは１０～９０質量部、より好ましくは２０～８０質量部である。 The content of the ion conductive polymer contained in the crosslinked film is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the entire crosslinked film.
架橋フィルムに含まれるリチウム塩化物の含有量リチウム塩化合物のモル数／イオン伝導性ポリマーのエーテル酸素原子の総モル数の値が０．０００１～５が好ましく、更に好ましくは０．００１～０．５の範囲がよい。 The value of lithium chloride content in the crosslinked film, number of moles of lithium salt compound/total number of moles of ether oxygen atoms in the ion-conductive polymer is preferably 0.0001 to 5, more preferably 0.001 to 0. A range of 5 is good.
また、架橋フィルムには、常温溶融塩が含まれていてもよい。常温溶融塩については、前述の通りである。 Further, the crosslinked film may contain a room temperature molten salt. The room temperature molten salt is as described above.
架橋フィルムに常温溶融塩が含まれる場合、その含有量としては、イオン伝導性ポリマー１００質量部に対して、好ましくは１０～１０００質量部、より好ましくは２０～５００質量部である。 When the crosslinked film contains a salt molten at room temperature, the content thereof is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, based on 100 parts by mass of the ion-conductive polymer.
架橋フィルムは、可塑剤などを含んでいてもよい。可塑剤については、前述の通りである。 The crosslinked film may contain a plasticizer and the like. The plasticizer is as described above.
架橋フィルムに可塑剤が含まれる場合、可塑剤の含有量としては、イオン伝導性ポリマー１００質量部に対して、好ましくは１０～１０００質量部、より好ましくは２０～５００質量部である。 When the crosslinked film contains a plasticizer, the content of the plasticizer is preferably 10 to 1000 parts by weight, more preferably 20 to 500 parts by weight, based on 100 parts by weight of the ion-conductive polymer.
リチウム塩化合物とイオン伝導性ポリマーを含む組成物に反応開始剤や架橋助剤を配合して、架橋フィルムを形成してもよい。反応開始剤としては、熱反応開始剤、光反応開始剤が挙げられる。 A crosslinked film may be formed by adding a reaction initiator and a crosslinking aid to a composition containing a lithium salt compound and an ion conductive polymer. Examples of the reaction initiator include thermal reaction initiators and photoreaction initiators.
熱反応開始剤、光反応開始剤、及び架橋助剤については、前述の通りである。 The thermal reaction initiator, photoreaction initiator, and crosslinking aid are as described above.
リチウム塩化合物とイオン伝導性ポリマーを含む組成物には、有機溶媒を配合してもよく、有機溶媒としては、トルエン、キシレン、ベンゼン、アセトニトリル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ＴＨＦ（テトラヒドロフラン）が挙げられる。 An organic solvent may be added to the composition containing the lithium salt compound and the ion conductive polymer. Examples of the organic solvent include toluene, xylene, benzene, acetonitrile, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, THF ( (tetrahydrofuran).
架橋フィルムの作製方法は、例えば、イオン伝導性ポリマー、必要に応じて反応開始剤、及びリチウム塩化合物を有機溶媒に混合して溶解して組成物を形成し、基材（例えばＰＥＴフィルムやテフロン（登録商標）板など）上に組成物をキャスティングし、溶媒を除去後、加熱又は紫外線などの活性エネルギー線照射によって架橋フィルムを作製する方法が挙げられる。また、直接、無機固体電解質の表面に当該組成物をキャスティングして、架橋フィルムを作製することもできる。 A method for producing a crosslinked film includes, for example, mixing an ion-conductive polymer, an optional reaction initiator, and a lithium salt compound in an organic solvent and dissolving it to form a composition, (registered trademark) board, etc.), and after removing the solvent, a crosslinked film is produced by heating or irradiating active energy rays such as ultraviolet rays. Alternatively, a crosslinked film can also be produced by directly casting the composition on the surface of an inorganic solid electrolyte.
架橋フィルムの膜厚は、好ましくは０．１μｍ～２００μｍ、より好ましくは０．５μｍ～１００μｍの範囲内である。 The thickness of the crosslinked film is preferably in the range of 0.1 μm to 200 μm, more preferably in the range of 0.5 μm to 100 μm.
本発明の無機固体電解質二次電池の積層構成としては、例えば、以下の構成が挙げられる。
正極、無機固体電解質、及び負極が順に積層された積層構成；
正極、架橋フィルム、無機固体電解質、架橋フィルム、及び負極が順に積層された積層構成；
正極、架橋フィルム、無機固体電解質、及び負極が順に積層された積層構成；
正極、無機固体電解質、架橋フィルム、及び負極が順に積層された積層構成。Examples of the laminated structure of the inorganic solid electrolyte secondary battery of the present invention include the following structure.
A laminated structure in which a positive electrode, an inorganic solid electrolyte, and a negative electrode are laminated in order;
A laminated structure in which a positive electrode, a crosslinked film, an inorganic solid electrolyte, a crosslinked film, and a negative electrode are laminated in this order;
A laminated structure in which a positive electrode, a crosslinked film, an inorganic solid electrolyte, and a negative electrode are laminated in this order;
A laminated structure in which a positive electrode, an inorganic solid electrolyte, a crosslinked film, and a negative electrode are laminated in this order.
本発明の無機固体電解質二次電池においては、無機固体電解質と前述の架橋フィルムとが接触していることが好ましい。無機固体電解質は、一般に、電解質を構成する無機固体粒子の集合体により形成されており、粒子間には空隙が存在している。架橋フィルムは、リチウム塩化合物を含むイオン伝導性ポリマーを含む組成物の架橋体であることから、イオン伝導性を有しており、かつ、無機材料と比較して高い柔軟性を有している。従って、当該架橋フィルムは、無機固体電解質との接触面積が大きくなり、その結果、無機固体電解質の界面抵抗が効果的に低下し、本発明の無機固体電解質二次電池は優れた充放電特性を発揮するものと考えられる。なお、電極材料層に含まれる活物質粒子なども空隙を形成することから、本発明の無機固体電解質二次電池においては、架橋フィルムが電極の電極材料層と接触していることも好ましいし、架橋フィルムが電極材料層と無機固体電解質の両方と接触していることも好ましい。 In the inorganic solid electrolyte secondary battery of the present invention, it is preferable that the inorganic solid electrolyte and the above-mentioned crosslinked film are in contact with each other. An inorganic solid electrolyte is generally formed of an aggregate of inorganic solid particles constituting the electrolyte, and voids exist between the particles. Since the crosslinked film is a crosslinked product of a composition containing an ion conductive polymer containing a lithium salt compound, it has ion conductivity and has high flexibility compared to inorganic materials. . Therefore, the crosslinked film has a large contact area with the inorganic solid electrolyte, and as a result, the interfacial resistance of the inorganic solid electrolyte is effectively reduced, and the inorganic solid electrolyte secondary battery of the present invention has excellent charge and discharge characteristics. This is considered to be effective. In addition, since the active material particles contained in the electrode material layer also form voids, in the inorganic solid electrolyte secondary battery of the present invention, it is also preferable that the crosslinked film is in contact with the electrode material layer of the electrode, It is also preferred that the crosslinked film is in contact with both the electrode material layer and the inorganic solid electrolyte.
固体電解質二次電池の製造方法
本発明の固体電解質二次電池の製造方法は特に限定されず、少なくとも、正極、負極、及び無機固体電解質で構成され、公知の方法にて製造される。例えば、コイン型のリチウムイオン電池の場合、正極、無機固体電解質、負極を配置して、外装缶に挿入する。その後、封口体とタブ溶接などで接合して、封口体を封入し、カシめることで蓄電池が得られる。電池の形状は限定されないが、例としてはコイン型、円筒型、シート型などがあげられ、２個以上の電池を積層した構造でもよい。 Method for manufacturing solid electrolyte secondary battery The method for manufacturing the solid electrolyte secondary battery of the present invention is not particularly limited, and it is composed of at least a positive electrode, a negative electrode, and an inorganic solid electrolyte, and is manufactured by a known method. For example, in the case of a coin-shaped lithium ion battery, a positive electrode, an inorganic solid electrolyte, and a negative electrode are arranged and inserted into an outer can. Thereafter, it is joined to the sealing body by tab welding or the like, the sealing body is encapsulated, and the storage battery is obtained by caulking. Although the shape of the battery is not limited, examples thereof include a coin shape, a cylindrical shape, a sheet shape, etc., and a structure in which two or more batteries are stacked may also be used.
以下の実施例において本発明をより具体的に説明するが、本発明はこれらに限定されない。 The present invention will be explained in more detail in the following examples, but the present invention is not limited thereto.
本実施例では、コイン電池を作製し、コイン電池の充放電特性の性能評価を以下の実験にて行った。 In this example, a coin battery was produced, and performance evaluation of the charge/discharge characteristics of the coin battery was performed in the following experiment.
［作製した電池の評価］
作製した電池の評価としては充放電装置を用いて充放電試験を行い、充電容量および放電容量を求めた。[Evaluation of the manufactured battery]
To evaluate the produced battery, a charging/discharging test was conducted using a charging/discharging device, and the charging capacity and discharging capacity were determined.
充放電測定
０．１Ｃ（１０時間率）に相当する電流で４．２ＶまでＣＣＣＶ充電（０．０１Ｃカット）後、０．１Ｃに相当する電流で、２．５ＶまでＣＣＣＶ放電（０．０１Ｃカット）を行った。試験温度は１００℃環境とした。 Charge/Discharge Measurement After CCCV charging (0.01C cut) to 4.2V with a current equivalent to 0.1C (10 hour rate), CCCV discharge to 2.5V (0.01C cut) with a current equivalent to 0.1C. ) was carried out. The test temperature was a 100°C environment.
［正極前駆体の実施作製例］
正極活物質としてＮＣＭ（ニッケル／コバルト／マンガン酸リチウム＝５／２／３）１００質量部に、導電助剤としてアセチレンブラック３質量部、黒鉛３質量部、バインダーとしてＰＶｄＦ３質量部を加え、さらにスラリーの固形分濃度が３５質量％となるようにＮＭＰ溶液中に加えて、十分に混合して正極用スラリーを得た。得られた正極スラリーを厚さ２０μｍのアルミ集電体上にダイコーターを用いて塗布し、１００℃で１２時間以上乾繰後、ロールプレス機にてプレスを行い、厚さ２０μｍの正極を作製した。正極活物質の目付量６．６ｍｇ／ｃｍ2、正極密度３．１ｇ／ｃｍ3、空隙率２６％。[Example of production of positive electrode precursor]
To 100 parts by mass of NCM (nickel/cobalt/lithium manganate = 5/2/3) as a positive electrode active material, 3 parts by mass of acetylene black and 3 parts by mass of graphite as conductive aids, and 3 parts by mass of PVdF as a binder, and further slurry was added to the NMP solution so that the solid content concentration was 35% by mass, and the mixture was thoroughly mixed to obtain a positive electrode slurry. The obtained positive electrode slurry was applied onto a 20 μm thick aluminum current collector using a die coater, dried at 100°C for 12 hours or more, and then pressed using a roll press to produce a 20 μm thick positive electrode. did. The basis weight of the positive electrode active material was 6.6 mg/cm 2 , the positive electrode density was 3.1 g/cm 3 , and the porosity was 26%.
［負極前駆体の実施作製例］
負極活物質として人造黒鉛（粒径１０μｍ） １００質量部に、導電助剤として気相成長炭素繊維（ＶＧＣＦ）２質量部、バインダーとしてＳＢＲ ３質量部、増粘剤としてカルボキシメチルセルロースのナトリウム塩 ２質量部を加え、さらにスラリーの固形分濃度が３５質量％となるように水を加えて、十分に混合して負極用スラリーを得た。得られた負極スラリーを厚さ１６．５μｍの銅集電体上にダイコーターを用いて塗布し、１００℃で１２時間以上乾繰後、ロールプレス機にてプレスを行い、厚さ２２μｍの負極を作製した。負極活物質の目付量３．１ｍｇ／ｃｍ2、負極密度１．２ｇ／ｃｍ3、空隙率２３％。[Example of production of negative electrode precursor]
100 parts by mass of artificial graphite (particle size 10 μm) as a negative electrode active material, 2 parts by mass of vapor grown carbon fiber (VGCF) as a conductive aid, 3 parts by mass of SBR as a binder, 2 parts by mass of sodium salt of carboxymethylcellulose as a thickener. %, water was further added so that the solid content concentration of the slurry was 35% by mass, and the mixture was sufficiently mixed to obtain a slurry for a negative electrode. The obtained negative electrode slurry was applied onto a 16.5 μm thick copper current collector using a die coater, dried at 100°C for 12 hours or more, and then pressed using a roll press machine to form a 22 μm thick negative electrode. was created. The basis weight of the negative electrode active material was 3.1 mg/cm 2 , the negative electrode density was 1.2 g/cm 3 , and the porosity was 23%.
［固体電解質二次電池用正極（正極前駆体にイオン伝導性ポリマー及びリチウム塩化合物を含浸した正極）の実施作製例］
側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーとしてエチレンオキシド／ジエチレングリコールメチルグリシジルエーテル／アリルグリシジルエーテル＝８０／１７／３モル％三元共重合体（重量平均分子量１５０万）１００質量部、リチウム塩化合物としてホウフッ化リチウム１２質量部、架橋助剤として、トリメチロールプロパントリアクリレート １０質量部、ラジカル開始剤としてベンゾイルパーオキシド（ナイパーＢＭＴ、日油株式会社製）０．３質量部をアセトニトリル ９００質量部に完全に溶解させた電極含浸用塗工溶液を調製した。実施作製例で得られた正極前駆体に、電極含浸用塗工溶液を１４０μｍ厚さとなるように塗工した。その後、２時間静置することにより、溶媒を除去しながら、正極前駆体内の空隙にイオン伝導性ポリマーとリチウム塩化合物を含浸した。１００℃で２時間、減圧下、含浸したイオン伝導性ポリマーの架橋を行い、固体電解質二次電池用正極を作製した。正極の断面をＳＥＭ（走査型電子顕微鏡）分析を行った。ＳＥＭにより、正極内の空隙にイオン伝導性ポリマーが観測された。[Example of production of positive electrode for solid electrolyte secondary battery (positive electrode in which positive electrode precursor is impregnated with ion conductive polymer and lithium salt compound)]
Ethylene oxide/diethylene glycol methyl glycidyl ether/allyl glycidyl ether = 80/17/3 mol% terpolymer (weight average molecular weight 1.5 million) 100 parts by mass as an ion conductive polymer having ethylene oxide units in the side chain, as a lithium salt compound 12 parts by mass of lithium borofluoride, 10 parts by mass of trimethylolpropane triacrylate as a crosslinking aid, 0.3 parts by mass of benzoyl peroxide (Niper BMT, manufactured by NOF Corporation) as a radical initiator, and 900 parts by mass of acetonitrile were completely added. A coating solution for electrode impregnation was prepared by dissolving . A coating solution for electrode impregnation was applied to the positive electrode precursor obtained in the example to a thickness of 140 μm. Thereafter, the ion conductive polymer and the lithium salt compound were impregnated into the voids in the positive electrode precursor while the solvent was removed by allowing the mixture to stand for 2 hours. The impregnated ion conductive polymer was crosslinked under reduced pressure at 100° C. for 2 hours to produce a positive electrode for a solid electrolyte secondary battery. A cross section of the positive electrode was analyzed using a scanning electron microscope (SEM). Ion-conducting polymer was observed in the voids within the positive electrode using SEM.
［固体電解質二次電池用正極の比較作製例］
実施作製例の固体電解質二次電池用正極において、側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーの代わりに、ポリエチレンオキシド１００質量部（重量平均分子量１１０万）を用いて、同様にして、比較用の固体電解質二次電池用正極を作製した。正極の断面について、ＳＥＭ分析を行った。ＳＥＭにより、正極内の空隙にポリエチレンオキシドが観測された。[Comparative production example of positive electrode for solid electrolyte secondary battery]
In the positive electrode for solid electrolyte secondary batteries of the practical production example, 100 parts by mass of polyethylene oxide (weight average molecular weight 1,100,000) was used instead of the ion-conductive polymer having ethylene oxide units in the side chain, and a comparative sample was prepared in the same manner. A positive electrode for a solid electrolyte secondary battery was fabricated. SEM analysis was performed on the cross section of the positive electrode. Polyethylene oxide was observed in the voids within the positive electrode by SEM.
［固体電解質二次電池用負極（負極前駆体にイオン伝導性ポリマー及びリチウム塩化合物を含浸した負極）の実施作製例］
側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーとしてエチレンオキシド／ジエチレングリコールメチルグリシジルエーテル／アリルグリシジルエーテル＝８０／１７／３モル％三元共重合体（重量平均分子量１５０万）１００質量部、リチウム塩化合物としてＬｉＴＦＳＩ３８質量部を、架橋助剤として、トリメチロールプロパントリアクリレート１０質量部、ラジカル開始剤としてベンゾイルパーオキシド（ナイパーＢＭＴ、日油株式会社製）０．３質量部をアセトニトリル９００質量部に完全に溶解させた電極含浸用塗工溶液を調製した。負極の実施作製例で得られた負極前駆体に、電極含浸用塗工溶液を１２０μｍ厚さとなるように塗工した。その後、２時間静置することにより、溶媒を除去しながら、負極前駆体内の空隙にイオン伝導性ポリマーとリチウム塩化合物を含浸した。１００℃で２時間、減圧下、含浸した側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーの架橋を行い、固体電解質二次電池用負極を作製した。負極の断面をＳＥＭ－ＥＤＸ（走査型電子顕微鏡／エネルギー分散型Ｘ線分光法）分析を行った。ＳＥＭにより、負極内の空隙にイオン伝導性ポリマーが観測され、また、ＥＤＸにより空隙にＦイオンの分布が観測され、これにより、ＬｉＴＦＳＩが空隙の中に含まれていることが確認できた。[Example of production of negative electrode for solid electrolyte secondary battery (negative electrode in which negative electrode precursor is impregnated with ion conductive polymer and lithium salt compound)]
Ethylene oxide/diethylene glycol methyl glycidyl ether/allyl glycidyl ether = 80/17/3 mol% terpolymer (weight average molecular weight 1.5 million) 100 parts by mass as an ion conductive polymer having ethylene oxide units in the side chain, as a lithium salt compound 38 parts by mass of LiTFSI, 10 parts by mass of trimethylolpropane triacrylate as a crosslinking aid, and 0.3 parts by mass of benzoyl peroxide (Niper BMT, manufactured by NOF Corporation) as a radical initiator were completely dissolved in 900 parts by mass of acetonitrile. A coating solution for electrode impregnation was prepared. An electrode impregnation coating solution was applied to the negative electrode precursor obtained in the negative electrode production example to a thickness of 120 μm. Thereafter, the voids in the negative electrode precursor were impregnated with the ion conductive polymer and the lithium salt compound while the solvent was removed by allowing the negative electrode precursor to stand for 2 hours. The impregnated ion conductive polymer having ethylene oxide units in its side chain was crosslinked under reduced pressure at 100° C. for 2 hours to produce a negative electrode for a solid electrolyte secondary battery. A cross section of the negative electrode was analyzed by SEM-EDX (scanning electron microscope/energy dispersive X-ray spectroscopy). Ion conductive polymer was observed in the voids in the negative electrode by SEM, and distribution of F ions in the voids was observed by EDX, thereby confirming that LiTFSI was contained in the voids.
［イオン伝導性ポリマー材料の架橋フィルムの作製例］
側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーとしてエチレンオキシド／ジエチレングリコールメチルグリシジルエーテル／アリルグリシジルエーテル＝８０／１７／３モル％三元共重合体（重量平均分子量１５０万）１００質量部、リチウム塩化合物としてＬｉＴＦＳＩ３８質量部を、架橋助剤として、トリメチロールプロパントリアクリレート １０質量部、ラジカル開始剤としてベンゾイルパーオキシド（ナイパーＢＭＴ、日油株式会社製）０．３質量部をアセトニトリル ９００質量部に溶解させた溶液を調製した。この溶液をポリテトラフルオロエチレン製モールド上にキャストして、室温で乾燥した後、１００℃、２時間、熱架橋を行い、厚さ２０μｍのイオン伝導性ポリマー材料の架橋フィルムを作製した。[Example of production of crosslinked film of ion conductive polymer material]
Ethylene oxide/diethylene glycol methyl glycidyl ether/allyl glycidyl ether = 80/17/3 mol% terpolymer (weight average molecular weight 1.5 million) 100 parts by mass as an ion conductive polymer having ethylene oxide units in the side chain, as a lithium salt compound 38 parts by mass of LiTFSI, 10 parts by mass of trimethylolpropane triacrylate as a crosslinking aid, and 0.3 parts by mass of benzoyl peroxide (Nipper BMT, manufactured by NOF Corporation) as a radical initiator were dissolved in 900 parts by mass of acetonitrile. A solution was prepared. This solution was cast onto a polytetrafluoroethylene mold, dried at room temperature, and then thermally crosslinked at 100° C. for 2 hours to produce a crosslinked film of ion conductive polymer material with a thickness of 20 μm.
電池の製造例
［固体電解質二次電池の実施製造例１］
ドライルーム内において、固体電解質二次電池用正極の実施作製例で得た正極、作製例のイオン伝導性ポリマー材料の架橋フィルム、無機固体電解質としてＬｉ7Ｌａ3Ｚｒ2Ｏ12（ＬＬＺ， 豊島製作所製 膜厚５００μｍ）、作製例のイオン伝導性ポリマー材料の架橋フィルム、負極としての金属リチウム箔の順に積層後、カシめ、試験用２０３２型コイン電池を製造した。
＜充放電条件＞
下限電圧２．５Ｖ－上限電圧４．２Ｖ、１００℃
ＣＣ（０．１Ｃ）－ＣＶ（０．０１Ｃ）充電
ＣＣ（０．１Ｃ）－ＣＶ（０．０１Ｃ）放電
＜充放電試験結果＞
充電容量１６８ｍＡｈ／ｇ、放電容量１６２ｍＡｈ／ｇ Example of manufacturing a battery [Example 1 of manufacturing a solid electrolyte secondary battery]
In a dry room, the positive electrode obtained in the example of manufacturing a positive electrode for a solid electrolyte secondary battery, the crosslinked film of the ion-conductive polymer material of the example, and Li 7 La 3 Zr 2 O 12 (LLZ, Toshima Manufacturing Co., Ltd.) as an inorganic solid electrolyte were prepared. After laminating in this order the crosslinked film of the ion conductive polymer material of the preparation example (film thickness: 500 μm), and the metal lithium foil as the negative electrode, they were caulked to produce a 2032 type coin battery for testing.
<Charge/discharge conditions>
Lower limit voltage 2.5V - Upper limit voltage 4.2V, 100℃
CC (0.1C) - CV (0.01C) charging CC (0.1C) - CV (0.01C) discharging <Charge/discharge test results>
Charge capacity 168mAh/g, discharge capacity 162mAh/g
［固体電解質二次電池の実施製造例２］
ドライルーム内において、固体電解質二次電池用正極の実施作製例で得た正極、作製例のイオン伝導性ポリマー材料の架橋フィルム、無機固体電解質としてＬｉ7Ｌａ3Ｚｒ2Ｏ12（ＬＬＺ， 豊島製作所製 膜厚５００μｍ）、作製例のイオン伝導性ポリマー材料の架橋フィルム、固体電解質二次電池用負極の実施作製例で得た負極の順に積層後、カシめ、試験用２０３２型コイン電池を製造した。
＜充放電条件＞
下限電圧２．５Ｖ－上限電圧４．２Ｖ、１００℃
ＣＣ（０．１Ｃ）－ＣＶ（０．０１Ｃ）充電
ＣＣ（０．１Ｃ）－ＣＶ（０．０１Ｃ）放電
＜充放電試験結果＞
充電容量１５５ｍＡｈ／ｇ 放電容量１４０ｍＡｈ／ｇ[Example 2 of production of solid electrolyte secondary battery]
In a dry room, the positive electrode obtained in the example of manufacturing a positive electrode for a solid electrolyte secondary battery, the crosslinked film of the ion-conductive polymer material of the example, and Li 7 La 3 Zr 2 O 12 (LLZ, Toshima Manufacturing Co., Ltd.) as an inorganic solid electrolyte were prepared. After laminating in this order the cross-linked film of the ion-conductive polymer material of the production example (film thickness 500 μm), and the negative electrode obtained in the practical production example of the negative electrode for solid electrolyte secondary batteries, they were caulked to produce a 2032-type coin battery for testing. .
<Charge/discharge conditions>
Lower limit voltage 2.5V - Upper limit voltage 4.2V, 100℃
CC (0.1C) - CV (0.01C) charging CC (0.1C) - CV (0.01C) discharging <Charge/discharge test results>
Charge capacity 155mAh/g Discharge capacity 140mAh/g
［固体電解質二次電池の比較製造例１］
ドライルーム内において、固体電解質二次電池用正極の比較例のポリエチレンオキシドを用いた正極、無機固体電解質としてＬｉ7Ｌａ3Ｚｒ2Ｏ12（ＬＬＺ， 豊島製作所製 膜厚５００μＭ）、作製例のイオン伝導性ポリマー材料の架橋フィルム、負極としての金属リチウム箔の順に積層後、カシめ、試験用２０３２型コイン電池を製造した。
＜充放電条件＞
下限電圧２．５Ｖ－上限電圧４．２Ｖ、１００℃
ＣＣ（０．１Ｃ）－ＣＶ（０．０１Ｃ）充電
ＣＣ（０．１Ｃ）－ＣＶ（０．０１Ｃ）放電
＜充放電試験結果＞
充電容量１００ｍＡｈ／ｇ 放電容量５０ｍＡｈ／ｇ[Comparative manufacturing example 1 of solid electrolyte secondary battery]
In a dry room, a positive electrode using polyethylene oxide as a comparative example of a positive electrode for a solid electrolyte secondary battery, Li 7 La 3 Zr 2 O 12 (LLZ, manufactured by Toshima Seisakusho, film thickness 500 μM) as an inorganic solid electrolyte, and ions of a fabrication example were prepared. A crosslinked film of a conductive polymer material and a metal lithium foil as a negative electrode were laminated in this order, and then caulked to produce a 2032 type coin battery for testing.
<Charge/discharge conditions>
Lower limit voltage 2.5V - Upper limit voltage 4.2V, 100℃
CC (0.1C) - CV (0.01C) charging CC (0.1C) - CV (0.01C) discharging <Charge/discharge test results>
Charge capacity 100mAh/g Discharge capacity 50mAh/g
電極材料の空隙がイオン伝導性ポリマー材料によって埋められた電極は、埋められていない電極、ポリエチレンオキシドによって埋められた電極と比較して、明らかに、充電および放電容量を向上させていることがわかる。ポリエチレンオキシドは、結晶性が高く、架橋できないので、１００℃の高温では溶融のため形状維持ができなくなり、結着性が弱くなっていることが原因であると考えられる。側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーは、柔軟性と結着性を有するので、無機固体電解質との界面での抵抗を下げる効果があるといえる。 It can be seen that the electrode in which the voids in the electrode material are filled with an ionically conductive polymer material clearly improves the charging and discharging capacity compared to the unfilled electrode, the electrode filled with polyethylene oxide. . This is thought to be due to the fact that polyethylene oxide has high crystallinity and cannot be crosslinked, so it cannot maintain its shape due to melting at a high temperature of 100° C., resulting in weak binding properties. Since the ion conductive polymer having ethylene oxide units in its side chain has flexibility and binding properties, it can be said to have the effect of lowering the resistance at the interface with the inorganic solid electrolyte.
本発明の固体電解質二次電池用電極は、固体電解質二次電池の電極として利用されることにより、優れた充放電特性を発揮させることができ、電気自動車やハイブリッド電気自動車などの車載用途や家庭用電力貯蔵用の蓄電池といった大型の電池用途に好適に利用可能である。 The electrode for a solid electrolyte secondary battery of the present invention can exhibit excellent charging and discharging characteristics when used as an electrode for a solid electrolyte secondary battery, and can be used for in-vehicle applications such as electric vehicles and hybrid electric vehicles, and for home use. It can be suitably used for large battery applications such as storage batteries for storing electric power.
Claims (9)
前記イオン伝導性ポリマーは、側鎖にエチレンオキシド単位を有するポリエーテルであり、
前記電極材料層を形成する電極材料間の空隙が前記イオン伝導性ポリマー材料によって埋められている、無機固体電解質二次電池用電極。 An electrode material layer containing an ion conductive polymer material containing an ion conductive polymer having an ethylene oxide unit in a side chain and a lithium salt compound, and an active material ,
The ion conductive polymer is a polyether having ethylene oxide units in the side chain,
An electrode for an inorganic solid electrolyte secondary battery , wherein gaps between electrode materials forming the electrode material layer are filled with the ion conductive polymer material .
An inorganic solid electrolyte secondary battery comprising the inorganic solid electrolyte secondary battery electrode according to any one of claims 1 to 6.
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| PCT/JP2019/045952 WO2020110993A1 (en) | 2018-11-26 | 2019-11-25 | Inorganic solid electrolyte secondary battery electrode and inorganic solid electrolyte secondary battery |
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