JP6920413B2 - All-solid-state secondary battery and its manufacturing method, and solid-state electrolyte membrane for all-solid-state secondary battery and its manufacturing method - Google Patents
All-solid-state secondary battery and its manufacturing method, and solid-state electrolyte membrane for all-solid-state secondary battery and its manufacturing method Download PDFInfo
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- JP6920413B2 JP6920413B2 JP2019504570A JP2019504570A JP6920413B2 JP 6920413 B2 JP6920413 B2 JP 6920413B2 JP 2019504570 A JP2019504570 A JP 2019504570A JP 2019504570 A JP2019504570 A JP 2019504570A JP 6920413 B2 JP6920413 B2 JP 6920413B2
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- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical class [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
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- 229910052794 bromium Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000013495 cobalt Nutrition 0.000 description 1
- GIPIUENNGCQCIT-UHFFFAOYSA-K cobalt(3+) phosphate Chemical class [Co+3].[O-]P([O-])([O-])=O GIPIUENNGCQCIT-UHFFFAOYSA-K 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
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- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011423 initialization method Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical class [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 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
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-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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- 238000007578 melt-quenching technique Methods 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical class [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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- H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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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
- H01M10/00—Secondary cells; Manufacture thereof
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- 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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Description
本発明は、全固体二次電池及びその製造方法に関する。また本発明は、全固体二次電池用固体電解質膜及びその製造方法に関する。 The present invention relates to an all-solid-state secondary battery and a method for manufacturing the same. The present invention also relates to a solid electrolyte membrane for an all-solid secondary battery and a method for producing the same.
リチウムイオン二次電池は、負極と、正極と、負極と正極との間に挟まれた電解質とを有し、両極間にリチウムイオンを往復移動させることにより充電と放電を可能とした蓄電池である。リチウムイオン二次電池には従来から、電解質として有機電解液が用いられてきた。しかし有機電解液は液漏れを生じやすく、また、過充電、過放電により電池内部で短絡が生じ発火するおそれもあり、信頼性と安全性のさらなる向上が求められている。
このような状況下、有機電解液に代えて、不燃性の無機固体電解質を用いた全固体二次電池の開発が進められている。全固体二次電池は負極、電解質及び正極のすべてが固体からなり、有機電解液を用いた電池の課題とされる安全性ないし信頼性を大きく改善することができ、また長寿命化も可能になるとされる。A lithium ion secondary battery is a storage battery that has a negative electrode, a positive electrode, and an electrolyte sandwiched between the negative electrode and the positive electrode, and can be charged and discharged by reciprocating lithium ions between the two electrodes. .. Conventionally, an organic electrolyte has been used as an electrolyte in a lithium ion secondary battery. However, the organic electrolyte is liable to leak, and there is a risk of short-circuiting and ignition inside the battery due to overcharging and overdischarging, and further improvement in reliability and safety is required.
Under such circumstances, the development of an all-solid secondary battery using a nonflammable inorganic solid electrolyte instead of the organic electrolyte is being promoted. In an all-solid-state secondary battery, the negative electrode, electrolyte, and positive electrode are all solid, which can greatly improve the safety and reliability of batteries using organic electrolytes, and can also extend the service life. It is said that it will be.
リチウムイオン二次電池は、充電時には正極から負極へと電子が移動し、同時に正極を構成するリチウム酸化物等からリチウムイオンが放出され、このリチウムイオンは電解質を通って負極へと到達して負極に溜め込まれる。こうして負極に溜め込まれたリチウムイオンの一部は電子を取り込み金属リチウムとして析出する現象が生じる。この金属リチウムの析出物が充放電の繰り返しによりデンドライト状に成長してしまうと、やがて正極へと達し、内部短絡が生じて二次電池として機能しなくなってしまう。デンドライトは非常に細く、電解質として固体を用いる全固体二次電池においても、固体電解質層に生じた亀裂ないしピンホール等を通って成長する。したがって、全固体二次電池においてもデンドライトの成長をブロックすることは、電池を長寿命化する上で重要である。
デンドライトによる内部短絡の問題に対処すべく特許文献1には、固体電解質層中に単体硫黄を過剰に添加し、デンドライトの成長を単体硫黄によりブロックする技術が記載されている。特許文献1記載の技術では、固体電解質粉末に単体硫黄を均一に分散させた混合物を用いて固体電解質層を形成しているため、この固体電解質層は単体硫黄粉末と固体電解質粉末との混合物からなる形態である。In a lithium ion secondary battery, electrons move from the positive electrode to the negative electrode during charging, and at the same time, lithium ions are released from lithium oxides and the like constituting the positive electrode, and these lithium ions reach the negative electrode through an electrolyte and reach the negative electrode. It is stored in. In this way, a part of the lithium ions stored in the negative electrode takes in electrons and precipitates as metallic lithium. When this metallic lithium precipitate grows like a dendrite due to repeated charging and discharging, it eventually reaches the positive electrode, causing an internal short circuit and failing to function as a secondary battery. Dendrite is very thin, and even in an all-solid-state secondary battery that uses a solid as an electrolyte, it grows through cracks or pinholes formed in the solid electrolyte layer. Therefore, blocking the growth of dendrites even in an all-solid-state secondary battery is important for extending the life of the battery.
In order to deal with the problem of internal short circuit due to dendrite, Patent Document 1 describes a technique of excessively adding elemental sulfur to the solid electrolyte layer to block the growth of dendrite with elemental sulfur. In the technique described in Patent Document 1, a solid electrolyte layer is formed by using a mixture in which simple sulfur is uniformly dispersed in the solid electrolyte powder. Therefore, the solid electrolyte layer is made from a mixture of the single sulfur powder and the solid electrolyte powder. It is a form of
電解質として有機電解液を用いたリチウムイオン二次電池は、正極、電解質及び負極からなる層構成の電池シートを軸心に巻きつけて電池シートをロール状(円筒型)の積層状態とし、これにより電池の高出力化が図られている。全固体二次電池においても、高出力化のために電池形状を円筒型にすることも検討されている。しかし、全固体二次電池を円筒型にする場合には、電解質層が固体であるがゆえに電解質層に亀裂、ピンホール等が生じやすい。その結果、デンドライトの成長による内部短絡の問題がより顕在化することになる。上記特許文献1記載の技術は、固体電解質層中に分散させた単体硫黄粉末によりデンドライトの成長をブロックするものであるが、固体電解質層中に単体硫黄粉末を混合するだけでは、固体電解質間の空隙を隙間なく埋めることは難しい。 In a lithium ion secondary battery using an organic electrolyte as an electrolyte, a battery sheet having a layer structure consisting of a positive electrode, an electrolyte and a negative electrode is wound around the axis to form a roll-shaped (cylindrical) laminated state of the battery sheet. The output of the battery has been increased. For all-solid-state secondary batteries, it is also being considered to make the battery shape cylindrical in order to increase the output. However, when the all-solid-state secondary battery has a cylindrical shape, cracks, pinholes, and the like are likely to occur in the electrolyte layer because the electrolyte layer is solid. As a result, the problem of internal short circuits due to the growth of dendrites becomes more apparent. The technique described in Patent Document 1 blocks the growth of dendrites by the simple sulfur powder dispersed in the solid electrolyte layer. However, simply mixing the single sulfur powder in the solid electrolyte layer is sufficient between the solid electrolytes. It is difficult to fill the voids without gaps.
本発明は、固体電解質層に生じた亀裂、ピンホール等の空隙が十分に塞がれた、充放電サイクル特性に優れた全固体二次電池及びその製造方法を提供することを課題とする。また本発明は、固体電解質層に生じた亀裂、ピンホール等の空隙が十分に塞がれ、全固体二次電池の固体電解質層として用いることにより、充放電サイクル特性に優れた全固体二次電池を得ることを可能とする固体電解質膜及びその製造方法を提供することを課題とする。 An object of the present invention is to provide an all-solid-state secondary battery having excellent charge / discharge cycle characteristics in which voids such as cracks and pinholes generated in the solid electrolyte layer are sufficiently closed, and a method for producing the same. Further, in the present invention, the voids such as cracks and pinholes generated in the solid electrolyte layer are sufficiently closed, and by using the solid electrolyte layer as the solid electrolyte layer of the all solid secondary battery, the all solid secondary having excellent charge / discharge cycle characteristics An object of the present invention is to provide a solid electrolyte membrane capable of obtaining a battery and a method for producing the same.
本発明者は上記課題に鑑み鋭意検討を重ねた結果、100℃においては固体であり、200℃以下の温度領域で熱溶融する電子絶縁性の充填材と、固体電解質とを含む混合物を用いて膜を形成し、その後、この膜を加熱して充填材を熱溶融させることにより、毛細管現象を利用して膜中の微小の欠陥(空隙)に充填材を浸透させることができ、膜欠陥が十分に塞がれた形態の固体電解質膜が得られること、この固体電解質膜を全固体二次電池の固体電解質層として用いることにより、負極から析出して成長してくるデンドライトを効果的にブロックすることができ、内部短絡を十分に抑制できることを見い出した。本発明はこれらの知見に基づきさらに検討を重ね、完成されるに至ったものである。 As a result of diligent studies in view of the above problems, the present inventor used a mixture containing an electronically insulating filler that is solid at 100 ° C. and melts thermally in a temperature range of 200 ° C. or lower, and a solid electrolyte. By forming a film and then heating the film to melt the filler, the filler can be permeated into minute defects (voids) in the film by utilizing the capillary phenomenon, and the film defects are formed. A sufficiently closed solid electrolyte membrane can be obtained, and by using this solid electrolyte membrane as the solid electrolyte layer of the all-solid secondary battery, the dendrite that precipitates from the negative electrode and grows can be effectively blocked. It was found that the internal short circuit can be sufficiently suppressed. The present invention has been further studied based on these findings and has been completed.
すなわち、上記の課題は以下の手段により解決された。
〔1〕
固体電解質層が、無機固体電解質材料に占有された電解質領域と、無機固体電解質材料間の空隙を塞ぐ充填材領域とを有し、
上記充填材領域が、100℃において固体でかつ200℃以下の温度領域で熱溶融する電子絶縁性材料の熱溶融物を用いて形成されたものであって、
上記固体電解質層が、上記無機固体電解質材料と上記電子絶縁性材料とを含む組成物の層であり、かつ、正極活物質層上に直接配されてなり、
上記固体電解質層中、上記無機固体電解質材料の含有量100体積%に対し、上記電子絶縁性材料の含有量が2体積%以上であり、
上記充填材領域が有機バインダーを含有する、全固体二次電池。
〔2〕
固体電解質層が、無機固体電解質材料に占有された電解質領域と、無機固体電解質材料間の空隙を塞ぐ充填材領域とを有し、
上記充填材領域が、100℃において固体でかつ200℃以下の温度領域で熱溶融する電子絶縁性材料を含み、
1辺が5μmの正方領域内に収まる充填材領域FRを平面視観察した場合に、FRの面積FAと、FRの外周長さFLとの比が、FL/FA≧0.81を満たし、
上記固体電解質層が、上記無機固体電解質材料と上記電子絶縁性材料とを含む組成物の層であり、かつ、正極活物質層上に直接配されてなり、
上記固体電解質層中、上記無機固体電解質材料の含有量100体積%に対し、上記電子絶縁性材料の含有量が2体積%以上であり、
上記充填材領域が有機バインダーを含有する、全固体二次電池。
〔3〕
固体電解質層が、無機固体電解質材料に占有された電解質領域と、無機固体電解質材料間の空隙を塞ぐ充填材領域とを有し、
上記充填材領域が、100℃において固体でかつ200℃以下の温度領域で熱溶融する電子絶縁性材料の熱溶融物を用いて形成されたものであって、
上記固体電解質層が、上記無機固体電解質材料と上記電子絶縁性材料とを含む組成物の層であり、かつ、正極活物質層上に直接配されてなり、
上記固体電解質層中、上記無機固体電解質材料の含有量100体積%に対し、上記電子絶縁性材料の含有量が2体積%以上であり、
上記無機固体電解質材料が大粒径の粒子と小粒径の粒子とを有し、[大粒径粒子の粒子径]>4×[小粒径粒子の粒子径]を満たす粒度分布を有する、全固体二次電池。
〔4〕
固体電解質層が、無機固体電解質材料に占有された電解質領域と、無機固体電解質材料間の空隙を塞ぐ充填材領域とを有し、
上記充填材領域が、100℃において固体でかつ200℃以下の温度領域で熱溶融する電子絶縁性材料を含み、
1辺が5μmの正方領域内に収まる充填材領域FRを平面視観察した場合に、FRの面積FAと、FRの外周長さFLとの比が、FL/FA≧0.81を満たし、
上記固体電解質層が、上記無機固体電解質材料と上記電子絶縁性材料とを含む組成物の層であり、かつ、正極活物質層上に直接配されてなり、
上記固体電解質層中、上記無機固体電解質材料の含有量100体積%に対し、上記電子絶縁性材料の含有量が2体積%以上であり、
上記無機固体電解質材料が大粒径の粒子と小粒径の粒子とを有し、[大粒径粒子の粒子径]>4×[小粒径粒子の粒子径]を満たす粒度分布を有する、全固体二次電池。
〔5〕
上記電子絶縁性材料が硫黄及び/又は改質硫黄である、〔1〕〜〔4〕のいずれか1つに記載の全固体二次電池。
〔6〕
上記充填材領域が、アルカリ金属を含む化合物及び/又はアルカリ土類金属を含む化合物を含有する、〔1〕〜〔5〕のいずれか1つに記載の全固体二次電池。
〔7〕
上記無機固体電解質材料が硫化物系無機固体電解質及び/又は酸化物系無機固体電解質である、〔1〕〜〔6〕のいずれか1つ記載の全固体二次電池。
〔8〕
上記充填材領域が、上記固体電解質層と正極活物質層との界面には存在しない、〔1〕〜〔7〕のいずれか1つに記載の全固体二次電池。
〔9〕
上記固体電解質層中、無機固体電解質材料の含有量100体積%に対し、上記電子絶縁性材料の含有量が15体積%未満である、〔1〕〜〔8〕のいずれか1つに記載の全固体二次電池。
〔10〕
無機固体電解質材料に占有された電解質領域と、無機固体電解質材料間の空隙を塞ぐ充填材領域とを有し、
上記充填材領域は、100℃において固体でかつ200℃以下の温度領域で熱溶融する電子絶縁性材料の熱溶融物を用いて形成されたものである、全固体二次電池用固体電解質膜であって、
上記全固体二次電池用固体電解質膜が、上記無機固体電解質材料と上記電子絶縁性材料とを含む組成物の膜であり、かつ、正極活物質層上に直接配して使用されるものであり、
上記全固体二次電池用固体電解質膜中、上記無機固体電解質材料の含有量100体積%に対し、上記電子絶縁性材料の含有量が2体積%以上であり、
前記無機固体電解質材料が大粒径の粒子と小粒径の粒子とを有し、[大粒径粒子の粒子径]>4×[小粒径粒子の粒子径]を満たす、全固体二次電池用固体電解質膜。
〔11〕
無機固体電解質材料に占有された電解質領域と、無機固体電解質材料間の空隙を塞ぐ充填材領域とを有し、
上記充填材領域が、100℃において固体でかつ200℃以下の温度領域で熱溶融する電子絶縁性材料を含み、
1辺が5μmの正方領域内に収まる充填材領域FRを平面視観察した場合に、FRの面積FAと、FRの外周長さFLとの比が、FL/FA≧0.81を満たす、全固体二次電池用固体電解質膜であって、
上記全固体二次電池用固体電解質膜が、上記無機固体電解質材料と上記電子絶縁性材料とを含む組成物の膜であり、かつ、正極活物質層上に直接配して使用されるものであり、
上記全固体二次電池用固体電解質膜中、上記無機固体電解質材料の含有量100体積%に対し、上記電子絶縁性材料の含有量が2体積%以上であり、
前記無機固体電解質材料が大粒径の粒子と小粒径の粒子とを有し、[大粒径粒子の粒子径]>4×[小粒径粒子の粒子径]を満たす、全固体二次電池用固体電解質膜。
〔12〕
上記電子絶縁性材料が硫黄及び/又は改質硫黄である、〔10〕又は〔11〕記載の全固体二次電池用固体電解質膜。
〔13〕
上記無機固体電解質材料が硫化物系無機固体電解質及び/又は酸化物系無機固体電解質である、〔10〕〜〔12〕のいずれか1つに記載の全固体二次電池用固体電解質膜。
〔14〕
無機固体電解質材料と硫黄及び/又は改質硫黄とを含有する無機固体電解質組成物を用いて形成した層を加熱し、この層中の硫黄及び/又は改質硫黄を熱溶融させ、次いで冷却して固体電解質層を形成することを含む、〔1〕〜〔9〕のいずれか1つに記載の全固体二次電池の製造方法。
〔15〕
無機固体電解質材料を用いて形成した層の外部から上記層の内部に向けて、熱溶融状態にある硫黄及び/又は改質硫黄を含浸させ、次いで冷却して固体電解質層を形成することを含む、全固体二次電池の製造方法であって、
上記固体電解質層が、上記無機固体電解質材料に占有された電解質領域と、上記無機固体電解質材料間の空隙を塞ぐ充填材領域とを有し、
上記充填材領域が、上記硫黄及び/又は上記改質硫黄の熱溶融物を用いて形成されたものであり、
上記固体電解質層中、上記無機固体電解質材料の含有量100体積%に対し、上記硫黄及び上記改質硫黄の含有量の合計が2体積%以上である、全固体二次電池の製造方法。
〔16〕
無機固体電解質材料と硫黄及び/又は改質硫黄とを含有する無機固体電解質組成物を用いて形成した膜を加熱し、この膜中の硫黄及び/又は改質硫黄を熱溶融させ、次いで冷却することを含む、〔10〕〜〔13〕のいずれか1つに記載の全固体二次電池用固体電解質膜の製造方法。
〔17〕
無機固体電解質材料を用いて形成した膜の外部から上記層の内部に向けて、熱溶融状態にある硫黄及び/又は改質硫黄を含浸させ、次いで冷却することを含む、全固体二次電池用固体電解質膜の製造方法であって、
上記固体電解質膜が、上記無機固体電解質材料に占有された電解質領域と、上記無機固体電解質材料間の空隙を塞ぐ充填材領域とを有し、
上記充填材領域が、上記硫黄及び/又は上記改質硫黄の熱溶融物を用いて形成されたものであり、
上記固体電解質膜中、上記無機固体電解質材料の含有量100体積%に対し、上記硫黄及び上記改質硫黄の含有量の合計が2体積%以上である、全固体二次電池用固体電解質膜の製造方法。
That is, the above problem was solved by the following means.
[1]
The solid electrolyte layer has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that closes the voids between the inorganic solid electrolyte materials.
The filler region is formed by using a thermal melt of an electron insulating material that is solid at 100 ° C. and thermally melts in a temperature region of 200 ° C. or lower.
The solid electrolyte layer is a layer of a composition containing the inorganic solid electrolyte material and the electron insulating material, and is arranged directly on the positive electrode active material layer.
The solid electrolyte layer, with respect to content 100% by volume of the inorganic solid electrolyte material state, and are content more than 2% by volume of the electronically insulating material,
The filler area you containing an organic binder, all-solid secondary battery.
[2]
The solid electrolyte layer has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that closes the voids between the inorganic solid electrolyte materials.
The filler region comprises an electronically insulating material that is solid at 100 ° C. and thermally melts in a temperature region of 200 ° C. or lower.
When the filler region FR that fits in the square region with one side of 5 μm is observed in a plan view, the ratio of the area FA of the FR to the outer peripheral length FL of the FR satisfies FL / FA ≧ 0.81.
The solid electrolyte layer is a layer of a composition containing the inorganic solid electrolyte material and the electron insulating material, and is arranged directly on the positive electrode active material layer.
The solid electrolyte layer, with respect to content 100% by volume of the inorganic solid electrolyte material state, and are content more than 2% by volume of the electronically insulating material,
The filler area you containing an organic binder, all-solid secondary battery.
[3]
The solid electrolyte layer has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that closes the voids between the inorganic solid electrolyte materials.
The filler region is formed by using a thermal melt of an electron insulating material that is solid at 100 ° C. and thermally melts in a temperature region of 200 ° C. or lower.
The solid electrolyte layer is a layer of a composition containing the inorganic solid electrolyte material and the electron insulating material, and is arranged directly on the positive electrode active material layer.
In the solid electrolyte layer, the content of the electronically insulating material is 2% by volume or more with respect to the content of the inorganic solid electrolyte material of 100% by volume.
The inorganic solid electrolyte material has a large particle size particle and a small particle size particle, and has a particle size distribution satisfying [particle size of large particle size particles]> 4 × [particle size of small particle size particles]. All-solid secondary battery.
[4]
The solid electrolyte layer has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that closes the voids between the inorganic solid electrolyte materials.
The filler region comprises an electronically insulating material that is solid at 100 ° C. and thermally melts in a temperature region of 200 ° C. or lower.
When the filler region FR that fits in the square region with one side of 5 μm is observed in a plan view, the ratio of the area FA of the FR to the outer peripheral length FL of the FR satisfies FL / FA ≧ 0.81.
The solid electrolyte layer is a layer of a composition containing the inorganic solid electrolyte material and the electron insulating material, and is arranged directly on the positive electrode active material layer.
In the solid electrolyte layer, the content of the electronically insulating material is 2% by volume or more with respect to the content of the inorganic solid electrolyte material of 100% by volume.
The inorganic solid electrolyte material has a large particle size particle and a small particle size particle, and has a particle size distribution satisfying [particle size of large particle size particles]> 4 × [particle size of small particle size particles]. All-solid secondary battery.
[ 5 ]
The all-solid-state secondary battery according to any one of [1] to [4], wherein the electronically insulating material is sulfur and / or modified sulfur.
[ 6 ]
The all-solid-state secondary battery according to any one of [1] to [5 ], wherein the filler region contains a compound containing an alkali metal and / or a compound containing an alkaline earth metal.
[ 7 ]
The all-solid-state secondary battery according to any one of [1] to [6 ], wherein the inorganic solid electrolyte material is a sulfide-based inorganic solid electrolyte and / or an oxide-based inorganic solid electrolyte.
[ 8 ]
The all-solid-state secondary battery according to any one of [1] to [7 ], wherein the filler region does not exist at the interface between the solid electrolyte layer and the positive electrode active material layer.
[9]
The method according to any one of [1] to [8], wherein the content of the electronically insulating material is less than 15% by volume with respect to 100% by volume of the content of the inorganic solid electrolyte material in the solid electrolyte layer. All-solid-state secondary battery.
[10]
It has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that closes the voids between the inorganic solid electrolyte materials.
The filler region is a solid electrolyte membrane for an all-solid secondary battery, which is formed by using a thermal melt of an electronically insulating material that is solid at 100 ° C. and thermally melts in a temperature region of 200 ° C. or lower. There,
The solid electrolyte film for an all-solid secondary battery is a film of a composition containing the inorganic solid electrolyte material and the electron insulating material, and is used by being directly arranged on the positive electrode active material layer. can be,
The all solid state secondary battery for a solid electrolyte membrane, to the content 100% by volume of the inorganic solid electrolyte material state, and are content more than 2% by volume of the electronically insulating material,
The inorganic solid electrolyte material has large particle size particles and small particle size particles, and satisfies [particle size of large particle size particles]> 4 × [particle size of small particle size particles]. Solid electrolyte membrane for batteries.
[11]
It has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that closes the voids between the inorganic solid electrolyte materials.
The filler region comprises an electronically insulating material that is solid at 100 ° C. and thermally melts in a temperature region of 200 ° C. or lower.
When the filler region FR that fits in the square region with one side of 5 μm is observed in a plan view, the ratio of the area FA of the FR to the outer peripheral length FL of the FR satisfies FL / FA ≧ 0.81. A solid electrolyte membrane for solid secondary batteries,
The solid electrolyte film for an all-solid secondary battery is a film of a composition containing the inorganic solid electrolyte material and the electron insulating material, and is used by being directly arranged on the positive electrode active material layer. can be,
The all solid state secondary battery for a solid electrolyte membrane, to the content 100% by volume of the inorganic solid electrolyte material state, and are content more than 2% by volume of the electronically insulating material,
The inorganic solid electrolyte material has large particle size particles and small particle size particles, and satisfies [particle size of large particle size particles]> 4 × [particle size of small particle size particles]. Solid electrolyte membrane for batteries.
[12]
The solid electrolyte membrane for an all-solid secondary battery according to [10] or [11], wherein the electronically insulating material is sulfur and / or modified sulfur.
[13]
The solid electrolyte membrane for an all-solid secondary battery according to any one of [10] to [12], wherein the inorganic solid electrolyte material is a sulfide-based inorganic solid electrolyte and / or an oxide-based inorganic solid electrolyte.
[ 14 ]
A layer formed using an inorganic solid electrolyte composition containing an inorganic solid electrolyte material and sulfur and / or modified sulfur is heated, and the sulfur and / or modified sulfur in this layer is thermally melted and then cooled. The method for producing an all-solid-state secondary battery according to any one of [1] to [9], which comprises forming a solid electrolyte layer.
[ 15 ]
This includes impregnating the layer formed with the inorganic solid electrolyte material from the outside to the inside of the layer with sulfur and / or modified sulfur in a heat-melted state, and then cooling to form a solid electrolyte layer. , A method of manufacturing an all-solid-state secondary battery,
The solid electrolyte layer has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that closes the voids between the inorganic solid electrolyte materials.
The filler region is formed by using the thermal melt of the sulfur and / or the modified sulfur.
A method for producing an all-solid secondary battery, wherein the total content of the sulfur and the modified sulfur in the solid electrolyte layer is 2% by volume or more with respect to 100% by volume of the content of the inorganic solid electrolyte material.
[ 16 ]
A film formed using an inorganic solid electrolyte composition containing an inorganic solid electrolyte material and sulfur and / or modified sulfur is heated, and the sulfur and / or modified sulfur in the film is thermally melted and then cooled. The method for producing a solid electrolyte membrane for an all-solid secondary battery according to any one of [10] to [ 13].
[ 17 ]
For all-solid-state secondary batteries, including impregnating hot-melted sulfur and / or modified sulfur from the outside of a film formed with an inorganic solid electrolyte material to the inside of the layer and then cooling. A method for producing a solid electrolyte membrane.
The solid electrolyte membrane has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that closes the gap between the inorganic solid electrolyte materials.
The filler region is formed by using the thermal melt of the sulfur and / or the modified sulfur.
In the solid electrolyte membrane, the total content of the sulfur and the modified sulfur is 2% by volume or more with respect to 100% by volume of the content of the inorganic solid electrolyte material. Production method.
本明細書において、「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。 In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
本発明の全固体二次電池は、充電時に負極から成長するデンドライトを効果的にブロックすることができ、内部短絡を十分に抑制することができる。また本発明の全固体二次電池用固体電解質膜は、全固体二次電池の固体電解質層として用いることにより、全固体二次電池の充電時に負極から成長するデンドライトを効果的にブロックすることができ、電池の内部短絡を十分に抑制することを可能とする。
また本発明の全固体二次電池の製造方法によれば、充電時に負極から成長するデンドライトを効果的にブロックすることができ、内部短絡を十分に抑制することができる全固体二次電池を得ることができる。また本発明の全固体二次電池用固体電解質膜の製造方法によれば、全固体二次電池の固体電解質層として用いることにより全固体二次電池の充電時に負極から成長するデンドライトを効果的にブロックすることができ、電池の内部短絡を十分に抑制することを可能とする全固体二次電池用固体電解質膜を得ることができる。The all-solid-state secondary battery of the present invention can effectively block dendrites growing from the negative electrode during charging, and can sufficiently suppress internal short circuits. Further, the solid electrolyte membrane for an all-solid-state secondary battery of the present invention can be used as a solid electrolyte layer of an all-solid-state secondary battery to effectively block dendrites growing from a negative electrode when the all-solid-state secondary battery is charged. It is possible to sufficiently suppress the internal short circuit of the battery.
Further, according to the method for manufacturing an all-solid-state secondary battery of the present invention, an all-solid-state secondary battery capable of effectively blocking dendrites growing from the negative electrode during charging and sufficiently suppressing an internal short circuit can be obtained. be able to. Further, according to the method for producing a solid electrolyte membrane for an all-solid-state secondary battery of the present invention, by using it as a solid electrolyte layer of an all-solid-state secondary battery, dendrites that grow from the negative electrode when the all-solid-state secondary battery is charged are effectively produced. It is possible to obtain a solid electrolyte film for an all-solid-state secondary battery that can be blocked and can sufficiently suppress an internal short circuit of the battery.
本発明の全固体二次電池は、固体電解質層中の無機固体電解質同士の間の空隙が特定の電子絶縁性材料により十分に塞がれており、固体電解質層の厚み方向に向けたデンドライトの成長を効果的にブロックすることができる。
本発明の好ましい実施形態について説明する。In the all-solid-state secondary battery of the present invention, the voids between the inorganic solid electrolytes in the solid electrolyte layer are sufficiently closed by a specific electron insulating material, and the dendrite in the thickness direction of the solid electrolyte layer is formed. Growth can be effectively blocked.
Preferred embodiments of the present invention will be described.
[全固体二次電池]
図1は、本発明の全固体二次電池の一実施形態について、電池を構成する各層の積層状態を模式化して示す断面図である。本実施形態の全固体二次電池10は、負極側からみて、負極集電体1、負極活物質層2、固体電解質層3、正極活物質層4、正極集電体5を、この順に積層してなる構造を有しており、隣接する層同士は直に接触している。このような構造を採用することで、充電時には、負極側に電子(e−)が供給され、同時に正極活物質を構成するアルカリ金属又はアルカリ土類金属がイオン化して固体電解質層3を通過(伝導)して移動し、負極に蓄積される。例えばリチウムイオン二次電池であれば、負極にリチウムイオン(Li+)が蓄積されることになる。
一方、放電時には、負極に蓄積された上記のアルカリ金属イオンないしアルカリ土類金属イオンが正極側に戻され、作動部位6に電子を供給することができる。図示した全固体二次電池の例では、作動部位6に電球を採用しており、放電によりこれが点灯するようにされている。[All-solid-state secondary battery]
FIG. 1 is a cross-sectional view schematically showing a laminated state of each layer constituting the battery for one embodiment of the all-solid-state secondary battery of the present invention. In the all-solid-state
On the other hand, at the time of discharge, the above-mentioned alkali metal ion or alkaline earth metal ion accumulated in the negative electrode is returned to the positive electrode side, and electrons can be supplied to the operating portion 6. In the illustrated example of the all-solid-state secondary battery, a light bulb is used for the operating portion 6, and the light bulb is turned on by electric discharge.
また、本発明の全固体二次電池は、負極活物質層2を有さずに、固体電解質層3と負極集電体1とが直に接する形態とすることも好ましい。この形態の全固体二次電池では、充電時に負極に蓄積したアルカリ金属イオンないしアルカリ土類金属イオンの一部が電子と結合し、金属として負極集電体表面に析出する現象を利用する。すなわち、この形態の全固体二次電池は、負極表面に析出した金属を負極活物質層として機能させるものである。例えば金属リチウムは、負極活物質として汎用されている黒鉛に比べて10倍以上の理論容量を有するとされている。したがって、負極に金属リチウムを析出させてこの析出した金属リチウムに固体電解質層を押しつけた形態とすることにより、集電体表面に金属リチウムの層を形成することができ、高エネルギー密度の二次電池を実現することが可能になるとされる。
また、負極活物質層を取り除いた形態の全固体二次電池は、電池の厚さが薄くなるために、電池をロール状に巻いた形態とする場合には、固体電解質層の亀裂等の発生をより抑えることが可能になる利点もある。
なお、本明細書において負極活物質層を有しない形態の全固体二次電池とは、あくまで電池製造における層形成工程において負極活物質層を形成しないことを意味し、上記の通り、充電により固体電解質層と負極集電体との間に負極活物質層が形成されるものである。Further, it is also preferable that the all-solid-state secondary battery of the present invention has a form in which the
Further, in the all-solid-state secondary battery in which the negative electrode active material layer is removed, the thickness of the battery becomes thin, so that when the battery is wound in a roll shape, cracks in the solid electrolyte layer occur. There is also an advantage that it becomes possible to further suppress.
In the present specification, the all-solid secondary battery having no negative electrode active material layer means that the negative electrode active material layer is not formed in the layer forming step in the battery manufacturing, and as described above, it is solid by charging. A negative electrode active material layer is formed between the electrolyte layer and the negative electrode current collector.
図2に示す円筒型全固体二次電池は、図1の層構成を円筒型の形態で実現したものである。この円筒型全固体二次電池は、図1の層構成を基本単位とする発電要素が軸心22の周りに積層状に形成されている。すなわち、負極集電体21d、負極活物質層21e、固体電解質層21a、正極活物質層21c及び正極集電体21bがこの順に積層された発電要素が複層化された形態を採る。この円筒型全固体二次電池において、隣接する2つの発電要素は集電体1つを共有する形態となる。すなわち、図2に示すように一の集電体の両面に負極活物質層が設けられ、また別の集電体の両面に正極活物質層が設けられた形態となる。また、円筒型全固体二次電池は、必要により電池カバー23を備えていてもよい。
図2に示すような積層構造とすることにより、電池を高出力化することが可能となる。The cylindrical all-solid-state secondary battery shown in FIG. 2 realizes the layer structure of FIG. 1 in a cylindrical form. In this cylindrical all-solid-state secondary battery, power generation elements having the layer structure of FIG. 1 as a basic unit are formed in a laminated manner around the
By adopting the laminated structure as shown in FIG. 2, it is possible to increase the output of the battery.
本発明の全固体二次電池において、正極活物質層、固体電解質層、負極活物質層の厚さは特に限定されない。一般的な電池の寸法を考慮すると、上記各層の厚さは10〜1000μmが好ましく、20μm以上500μm未満がより好ましい。 In the all-solid-state secondary battery of the present invention, the thicknesses of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer are not particularly limited. Considering the dimensions of a general battery, the thickness of each layer is preferably 10 to 1000 μm, more preferably 20 μm or more and less than 500 μm.
本明細書において、正極活物質層と負極活物質層とを合わせて電極層と称することがある。正極活物質層には正極活物質が含有され、負極活物質層には負極活物質が含有される。正極活物質及び負極活物質のいずれかを示すのに、あるいは両方を合わせて示すのに、単に活物質または電極活物質と称することがある。固体電解質層は通常は正極活物質及び/又は負極活物質を含まない。固体電解質層を構成する無機固体電解質、あるいは固体電解質層を構成する無機固体電解質と活物質との組み合わせを無機固体電解質材料という。 In the present specification, the positive electrode active material layer and the negative electrode active material layer may be collectively referred to as an electrode layer. The positive electrode active material layer contains a positive electrode active material, and the negative electrode active material layer contains a negative electrode active material. To indicate either the positive electrode active material and the negative electrode active material, or both, they may be simply referred to as an active material or an electrode active material. The solid electrolyte layer usually does not contain a positive electrode active material and / or a negative electrode active material. The inorganic solid electrolyte constituting the solid electrolyte layer, or the combination of the inorganic solid electrolyte constituting the solid electrolyte layer and the active material is referred to as an inorganic solid electrolyte material.
<固体電解質層>
本発明の全固体二次電池は、固体電解質層が無機固体電解質材料に占有された電解質領域と、この無機固体電解質材料間の空隙を塞ぐ充填材領域とを有する。この充填材領域は、デンドライトが貫通可能な固体電解質層中の亀裂ないしピンホール等を塞いでデンドライトの成長をブロックするものである。本発明において「無機固体電解質材料間の空隙を塞ぐ充填材領域を有する」とは、固体電解質層中に存在する無機固体電解質材料間の空隙のうち少なくとも一部が特定の充填材により塞がれ、この充填材により埋められた充填材領域がデンドライトの成長をブロック可能な状態にあることを意味する。<Solid electrolyte layer>
The all-solid secondary battery of the present invention has an electrolyte region in which the solid electrolyte layer is occupied by the inorganic solid electrolyte material, and a filler region that closes the voids between the inorganic solid electrolyte materials. This filler region blocks the growth of dendrites by blocking cracks, pinholes, etc. in the solid electrolyte layer through which the dendrites can penetrate. In the present invention, "having a filler region that closes the voids between the inorganic solid electrolyte materials" means that at least a part of the voids between the inorganic solid electrolyte materials existing in the solid electrolyte layer is closed by the specific filler. This means that the filler area filled with this filler is in a state where the growth of dendrite can be blocked.
(充填材領域)
本発明において充填材領域は、単に粒子状の充填材が存在しているのではなく、無機固体電解質材料間の形状に沿って、事実上隙間なく、充填材である電子絶縁性材料が存在している。このような電子絶縁性材料の充填を実現するために、上記電子絶縁性材料としては、100℃において固体(すなわち融点が100℃越え)である一方、200℃以下の温度領域において熱溶融する物性のものを用いる。「200℃以下の温度領域で熱溶融する」とは、1気圧下において、200℃以下の温度領域で熱溶融することを意味する。このような電子絶縁性材料を用いることにより、無機固体電解質粉末と電子絶縁性材料とを含む混合物を用いて層を形成した後、電子絶縁性材料が溶融する温度まで容易に加熱することができ、この加熱により、溶融した充填材を毛細管現象によって無機固体電解質材料間の空隙へと移動させることができる。その後冷却して充填材を固化させることにより、無機固体電解質材料間の形状に沿って事実上隙間なく、充填材を埋め込んだ状態を作り出すことができる。
すなわち、本発明の全固体二次電池において、固体電解質層の充填材領域は、100℃において固体状でかつ200℃以下の温度領域で熱溶融する電子絶縁性材料の熱溶融物を用いて形成されたもの(すなわち熱溶融凝固物で形成されたもの)である。
ここで「電子絶縁性」とは、電子を通過させない性質をいう。本発明において「電子絶縁性材料」という場合、測定温度25℃において導電率が10−9S/cm以下の材料であることが好ましい。(Filler area)
In the present invention, the filler region does not simply have a particulate filler, but an electronically insulating material that is a filler along the shape between the inorganic solid electrolyte materials with virtually no gaps. ing. In order to realize such filling of the electronically insulating material, the electronically insulating material is a solid at 100 ° C. (that is, the melting point exceeds 100 ° C.), while it has a physical property of being thermally melted in a temperature range of 200 ° C. or lower. Use the one. "Thermal melting in the temperature range of 200 ° C. or lower" means that the thermal melting is performed in the temperature range of 200 ° C. or lower under 1 atm. By using such an electronically insulating material, after forming a layer using a mixture containing an inorganic solid electrolyte powder and an electronically insulating material, it can be easily heated to a temperature at which the electronically insulating material melts. By this heating, the molten filler can be moved to the voids between the inorganic solid electrolyte materials by capillarity. After that, by cooling and solidifying the filler, it is possible to create a state in which the filler is embedded with virtually no gap along the shape between the inorganic solid electrolyte materials.
That is, in the all-solid secondary battery of the present invention, the filler region of the solid electrolyte layer is formed by using a thermal melt of an electronically insulating material that is solid at 100 ° C. and thermally melts in a temperature region of 200 ° C. or lower. (Ie, one formed of a hot melt solidified product).
Here, "electron insulation" refers to a property that does not allow electrons to pass through. In the present invention, the term "electronically insulating material" is preferably a material having a conductivity of 10-9 S / cm or less at a measurement temperature of 25 ° C.
本発明において、充填材領域は電子絶縁性材料の他に、デンドライトの成長をブロック可能な他の材料を含んでもよい。すなわち、本発明において「電子絶縁性材料の熱溶融物を用いて形成された」とは、電子絶縁性材料のみを用いて形成された形態の他、電子絶縁性材料と、電子絶縁性材料以外の他の材料とを組合せて用いて形成された形態を含む意味である。他の材料として、例えば酸化アルミニウム、酸化ケイ素、窒化ホウ素、酸化セリウム、ダイヤモンド、ゼオライト等を挙げることができる。他の材料は通常は微粒子であり、その体積平均粒子径は1μm以下が好ましく、700nm以下がより好ましい。これらの材料を充填材領域に存在させることにより、熱溶融物が毛細管現象によって固体電解質間の隙間に染み込みやすくなり、デンドライトのブロック作用をより高めることができる。
充填材領域が電子絶縁性材料に加えて他の材料を含む場合、固体電解質層中において、無機固体電解質材料の含有量100質量部に対し、他の材料の含有量を15質量部以下とすることが好ましく、10質量部以下とすることがより好ましい。In the present invention, the filler region may include other materials capable of blocking the growth of dendrites, in addition to the electronically insulating material. That is, in the present invention, "formed by using a thermal melt of an electronically insulating material" means a form formed by using only an electronically insulating material, and other than an electronically insulating material and an electronically insulating material. It means to include a form formed by using in combination with other materials. Examples of other materials include aluminum oxide, silicon oxide, boron nitride, cerium oxide, diamond, zeolite and the like. The other material is usually fine particles, and the volume average particle diameter thereof is preferably 1 μm or less, more preferably 700 nm or less. By allowing these materials to exist in the filler region, the thermal melt easily permeates into the gaps between the solid electrolytes due to the capillary phenomenon, and the dendrite blocking action can be further enhanced.
When the filler region contains other materials in addition to the electronically insulating material, the content of the other material in the solid electrolyte layer is 15 parts by mass or less with respect to 100 parts by mass of the inorganic solid electrolyte material. It is preferably 10 parts by mass or less, and more preferably 10 parts by mass or less.
上記のような、無機固体電解質材料間の形状に沿って事実上隙間なく、電子絶縁性材料を含む充填材が埋め込まれた状態は、充填材領域のうち一辺が5μmの正方領域内に収まる充填材領域FR(この充填材領域FRの外周(電解質領域との境界)のすべてが5μmの正方領域内に収まることを意味する)を、固体電解質層の厚み方向に向けて平面視観察(固体電解質層の厚み方向に対して垂直な面を観察)した場合に、FRの面積FA(μm2)と、FRの外周長さFL(μm)との比が、FL/FA≧0.81を満たすことが好ましい。
この平面視観察では、固体電解質層を、走査型電子顕微鏡−エネルギー分散型X線分光法(SEM−EDX)を用いて倍率5000倍で観察して、1辺が5μmの正方領域内に収まる充填材領域FRを無作為に10個選抜する。これら10個の各充填材領域FRにおけるFL/FAを決定し、決定した10個のFL/FAの平均が0.81以上である場合に、FL/FA≧0.81を満たすものとする。なお、1つの、1辺が5μmの正方領域内において、測定する充填材領域の数は1つとする。FL/FA≧0.81を満たすことは、充填材領域が単なる粒子(球状)ではなく、充填材領域の外周が無機固体電解質材料間の形状に追従していることを示す指標となる。
FL/FAは1.0以上が好ましく、1.5以上がより好ましく、2.0以上がさらに好ましい。また、FL/FAは通常は100以下であり、50以下であってもよく、20以下であってもよく、10以下であってもよい。When the filler containing the electronically insulating material is embedded without any gap along the shape between the inorganic solid electrolyte materials as described above, the filler region is filled within a square region having a side of 5 μm. Observing the material region FR (meaning that the entire outer circumference (boundary with the electrolyte region) of the filler region FR is within a square region of 5 μm) in a plan view toward the thickness direction of the solid electrolyte layer (solid electrolyte). When observing a plane perpendicular to the thickness direction of the layer), the ratio of the FR area FA (μm 2 ) to the FR outer peripheral length FL (μm) satisfies FL / FA ≧ 0.81. Is preferable.
In this plan view, the solid electrolyte layer is observed at a magnification of 5000 times using a scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDX), and is filled within a square region having a side of 5 μm. Ten material area FRs are randomly selected. The FL / FA in each of these 10 filler region FRs is determined, and when the average of the determined 10 FL / FAs is 0.81 or more, FL / FA ≧ 0.81 is satisfied. The number of filler regions to be measured is one in one square region having a side of 5 μm. Satisfying FL / FA ≥ 0.81 is an index indicating that the filler region is not a mere particle (spherical) but the outer periphery of the filler region follows the shape between the inorganic solid electrolyte materials.
FL / FA is preferably 1.0 or more, more preferably 1.5 or more, and even more preferably 2.0 or more. Further, FL / FA is usually 100 or less, may be 50 or less, 20 or less, or 10 or less.
本発明において、固体電解質層の充填材領域を構成する電子絶縁性材料は、デンドライトの成長をブロックするために、固体状態においてデンドライトよりも硬い材料であることが好ましい。
上記電子絶縁性材料としては、硫黄、改質硫黄、ヨウ素、硫黄とヨウ素の混合物等を挙げることができ、なかでも硫黄及び/又は改質硫黄を好適に用いることができる。充填材として用いうる硫黄は単体硫黄(硫黄そのもののほか多量体で存在するものも含む。)を意味する。
また、改質硫黄は、硫黄と改質剤とを混練して得られるものである。例えば、純硫黄と改質添加剤であるオレフィン系化合物とを混練し、硫黄の一部を硫黄ポリマーに改質した改質硫黄を得ることができる。充填材領域に硫黄ないし改質硫黄が存在することにより、この充填材領域へと成長してきたデンドライト(アルカリ金属ないしアルカリ土類金属)を物理的にブロックすることができる。
また、デンドライトと硫黄とが接触することにより、デンドライトと硫黄との反応も生じ得る。例えば金属リチウムのデンドライトと硫黄とが接触すると、2Li+S→Li2Sの反応が生じ、デンドライトの成長が止まる。このような反応が生じると、充填材領域中には反応生成物も共存した状態となる。この反応生成物はデンドライト金属よりも硬い電子絶縁性の化合物であるため、デンドライトの成長をブロックすることができる。すなわち、上記充填材領域は、上記の反応により生じたアルカリ金属を含む化合物及び/又はアルカリ土類金属を含む化合物を含有する形態であることも好ましい。このような形態をとることにより、充填材領域の体積が広がり、充填材領域と電解質領域との間にわずかに残っていた空隙をより確実に塞ぐ効果も期待できる。In the present invention, the electronically insulating material constituting the filler region of the solid electrolyte layer is preferably a material harder than the dendrite in the solid state in order to block the growth of the dendrite.
Examples of the electronically insulating material include sulfur, modified sulfur, iodine, and a mixture of sulfur and iodine, and among them, sulfur and / or modified sulfur can be preferably used. Sulfur that can be used as a filler means elemental sulfur (including sulfur itself and those existing in multimers).
The modified sulfur is obtained by kneading sulfur and a modifier. For example, pure sulfur and an olefin compound which is a modifying additive can be kneaded to obtain modified sulfur in which a part of sulfur is modified into a sulfur polymer. The presence of sulfur or modified sulfur in the filler region can physically block the dendrites (alkali metals or alkaline earth metals) that have grown into the filler region.
In addition, the contact between the dendrite and sulfur may cause a reaction between the dendrite and sulfur. For example, the dendrites and the sulfur of the metal lithium is in contact, 2Li + S → Li 2 S reaction occurs, the growth of dendrite is stopped. When such a reaction occurs, the reaction product also coexists in the filler region. Since this reaction product is an electron-insulating compound that is harder than the dendrite metal, it can block the growth of dendrites. That is, it is also preferable that the filler region contains a compound containing an alkali metal and / or a compound containing an alkaline earth metal generated by the above reaction. By taking such a form, the volume of the filler region is expanded, and the effect of more reliably closing the gap slightly remaining between the filler region and the electrolyte region can be expected.
上記充填材領域は、有機バインダーを含有してもよい。有機バインダーを含有することにより、例えば全固体二次電池の製造を、電池シートを巻き取りながら製造するような場合においても、固体電解質と基材となる電極層や集電体との密着性を高めて固体電解質層の欠陥の発生を抑えることが可能となる。また、有機バインダーは、無機固体電解質同士の結着性等も高めることができ、よりまとまりのある層構成とすることができるため好ましい。 The filler region may contain an organic binder. By containing an organic binder, for example, even in the case of manufacturing an all-solid-state secondary battery while winding up a battery sheet, the adhesion between the solid electrolyte and the electrode layer or the current collector as the base material can be maintained. It is possible to suppress the occurrence of defects in the solid electrolyte layer. Further, the organic binder is preferable because it can enhance the binding property between the inorganic solid electrolytes and the like, and can form a more cohesive layer structure.
− 有機バインダー −
上記有機バインダーとしては有機ポリマーが挙げられる。例えば、以下に述べる樹脂からなる有機バインダーが好ましく使用される。− Organic binder −
Examples of the organic binder include organic polymers. For example, an organic binder made of the resin described below is preferably used.
含フッ素樹脂としては、例えば、ポリテトラフルオロエチレン(PTFE)、ポリビニレンジフルオリド(PVdF)、ポリビニレンジフルオリドとヘキサフルオロプロピレンとの共重合体(PVdF−HFP)が挙げられる。
炭化水素系熱可塑性樹脂としては、例えば、ポリエチレン、ポリプロピレン、スチレンブタジエンゴム(SBR)、水素添加スチレンブタジエンゴム(HSBR)、ブチレンゴム、アクリロニトリル−ブタジエンゴム、ポリブタジエン、ポリイソプレンが挙げられる。
アクリル樹脂としては、各種の(メタ)アクリルモノマー類、(メタ)アクリルアミドモノマー類、およびこれら樹脂を構成するモノマーの共重合体(好ましくは、アクリル酸とアクリル酸メチルとの共重合体)が挙げられる。
また、そのほかのビニル系モノマーとの共重合体(コポリマー)も好適に用いられる。例えば、(メタ)アクリル酸メチルとスチレンとの共重合体、(メタ)アクリル酸メチルとアクリロニトリルとの共重合体、(メタ)アクリル酸ブチルとアクリロニトリルとスチレンとの共重合体が挙げられる。本願明細書において、コポリマーは、統計コポリマーおよび周期コポリマーのいずれでもよく、ブロックコポリマーが好ましい。
その他の樹脂としては例えばポリウレタン樹脂、ポリウレア樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリエステル樹脂、ポリエーテル樹脂、ポリカーボネート樹脂、セルロース誘導体樹脂等が挙げられる。
これらは1種を単独で用いても、2種以上を組み合わせて用いてもよい。Examples of the fluororesin include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP).
Examples of the hydrocarbon-based thermoplastic resin include polyethylene, polypropylene, styrene-butadiene rubber (SBR), hydrogenated styrene-butadiene rubber (HSBR), butylene rubber, acrylonitrile-butadiene rubber, polybutadiene, and polyisoprene.
Examples of the acrylic resin include various (meth) acrylic monomers, (meth) acrylamide monomers, and copolymers of the monomers constituting these resins (preferably copolymers of acrylic acid and methyl acrylate). Be done.
Further, a copolymer (copolymer) with other vinyl-based monomers is also preferably used. For example, a copolymer of methyl (meth) acrylate and styrene, a copolymer of methyl (meth) acrylate and acrylonitrile, and a copolymer of butyl (meth) acrylate, acrylonitrile and styrene can be mentioned. In the present specification, the copolymer may be either a statistical copolymer or a periodic copolymer, and a block copolymer is preferable.
Examples of other resins include polyurethane resin, polyurea resin, polyamide resin, polyimide resin, polyester resin, polyether resin, polycarbonate resin, cellulose derivative resin and the like.
These may be used individually by 1 type, or may be used in combination of 2 or more type.
上記有機バインダーは、強い結着性を示す(集電体からの剥離抑制および、固体界面の結着によるサイクル寿命の向上)ため、上述のアクリル樹脂、ポリウレタン樹脂、ポリウレア樹脂、ポリイミド樹脂、含フッ素樹脂および炭化水素系熱可塑性樹脂からなる群から選択される少なくとも1種であることが好ましい。 Since the organic binder exhibits strong binding properties (suppression of peeling from the current collector and improvement of cycle life due to binding at the solid interface), the above-mentioned acrylic resin, polyurethane resin, thermoplastic resin, polyimide resin, and fluorine-containing binder are used. It is preferably at least one selected from the group consisting of resins and hydrocarbon-based thermoplastic resins.
上記有機バインダーは、粒子表面への濡れ性や吸着性を高めるため、極性基を有することが好ましい。極性基とは、ヘテロ原子を含む1価の基、例えば、酸素原子、窒素原子および硫黄原子のいずれかと水素原子が結合した構造を含む1価の基が好ましく、具体例としては、カルボキシ基、ヒドロキシ基、アミノ基、リン酸基およびスルホ基等が挙げられる。 The organic binder preferably has a polar group in order to enhance the wettability and adsorptivity to the particle surface. The polar group is preferably a monovalent group containing a hetero atom, for example, a monovalent group containing a structure in which a hydrogen atom is bonded to any one of an oxygen atom, a nitrogen atom and a sulfur atom, and specific examples thereof include a carboxy group. Examples thereof include a hydroxy group, an amino group, a phosphoric acid group and a sulfo group.
上記有機バインダーの平均粒子径は、通常10nm〜30μmが好ましく、10〜1000nmのナノ粒子がより好ましい。 The average particle size of the organic binder is usually preferably 10 nm to 30 μm, and more preferably nanoparticles of 10 to 1000 nm.
上記有機バインダーの重量平均分子量(Mw)は10,000以上が好ましく、20,000以上がより好ましく、30,000以上がさらに好ましい。上限としては、1,000,000以下が好ましく、200,000以下がより好ましく、100,000以下がさらに好ましい。
上記充填材領域が有機バインダーを含む場合、固体電解質層中の有機バインダーの含有量として、1〜10質量%が好ましく、2〜5質量%がより好ましい。The weight average molecular weight (Mw) of the organic binder is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more. The upper limit is preferably 1,000,000 or less, more preferably 200,000 or less, still more preferably 100,000 or less.
When the filler region contains an organic binder, the content of the organic binder in the solid electrolyte layer is preferably 1 to 10% by mass, more preferably 2 to 5% by mass.
本発明の全固体二次電池において、固体電解質層の充填材領域は、固体電解質層と正極活物質層との界面には存在しないことが好ましい。電子絶縁性材料(例えば硫黄及び/又は改質硫黄)と正極活物質層とが接触すると、電池容量が低下する場合がある。
本発明において、充填材領域が固体電解質層と正極活物質層との界面に存在しない、とは、充填材領域が固体電解質層と正極活物質層との界面に事実上存在しないことを意味する。すなわち、電池容量を大きく低下させないレベルで、充填材領域が固体電解質層と正極活物質層との界面に存在する形態を排除するものではない。In the all-solid-state secondary battery of the present invention, it is preferable that the filler region of the solid electrolyte layer does not exist at the interface between the solid electrolyte layer and the positive electrode active material layer. Contact between the electronically insulating material (eg sulfur and / or modified sulfur) and the cathode active material layer may reduce the battery capacity.
In the present invention, the fact that the filler region does not exist at the interface between the solid electrolyte layer and the positive electrode active material layer means that the filler region does not substantially exist at the interface between the solid electrolyte layer and the positive electrode active material layer. .. That is, it does not exclude the form in which the filler region exists at the interface between the solid electrolyte layer and the positive electrode active material layer at a level that does not significantly reduce the battery capacity.
本発明の二次電池を構成する固体電解質層中、後述する無機固体電解質材料の含有量を100体積%とした場合、電子絶縁性材料の含有量は15体積%未満が好ましく、12体積%未満がより好ましく、10体積%未満であることも好ましい。電子絶縁性材料をこのような含有量とすることにより、イオンの伝導性をあまり損なわずに、デンドライトの成長を効果的にブロックすることができる。固体電解質層中の無機固体電解質材料の含有量を100体積%とした場合、電子絶縁性材料の含有量は、通常は2体積%以上であり、5体積%以上が好ましく、7体積%以上がより好ましい。 When the content of the inorganic solid electrolyte material described later in the solid electrolyte layer constituting the secondary battery of the present invention is 100% by volume, the content of the electronically insulating material is preferably less than 15% by volume, preferably less than 12% by volume. Is more preferable, and it is also preferable that it is less than 10% by volume. By setting the content of the electronically insulating material to such a content, it is possible to effectively block the growth of dendrites without significantly impairing the conductivity of ions. When the content of the inorganic solid electrolyte material in the solid electrolyte layer is 100% by volume, the content of the electronically insulating material is usually 2% by volume or more, preferably 5% by volume or more, and 7% by volume or more. More preferred.
(電解質領域)
本発明の固体電解質層を構成する無機固体電解質材料は、無機固体電解質であるか、あるいは無機固体電解質と活物質との混合物であり、通常は無機固体電解質からなる。無機固体電解質の好ましい形態について以下に説明する。なお、活物質については後述する。(Electrolyte area)
The inorganic solid electrolyte material constituting the solid electrolyte layer of the present invention is an inorganic solid electrolyte or a mixture of an inorganic solid electrolyte and an active material, and is usually composed of an inorganic solid electrolyte. Preferred forms of the inorganic solid electrolyte will be described below. The active material will be described later.
無機固体電解質とは、無機の固体電解質のことであり、固体電解質とは、その内部においてイオンを移動させることができる固体状の電解質のことである。主たるイオン伝導性材料として有機物を含むものではないことから、有機固体電解質(ポリエチレンオキシド(PEO)などに代表される高分子電解質、リチウムビス(トリフルオロメタンスルホニル)イミド(LiTFSI)などに代表される有機電解質塩)とは明確に区別される。また、無機固体電解質は定常状態では固体であるため、通常カチオンおよびアニオンに解離または遊離していない。この点で、電解液やポリマー中でカチオンおよびアニオンが解離または遊離している無機電解質塩(LiPF6、LiBF4、LiFSI、LiClなど)とも明確に区別される。無機固体電解質は周期律表第1族または第2族に属する金属のイオンの伝導性を有するものであれば特に限定されず電子伝導性を有さないものが一般的である。The inorganic solid electrolyte is an inorganic solid electrolyte, and the solid electrolyte is a solid electrolyte capable of transferring ions inside the solid electrolyte. Since it does not contain organic substances as the main ionic conductive material, it is an organic solid electrolyte (polymer electrolyte typified by polyethylene oxide (PEO), organic typified by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), etc. It is clearly distinguished from electrolyte salts). In addition, since the inorganic solid electrolyte is solid in the steady state, it is usually not dissociated or liberated into cations and anions. In this respect, it is also clearly distinguished from inorganic electrolyte salts (LiPF 6 , LiBF 4 , LiFSI, LiCl, etc.) in which cations and anions are dissociated or released in the electrolyte or polymer. The inorganic solid electrolyte is not particularly limited as long as it has the ionic conductivity of a metal belonging to Group 1 or
本発明において、無機固体電解質は、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する。上記無機固体電解質は、この種の製品に適用される固体電解質材料を適宜選定して用いることができる。無機固体電解質として、一般的には(i)硫化物系無機固体電解質及び/又は(ii)酸化物系無機固体電解質が用いられる。
In the present invention, the inorganic solid electrolyte has ionic conductivity of a metal belonging to Group 1 or
(i)硫化物系無機固体電解質
硫化物系無機固体電解質は、硫黄原子(S)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が好ましい。硫化物系無機固体電解質は、元素として少なくともLi、SおよびPを含有し、リチウムイオン伝導性を有しているものが好ましいが、目的または場合に応じて、Li、SおよびP以外の他の元素を含んでもよい。
例えば下記式(I)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。
La1Mb1Pc1Sd1Ae1 式(I)
式中、LはLi、NaおよびKから選択される元素を示し、Liが好ましい。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。Aは、I、Br、Cl及びFから選択される元素を示す。a1〜e1は各元素の組成比を示し、a1:b1:c1:d1:e1は1〜12:0〜5:1:2〜12:0〜10を満たす。a1はさらに、1〜9が好ましく、1.5〜7.5がより好ましい。b1は0〜3が好ましい。d1はさらに、2.5〜10が好ましく、3.0〜8.5がより好ましい。e1はさらに、0〜5が好ましく、0〜3がより好ましい。(I) Sulfide-based inorganic solid electrolyte The sulfide-based inorganic solid electrolyte contains a sulfur atom (S), has ionic conductivity of a metal belonging to Group 1 or
For example, a lithium ion conductive inorganic solid electrolyte satisfying the composition represented by the following formula (I) can be mentioned.
La1 M b1 P c1 S d1 A e1 equation (I)
In the formula, L represents an element selected from Li, Na and K, with Li being preferred. M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al and Ge. A represents an element selected from I, Br, Cl and F. a1 to e1 indicate the composition ratio of each element, and a1: b1: c1: d1: e1 satisfy 1 to 12:00 to 5: 1: 2 to 12:00 to 10. Further, a1 is preferably 1 to 9, and more preferably 1.5 to 7.5. b1 is preferably 0 to 3. d1 is further preferably 2.5 to 10 and more preferably 3.0 to 8.5. e1 is further preferably 0 to 5, more preferably 0 to 3.
各元素の組成比は、下記のように、硫化物系無機固体電解質を製造する際の原料化合物の配合量を調整することにより制御できる。 The composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte as described below.
硫化物系無機固体電解質は、非結晶(ガラス)であっても結晶化(ガラスセラミックス化)していてもよく、一部のみが結晶化していてもよい。例えば、Li、PおよびSを含有するLi−P−S系ガラス、またはLi、PおよびSを含有するLi−P−S系ガラスセラミックスを用いることができる。
硫化物系無機固体電解質は、例えば硫化リチウム(Li2S)、硫化リン(例えば五硫化二燐(P2S5))、単体燐、単体硫黄、硫化ナトリウム、硫化水素、ハロゲン化リチウム(例えばLiI、LiBr、LiCl)及び上記Mであらわされる元素の硫化物(例えばSiS2、SnS、GeS2)の中の少なくとも2つ以上の原料の反応により製造することができる。The sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass-ceramic), or only a part thereof may be crystallized. For example, Li-PS-based glass containing Li, P and S, or Li-PS-based glass ceramics containing Li, P and S can be used.
Sulfide-based inorganic solid electrolytes include, for example, lithium sulfide (Li 2 S), phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), simple phosphorus, simple sulfur, sodium sulfide, hydrogen sulfide, and lithium halide (for example). It can be produced by the reaction of at least two or more raw materials in sulfides of LiI, LiBr, LiCl) and the element represented by M (for example, SiS 2 , SnS, GeS 2).
Li−P−S系ガラスおよびLi−P−S系ガラスセラミックスにおける、Li2SとP2S5との比率は、Li2S:P2S5のモル比で、好ましくは60:40〜90:10、より好ましくは68:32〜78:22である。Li2SとP2S5との比率をこの範囲にすることにより、リチウムイオン伝導度を高いものとすることができる。具体的には、リチウムイオン伝導度を好ましくは1×10−4S/cm以上、より好ましくは1×10−3S/cm以上とすることができる。上限は特にないが、1×10−1S/cm以下であることが実際的である。The ratio of Li 2 S to P 2 S 5 in Li-PS-based glass and Li-PS-based glass ceramics is a molar ratio of Li 2 S: P 2 S 5, preferably 60:40 to It is 90:10, more preferably 68:32 to 78:22. By setting the ratio of Li 2 S and P 2 S 5 in this range, the lithium ion conductivity can be made high. Specifically, the lithium ion conductivity can be preferably 1 × 10 -4 S / cm or more, and more preferably 1 × 10 -3 S / cm or more. There is no particular upper limit, but it is practical that it is 1 × 10 -1 S / cm or less.
具体的な硫化物系無機固体電解質の例として、原料の組み合わせ例を下記に示す。たとえばLi2S−P2S5、Li2S−P2S5−LiCl、Li2S−P2S5−H2S、Li2S−P2S5−H2S−LiCl、Li2S−LiI−P2S5、Li2S−LiI−Li2O−P2S5、Li2S−LiBr−P2S5、Li2S−Li2O−P2S5、Li2S−Li3PO4−P2S5、Li2S−P2S5−P2O5、Li2S−P2S5−SiS2、Li2S−P2S5−SiS2−LiCl、Li2S−P2S5−SnS、Li2S−P2S5−Al2S3、Li2S−GeS2、Li2S−GeS2−ZnS、Li2S−Ga2S3、Li2S−GeS2−Ga2S3、Li2S−GeS2−P2S5、Li2S−GeS2−Sb2S5、Li2S−GeS2−Al2S3、Li2S−SiS2、Li2S−Al2S3、Li2S−SiS2−Al2S3、Li2S−SiS2−P2S5、Li2S−SiS2−P2S5−LiI、Li2S−SiS2−LiI、Li2S−SiS2−Li4SiO4、Li2S−SiS2−Li3PO4、Li10GeP2S12などが挙げられる。ただし、各原料の混合比は問わない。このような原料組成物を用いて硫化物系無機固体電解質材料を合成する方法としては、例えば非晶質化法を挙げることができる。非晶質化法としては、例えば、メカニカルミリング法、溶液法および溶融急冷法を挙げられる。常温での処理が可能になり、製造工程の簡略化を図ることができるからである。As an example of a specific sulfide-based inorganic solid electrolyte, a combination example of raw materials is shown below. For example Li 2 S-P 2 S 5 ,
(ii)酸化物系無機固体電解質
酸化物系無機固体電解質は、酸素原子(O)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化合物が好ましい。(Ii) Oxide-based Inorganic Solid Electrolyte The oxide-based inorganic solid electrolyte contains an oxygen atom (O), has ionic conductivity of a metal belonging to Group 1 or
具体的な化合物例としては、例えばLixaLayaTiO3〔xa=0.3〜0.7、ya=0.3〜0.7〕(LLT)、LixbLaybZrzbMbb mbOnb(Mbb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xbは5≦xb≦10を満たし、ybは1≦yb≦4を満たし、zbは1≦zb≦4を満たし、mbは0≦mb≦2を満たし、nbは5≦nb≦20を満たす。)、LixcBycMcc zcOnc(Mcc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xcは0≦xc≦5を満たし、ycは0≦yc≦1を満たし、zcは0≦zc≦1を満たし、ncは0≦nc≦6を満たす。)、Lixd(Al,Ga)yd(Ti,Ge)zdSiadPmdOnd(ただし、1≦xd≦3、0≦yd≦1、0≦zd≦2、0≦ad≦1、1≦md≦7、3≦nd≦13)、Li(3−2xe)Mee xeDeeO(xeは0以上0.1以下の数を表し、Meeは2価の金属原子を表す。Dee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。)、LixfSiyfOzf(1≦xf≦5、0<yf≦3、1≦zf≦10)、LixgSygOzg(1≦xg≦3、0<yg≦2、1≦zg≦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、Li1+xh+yh(Al,Ga)xh(Ti,Ge)2−xhSiyhP3−yhO12(ただし、0≦xh≦1、0≦yh≦1)、ガーネット型結晶構造を有するLi7La3Zr2O12(LLZ)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、LiPOD1(D1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、LiA1ON(A1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 examples of the compound include, for example, Li xa La ya TiO 3 [xa = 0.3 to 0.7, ya = 0.3 to 0.7] (LLT), Li xb La yb Zr zb M bb mb O. nb (M bb is at least one element of Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, Sn, xb satisfies 5 ≦ xb ≦ 10, and yb is 1 ≦ yb. ≦ 4 was filled, zb satisfies 1 ≦ zb ≦ 4, mb satisfies 0 ≦ mb ≦ 2, nb satisfies 5 ≦ nb ≦ 20.), Li xc B yc M cc zc O nc (M cc is At least one or more elements of C, S, Al, Si, Ga, Ge, In, Sn, xc satisfies 0 ≦ xc ≦ 5, yc satisfies 0 ≦ yc ≦ 1, and zc satisfies 0 ≦ zc ≦. met 1, nc satisfies 0 ≦ nc ≦ 6.), Li xd (Al, Ga) yd (Ti, Ge) zd Si ad P md O nd ( provided that, 1 ≦ xd ≦ 3,0 ≦ yd ≦ 1 , 0 ≦ zd ≦ 2,0 ≦ ad ≦ 1,1 ≦ md ≦ 7,3 ≦ nd ≦ 13), the number of Li (3-2xe) M ee xe D ee O (xe 0 to 0.1 represents, M ee is .D ee representing the divalent metal atom represent a combination of a halogen atom, or two or more halogen atoms.), Li xf Si yf O zf (1 ≦ xf ≦ 5,0 <yf ≦ 3 , 1 ≦ zf ≦ 10), Li xg S yg O zg (1 ≦ xg ≦ 3,0 <yg ≦ 2,1 ≦ zg ≦ 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 is w <1), LISION (Lithium superionic compound) ) Type crystal structure Li 3.5 Zn 0.25 GeO 4 , La 0.55 Li 0.35 TIO 3 having a perovskite type crystal structure, LiTi 2 P 3 having a NASICON (Naturium superionic compound) type crystal structure O 12 , Li 1 + xh + yh (Al, Ga) xh (Ti, Ge) 2-xh Si yh P 3-yh O 12 (however, 0 ≦ xh ≦ 1, 0 ≦ yh ≦ 1), Li having a garnet-type crystal structure 7 La 3 Zr 2 O 12 (LLZ) and the like can be mentioned. Phosphorus compounds containing Li, P and O are also desirable. For example, lithium phosphate (Li 3 PO 4 ), LiPON in which a part of oxygen of lithium phosphate is replaced with nitrogen, LiPOD 1 (D 1 is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr. , Nb, Mo, Ru, Ag, Ta, W, Pt, Au and the like (at least one selected) and the like. Further, LiA 1 ON (A 1 is at least one selected from Si, B, Ge, Al, C, Ga and the like) and the like can also be preferably used.
無機固体電解質の粒子径(体積平均粒子径)は特に限定されないが、0.01μm以上であることが好ましく、0.1μm以上であることがより好ましい。上限としては、100μm以下であることが好ましく、50μm以下であることがより好ましい。なお、無機固体電解質粒子の平均粒子径の測定は、以下の手順で行う。無機固体電解質粒子を、水(水に不安定な物質の場合はヘプタン)を用いて20mlサンプル瓶中で1質量%の分散液を希釈調整する。希釈後の分散試料は、1kHzの超音波を10分間照射し、その直後に試験に使用する。この分散液試料を用い、レーザ回折/散乱式粒度分布測定装置LA−920(HORIBA社製)を用いて、温度25℃で測定用石英セルを使用してデータ取り込みを50回行い、体積平均粒子径を得る。その他の詳細な条件等は必要によりJISZ8828:2013「粒子径解析−動的光散乱法」の記載を参照する。1水準につき5つの試料を作製しその平均値を採用する。 The particle size (volume average particle size) of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 μm or more, and more preferably 0.1 μm or more. The upper limit is preferably 100 μm or less, and more preferably 50 μm or less. The average particle size of the inorganic solid electrolyte particles is measured by the following procedure. The inorganic solid electrolyte particles are diluted and adjusted by 1% by mass of a dispersion in a 20 ml sample bottle with water (heptane in the case of a water-unstable substance). The diluted dispersed sample is irradiated with 1 kHz ultrasonic waves for 10 minutes, and immediately after that, it is used for the test. Using this dispersion sample, data was captured 50 times using a laser diffraction / scattering particle size distribution measuring device LA-920 (manufactured by HORIBA) at a temperature of 25 ° C. using a measuring quartz cell, and the volume average particles were used. Get the diameter. For other detailed conditions and the like, refer to the description of JISZ8828: 2013 "Particle size analysis-Dynamic light scattering method" as necessary. Five samples are prepared for each level and the average value is adopted.
本発明において無機固体電解質材料は、大粒径の粒子とそれより小粒径の粒子とが混在し、[大粒径粒子の粒子径]>4×[小粒径粒子の粒子径]を満たす粒子が存在する粒度分布を有することが好ましい。このような粒度分布を有することにより、上述のFL/FAをより高めることができる。すなわち、無機固体電解質材料間の空隙をより低減することができ、かつ、この空隙に充填材が、より隙間なく充填された形態とすることができる。 In the present invention, the inorganic solid electrolyte material is a mixture of large particle size particles and smaller particle size particles, and satisfies [particle size of large particle size particles]> 4 × [particle size of small particle size particles]. It is preferable to have a particle size distribution in which particles are present. By having such a particle size distribution, the above-mentioned FL / FA can be further enhanced. That is, the gaps between the inorganic solid electrolyte materials can be further reduced, and the gaps can be filled with the filler without any gaps.
<正極活物質層>
上記正極活物質層4は、上述した無機固体電解質と、正極活物質とを含有する。
正極活物質の好ましい形態について説明する。<Cathode active material layer>
The positive electrode active material layer 4 contains the above-mentioned inorganic solid electrolyte and the positive electrode active material.
A preferable form of the positive electrode active material will be described.
(正極活物質)
正極活物質は、可逆的にリチウムイオンを挿入および放出できるものが好ましい。その材料は、上記特性を有するものであれば、特に制限はなく、遷移金属酸化物や、有機物、硫黄などのLiと複合化できる元素や硫黄と金属の複合物などでもよい。
中でも、正極活物質としては、遷移金属酸化物を用いることが好ましく、遷移金属元素Ma(Co、Ni、Fe、Mn、CuおよびVから選択される1種以上の元素)を有する遷移金属酸化物がより好ましい。また、この遷移金属酸化物に元素Mb(リチウム以外の金属周期律表の第1(Ia)族の元素、第2(IIa)族の元素、Al、Ga、In、Ge、Sn、Pb、Sb、Bi、Si、PまたはBなどの元素)を混合してもよい。混合量としては、遷移金属元素Maの量(100mol%)に対して0〜30mol%が好ましい。Li/Maのモル比が0.3〜2.2になるように混合して合成されたものが、より好ましい。
遷移金属酸化物の具体例としては、(MA)層状岩塩型構造を有する遷移金属酸化物、(MB)スピネル型構造を有する遷移金属酸化物、(MC)リチウム含有遷移金属リン酸化合物、(MD)リチウム含有遷移金属ハロゲン化リン酸化合物および(ME)リチウム含有遷移金属ケイ酸化合物等が挙げられる。(Positive electrode active material)
The positive electrode active material is preferably one capable of reversibly inserting and releasing lithium ions. The material is not particularly limited as long as it has the above-mentioned properties, and may be a transition metal oxide, an organic substance, an element that can be composited with Li such as sulfur, or a composite of sulfur and a metal.
Among them, as the positive electrode active material, a transition metal oxide having preferably used a transition metal oxide, a transition metal element M a a (Co, Ni, Fe, Mn , 1 or more elements selected from Cu and V) The thing is more preferable. Further, the 1 (Ia) group elements of the transition metal oxide to elemental M b (Table metal periodic other than lithium, the elements of the 2 (IIa) group, Al, Ga, In, Ge , Sn, Pb, Elements such as Sb, Bi, Si, P or B) may be mixed. The mixing amount, 0~30mol% is preferred for the amount of the transition metal element M a (100mol%). It is more preferable that the mixture is synthesized by mixing so that the molar ratio of Li / Ma is 0.3 to 2.2.
Specific examples of the transition metal oxide include (MA) a transition metal oxide having a layered rock salt type structure, (MB) a transition metal oxide having a spinel type structure, (MC) a lithium-containing transition metal phosphoric acid compound, and (MD). ) Lithium-containing transition metal halide phosphate compounds, (ME) lithium-containing transition metal silicic acid compounds, and the like.
(MA)層状岩塩型構造を有する遷移金属酸化物の具体例として、LiCoO2(コバルト酸リチウム[LCO])、LiNi2O2(ニッケル酸リチウム)LiNi0.85Co0.10Al0.05O2(ニッケルコバルトアルミニウム酸リチウム[NCA])、LiNi1/3Co1/3Mn1/3O2(ニッケルマンガンコバルト酸リチウム[NMC])およびLiNi0.5Mn0.5O2(マンガンニッケル酸リチウム)が挙げられる。
(MB)スピネル型構造を有する遷移金属酸化物の具体例として、LiMn2O4(LMO)、LiCoMnO4、Li2FeMn3O8、Li2CuMn3O8、Li2CrMn3O8およびLi2NiMn3O8が挙げられる。 (MC)リチウム含有遷移金属リン酸化合物としては、例えば、LiFePO4およびLi3Fe2(PO4)3等のオリビン型リン酸鉄塩、LiFeP2O7等のピロリン酸鉄類、LiCoPO4等のリン酸コバルト類ならびにLi3V2(PO4)3(リン酸バナジウムリチウム)等の単斜晶ナシコン型リン酸バナジウム塩が挙げられる。
(MD)リチウム含有遷移金属ハロゲン化リン酸化合物としては、例えば、Li2FePO4F等のフッ化リン酸鉄塩、Li2MnPO4F等のフッ化リン酸マンガン塩およびLi2CoPO4F等のフッ化リン酸コバルト類が挙げられる。
(ME)リチウム含有遷移金属ケイ酸化合物としては、例えば、Li2FeSiO4、Li2MnSiO4およびLi2CoSiO4等が挙げられる。
本発明では、(MA)層状岩塩型構造を有する遷移金属酸化物が好ましく、LCO、LMO、NCA又はNMCがより好ましい。(MA) Specific examples of transition metal oxides having a layered rock salt structure include LiCoO 2 (lithium cobalt oxide [LCO]) and LiNi 2 O 2 (lithium nickel oxide) LiNi 0.85 Co 0.10 Al 0.05. O 2 (Lithium Nickel Cobalt Oxide [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (Lithium Nickel Manganese Cobalt Oxide [NMC]) and LiNi 0.5 Mn 0.5 O 2 (Manganese) Lithium nickel oxide).
(MB) Specific examples of the transition metal oxide having a spinel structure, LiMn 2 O 4 (LMO) , LiCoMnO 4,
(MD) as the lithium-containing transition metal halogenated phosphate compound, for example,
Examples of the (ME) lithium-containing transition metal silicic acid compound include Li 2 FeSiO 4 , Li 2 MnSiO 4, and Li 2 CoSiO 4 .
In the present invention, a transition metal oxide having a (MA) layered rock salt type structure is preferable, and LCO, LMO, NCA or NMC is more preferable.
正極活物質の形状は特に制限されないが粒子状が好ましい。正極活物質の体積平均粒子径(球換算平均粒子径)は特に限定されない。例えば、0.1〜50μmとすることができる。正極活物質を所定の粒子径にするには、通常の粉砕機や分級機を用いればよい。焼成法によって得られた正極活物質は、水、酸性水溶液、アルカリ性水溶液、有機溶剤にて洗浄した後使用してもよい。正極活物質粒子の体積平均粒子径(球換算平均粒子径)は、レーザ回折/散乱式粒度分布測定装置LA−920(商品名、HORIBA社製)を用いて測定することができる。 The shape of the positive electrode active material is not particularly limited, but is preferably in the form of particles. The volume average particle size (sphere-equivalent average particle size) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 μm. In order to make the positive electrode active material have a predetermined particle size, a normal crusher or classifier may be used. The positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent. The volume average particle size (sphere-equivalent average particle size) of the positive electrode active material particles can be measured using a laser diffraction / scattering type particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA).
上記正極活物質は、1種を単独で用いても、2種以上を組み合わせて用いてもよい。
正極活物質層を形成する場合、正極活物質層の単位面積(cm2)当たりの正極活物質の質量(mg)(目付量)は特に限定されるものではない。設計された電池容量に応じて、適宜に決めることができる。The positive electrode active material may be used alone or in combination of two or more.
When forming the positive electrode active material layer, the mass (mg) (grain amount) of the positive electrode active material per unit area (cm 2) of the positive electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity.
正極活物質の、固体電解質組成物中における含有量は、特に限定されず、固形分100質量%において、10〜95質量%が好ましく、30〜90質量%がより好ましく、50〜85質量がさらに好ましく、55〜80質量%が特に好ましい。 The content of the positive electrode active material in the solid electrolyte composition is not particularly limited, and is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and further 50 to 85% by mass based on 100% by mass of the solid content. It is preferable, and 55 to 80% by mass is particularly preferable.
<負極活物質層>
上記負極活物質層2は、上述した無機固体電解質と、負極活物質とを含有する。なお、上述した通り、本発明の全固体二次電池は負極活物質層を予め形成しない形態とすることも好ましい。
負極活物質の好ましい形態について説明する。<Negative electrode active material layer>
The negative electrode
A preferable form of the negative electrode active material will be described.
(負極活物質)
負極活物質は、可逆的にリチウムイオンを挿入および放出できるものが好ましい。その材料は、上記特性を有するものであれば、特に制限はなく、炭素質材料、酸化錫等の金属酸化物、酸化ケイ素、金属複合酸化物、リチウム単体およびリチウムアルミニウム合金等のリチウム合金、並びに、Sn、Si、AlおよびIn等のリチウムと合金形成可能な金属等が挙げられる。中でも、炭素質材料又はリチウム複合酸化物が信頼性の点から好ましく用いられる。また、金属複合酸化物としては、リチウムを吸蔵および放出可能であることが好ましい。その材料は、特には制限されないが、構成成分としてチタン及び/又はリチウムを含有していることが、高電流密度充放電特性の観点で好ましい。(Negative electrode active material)
The negative electrode active material is preferably one capable of reversibly inserting and releasing lithium ions. The material is not particularly limited as long as it has the above characteristics, and is a carbonaceous material, a metal oxide such as tin oxide, a silicon oxide, a metal composite oxide, a lithium alloy such as lithium simple substance and a lithium aluminum alloy, and a lithium alloy. , Sn, Si, Al, In and other metals that can be alloyed with lithium. Of these, carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of reliability. Further, as the metal composite oxide, it is preferable that lithium can be occluded and released. The material is not particularly limited, but it is preferable that the material contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
負極活物質として用いられる炭素質材料とは、実質的に炭素からなる材料である。例えば、石油ピッチ、アセチレンブラック(AB)等のカーボンブラック、黒鉛(天然黒鉛、気相成長黒鉛等の人造黒鉛等)、及びPAN(ポリアクリロニトリル)系の樹脂やフルフリルアルコール樹脂等の各種の合成樹脂を焼成した炭素質材料を挙げることができる。さらに、PAN系炭素繊維、セルロース系炭素繊維、ピッチ系炭素繊維、気相成長炭素繊維、脱水PVA(ポリビニルアルコール)系炭素繊維、リグニン炭素繊維、ガラス状炭素繊維および活性炭素繊維等の各種炭素繊維類、メソフェーズ微小球体、グラファイトウィスカーならびに平板状の黒鉛等を挙げることもできる。 The carbonaceous material used as the negative electrode active material is a material substantially composed of carbon. For example, various synthesis of petroleum pitch, carbon black such as acetylene black (AB), graphite (artificial graphite such as natural graphite and vapor-grown graphite), and PAN (polyacrylonitrile) -based resin and furfuryl alcohol resin. A carbonaceous material obtained by calcining a resin can be mentioned. Further, various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-phase-grown carbon fiber, dehydrated PVA (polypoly alcohol) -based carbon fiber, lignin carbon fiber, graphitic carbon fiber and activated carbon fiber. Kind, mesophase microspheres, graphite whisker, flat graphite and the like can also be mentioned.
負極活物質として適用される金属酸化物及び金属複合酸化物としては、特に非晶質酸化物が好ましく、さらに金属元素と周期律表第16族の元素との反応生成物であるカルコゲナイトも好ましく用いられる。ここでいう非晶質とは、CuKα線を用いたX線回折法で、2θ値で20°〜40°の領域に頂点を有するブロードな散乱帯を有するものを意味し、結晶性の回折線を有してもよい。 As the metal oxide and the metal composite oxide applied as the negative electrode active material, an amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. Be done. Amorphous here means an X-ray diffraction method using CuKα rays, which has a broad scattering band having an apex in a region of 20 ° to 40 ° in 2θ value, and is a crystalline diffraction line. May have.
上記非晶質酸化物及びカルコゲナイドからなる化合物群の中でも、半金属元素の非晶質酸化物、及びカルコゲナイドがより好ましく、周期律表第13(IIIB)族〜15(VB)族の元素、Al、Ga、Si、Sn、Ge、Pb、SbおよびBiの1種単独あるいはそれらの2種以上の組み合わせからなる酸化物、ならびにカルコゲナイドが特に好ましい。好ましい非晶質酸化物及びカルコゲナイドの具体例としては、例えば、Ga2O3、SiO、GeO、SnO、SnO2、PbO、PbO2、Pb2O3、Pb2O4、Pb3O4、Sb2O3、Sb2O4、Sb2O8Bi2O3、Sb2O8Si2O3、Bi2O4、SnSiO3、GeS、SnS、SnS2、PbS、PbS2、Sb2S3、Sb2S5およびSnSiS3が好ましく挙げられる。また、これらは、酸化リチウムとの複合酸化物、例えば、Li2SnO2であってもよい。Among the compound group consisting of the amorphous oxide and the chalcogenide, the amorphous oxide of the metalloid element and the chalcogenide are more preferable, and the elements of the groups 13 (IIIB) to 15 (VB) of the periodic table, Al. , Ga, Si, Sn, Ge, Pb, Sb and Bi alone or in combination of two or more oxides, and chalcogenides are particularly preferred. Specific examples of preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 8 Bi 2 O 3 , Sb 2 O 8 Si 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 and SnSi S 3 are preferred. Further, these may be a composite oxide with lithium oxide, for example, Li 2 SnO 2 .
負極活物質はチタン原子を含有することも好ましい。より具体的にはLi4Ti5O12(チタン酸リチウム[LTO])がリチウムイオンの吸蔵放出時の体積変動が小さいことから急速充放電特性に優れ、電極の劣化が抑制されリチウムイオン二次電池の寿命向上が可能となる点で好ましい。It is also preferable that the negative electrode active material contains a titanium atom. More specifically, Li 4 Ti 5 O 12 (lithium titanate [LTO]) has excellent rapid charge / discharge characteristics due to small volume fluctuations during storage and release of lithium ions, and electrode deterioration is suppressed and lithium ion secondary It is preferable in that the life of the battery can be improved.
本発明においては、Si系の負極を適用することもまた好ましい。一般的にSi負極は、炭素負極(黒鉛およびアセチレンブラックなど)に比べて、より多くのLiイオンを吸蔵できる。すなわち、単位質量あたりのLiイオンの吸蔵量が増加する。そのため、電池容量を大きくすることができる。その結果、バッテリー駆動時間を長くすることができるという利点がある。 In the present invention, it is also preferable to apply a Si-based negative electrode. In general, the Si negative electrode can occlude more Li ions than the carbon negative electrode (graphite, acetylene black, etc.). That is, the amount of Li ions occluded per unit mass increases. Therefore, the battery capacity can be increased. As a result, there is an advantage that the battery drive time can be lengthened.
負極活物質の形状は特に制限されないが粒子状が好ましい。負極活物質の粒子径(体積平均粒子径)は、0.1〜60μmが好ましい。所定の粒子径にするには、通常の粉砕機や分級機が用いられる。例えば、乳鉢、ボールミル、サンドミル、振動ボールミル、衛星ボールミル、遊星ボールミルおよび旋回気流型ジェットミルや篩などが好適に用いられる。粉砕時には水、あるいはメタノール等の有機溶媒を共存させた湿式粉砕も必要に応じて行うことができる。所望の粒子径とするためには分級を行うことが好ましい。分級方法としては特に限定はなく、篩、風力分級機などを必要に応じて用いることができる。分級は乾式および湿式ともに用いることができる。負極活物質粒子の平均粒子径は、前述の正極活物質の体積平均粒子径の測定方法と同様の方法により測定することができる。 The shape of the negative electrode active material is not particularly limited, but is preferably in the form of particles. The particle size (volume average particle size) of the negative electrode active material is preferably 0.1 to 60 μm. A normal crusher or classifier is used to obtain a predetermined particle size. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow type jet mill, a sieve, and the like are preferably used. At the time of pulverization, wet pulverization in which water or an organic solvent such as methanol coexists can also be performed, if necessary. It is preferable to perform classification in order to obtain a desired particle size. The classification method is not particularly limited, and a sieve, a wind power classifier, or the like can be used as needed. Classification can be used for both dry and wet types. The average particle size of the negative electrode active material particles can be measured by the same method as the above-mentioned method for measuring the volume average particle size of the positive electrode active material.
上記焼成法により得られた化合物の化学式は、測定方法として誘導結合プラズマ(ICP)発光分光分析法、簡便法として、焼成前後の粉体の質量差から算出できる。 The chemical formula of the compound obtained by the above firing method can be calculated from the inductively coupled plasma (ICP) emission spectroscopic analysis method as a measuring method and the mass difference of the powder before and after firing as a simple method.
上記負極活物質は、1種を単独で用いても、2種以上を組み合わせて用いてもよい。
負極活物質層を形成する場合、負極活物質層の単位面積(cm2)当たりの負極活物質の質量(mg)(目付量)は特に限定されるものではない。設計された電池容量に応じて、適宜に決めることができる。The negative electrode active material may be used alone or in combination of two or more.
When the negative electrode active material layer is formed, the mass (mg) (grain amount) of the negative electrode active material per unit area (cm 2) of the negative electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity.
負極活物質の、固体電解質組成物中における含有量は、特に限定されず、固形分100質量%において、10〜80質量%であることが好ましく、20〜80質量%がより好ましい。 The content of the negative electrode active material in the solid electrolyte composition is not particularly limited, and is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, based on 100% by mass of the solid content.
正極活物質または負極活物質を含む電極表面は硫黄またはリンで表面処理されていてもよい。また、正極活物質または負極活物質の粒子表面は、上記表面被覆の前後において活性光線または活性気体(プラズマ等)により表面処理を施されていても良い。 The surface of the electrode containing the positive electrode active material or the negative electrode active material may be surface-treated with sulfur or phosphorus. Further, the surface of the positive electrode active material or the particle surface of the negative electrode active material may be surface-treated with active light rays or an active gas (plasma or the like) before and after the surface coating.
本発明の全固体二次電池において、固体電解質層、正極活物質層及び負極活物質層には、リチウム塩、導電助剤、バインダー(上記充填材領域に含まれ得る有機バインダーが好ましい)、分散剤等が含まれていることも好ましい。 In the all-solid-state secondary battery of the present invention, the solid electrolyte layer, the positive electrode active material layer and the negative electrode active material layer include a lithium salt, a conductive auxiliary agent, a binder (preferably an organic binder that can be contained in the filler region), and dispersion. It is also preferable that an agent or the like is contained.
〔集電体(金属箔)〕
正極集電体5及び負極集電体1は、電子伝導体が好ましい。
本発明において、正極集電体及び負極集電体のいずれか、又は、両方を合わせて、単に、集電体と称することがある。
正極集電体を形成する材料としては、アルミニウム、アルミニウム合金、ステンレス鋼、ニッケルおよびチタンなどの他に、アルミニウムまたはステンレス鋼の表面にカーボン、ニッケル、チタンあるいは銀を処理させたもの(薄膜を形成したもの)が好ましく、その中でも、アルミニウムおよびアルミニウム合金がより好ましい。
負極集電体を形成する材料としては、アルミニウム、銅、銅合金、ステンレス鋼、ニッケルおよびチタンなどの他に、アルミニウム、銅、銅合金またはステンレス鋼の表面にカーボン、ニッケル、チタンあるいは銀を処理させたものが好ましく、アルミニウム、銅、銅合金およびステンレス鋼がより好ましい。[Current collector (metal leaf)]
The positive electrode
In the present invention, either or both of the positive electrode current collector and the negative electrode current collector may be collectively referred to as a current collector.
As a material for forming the positive electrode current collector, in addition to aluminum, aluminum alloy, stainless steel, nickel and titanium, the surface of aluminum or stainless steel is treated with carbon, nickel, titanium or silver (a thin film is formed). Of these, aluminum and aluminum alloys are more preferable.
As a material for forming the negative electrode current collector, in addition to aluminum, copper, copper alloy, stainless steel, nickel and titanium, carbon, nickel, titanium or silver is treated on the surface of aluminum, copper, copper alloy or stainless steel. Preferably, aluminum, copper, copper alloy and stainless steel are more preferable.
集電体の形状は、通常フィルムシート状のものが使用されるが、ネット、パンチされたもの、ラス体、多孔質体、発泡体、繊維群の成形体なども用いることができる。
集電体の厚みは、特に限定されないが、1〜500μmが好ましい。また、集電体表面は、表面処理により凹凸を付けることも好ましい。The shape of the current collector is usually a film sheet, but a net, a punched body, a lath body, a porous body, a foam body, a molded body of a fiber group, or the like can also be used.
The thickness of the current collector is not particularly limited, but is preferably 1 to 500 μm. Further, it is also preferable that the surface of the current collector is made uneven by surface treatment.
本発明において、負極集電体、負極活物質層、固体電解質層、正極活物質層及び正極集電体の各層の間又はその外側には、機能性の層や部材等を適宜介在ないし配設してもよい。また、各層は単層で構成されていても、複層で構成されていてもよい。 In the present invention, a functional layer, a member, or the like is appropriately interposed or arranged between or outside each of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector. You may. Further, each layer may be composed of a single layer or a plurality of layers.
<全固体二次電池の製造>
本発明において、全固体二次電池は、固体電解質層を本発明で規定する形態とすること以外は、常法により製造することができる。本発明の全固体二次電池の製造方法の一例を以下に示すが、本発明の全固体二次電池の製造方法はこれらの形態に限定されるものではない。<Manufacturing of all-solid-state secondary batteries>
In the present invention, the all-solid-state secondary battery can be manufactured by a conventional method except that the solid electrolyte layer is in the form specified in the present invention. An example of the method for manufacturing the all-solid-state secondary battery of the present invention is shown below, but the method for manufacturing the all-solid-state secondary battery of the present invention is not limited to these forms.
基材(例えば、集電体となる金属箔)上に、正極活物質層を構成する成分を含む組成物(正極用組成物)を塗布して正極活物質層を形成し、全固体二次電池用正極シートを作製する。次いで、この正極活物質層の上に、少なくとも上記無機固体電解質材料と上記電子絶縁性材料とを含有する組成物を塗布して層を形成する。次いでこの層の上に負極集電体を重ねる。次いでこの積層体を、電子絶縁性材料が熱溶融する温度(この温度は好ましくは200℃以下である)まで加熱し、電子絶縁性材料の溶融物を毛細管現象により無機固体電解質材料間の隙間に浸透させる。この毛細管現象により、固体電解質粒子の表層に存在する電子絶縁性材料が層内部の空隙へと移動するため、固体電解質層から正極活物質層への充填材の過剰な染み出しを防ぐことができる。
その後、冷却して充填材を固化することにより、無機固体電解質材料間の空隙の少なくとも一部が塞がれた固体電解質層を形成することができる。
こうして、正極活物質層と負極集電体との間に固体電解質層が挟まれた構造の全固体二次電池を得ることができる。必要によりこれを筐体に封入して所望の全固体二次電池とすることができる。また、固体電解質層の上に、負極活物質層と負極集電体と順次重ねることにより、正極活物質層と負極活物質層との間に固体電解質層が挟まれた構造の全固体二次電池を得ることもできる。
また、各層の形成方法を逆にして、負極集電体上に、負極活物質層、固体電解質層及び正極活物質層を形成し、正極集電体を重ねて、全固体二次電池を製造することもできる。また、基材/負極活物質層からなる2層構造の積層体と、基材/正極活物質層/固体電解質層からなる3層構造の積層体とを調製し、これらを重ねあわせて本発明の全固体二次電池を得ることもできる。また基材/正極活物質層からなる2層構造の積層体と、基材/負極活物質層/固体電解質層からなる3層構造の積層体とを調製し、これらを重ねあわせて本発明の全固体二次電池を得ることもできる。A composition (composition for a positive electrode) containing components constituting a positive electrode active material layer is applied onto a base material (for example, a metal foil serving as a current collector) to form a positive electrode active material layer, and an all-solid secondary A positive electrode sheet for a battery is produced. Next, a composition containing at least the inorganic solid electrolyte material and the electron insulating material is applied onto the cathode active material layer to form a layer. Next, the negative electrode current collector is superposed on this layer. Next, the laminate is heated to a temperature at which the electronically insulating material is thermally melted (this temperature is preferably 200 ° C. or lower), and the melt of the electronically insulating material is placed in the gap between the inorganic solid electrolyte materials by capillarity. Infiltrate. Due to this capillary phenomenon, the electron insulating material existing on the surface layer of the solid electrolyte particles moves to the voids inside the layer, so that excessive exudation of the filler from the solid electrolyte layer to the positive electrode active material layer can be prevented. ..
Then, by cooling and solidifying the filler, a solid electrolyte layer in which at least a part of the voids between the inorganic solid electrolyte materials is closed can be formed.
In this way, an all-solid-state secondary battery having a structure in which a solid electrolyte layer is sandwiched between the positive electrode active material layer and the negative electrode current collector can be obtained. If necessary, this can be enclosed in a housing to obtain a desired all-solid-state secondary battery. Further, by sequentially stacking the negative electrode active material layer and the negative electrode current collector on the solid electrolyte layer, the solid electrolyte layer is sandwiched between the positive electrode active material layer and the negative electrode active material layer. You can also get batteries.
Further, by reversing the forming method of each layer, a negative electrode active material layer, a solid electrolyte layer and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collectors are superposed to manufacture an all-solid secondary battery. You can also do it. Further, a two-layer structure laminate composed of a base material / negative electrode active material layer and a three-layer structure laminate composed of a base material / positive electrode active material layer / solid electrolyte layer are prepared, and these are laminated to form the present invention. All-solid-state secondary batteries can also be obtained. Further, a two-layer structure laminate composed of a base material / positive electrode active material layer and a three-layer structure laminate composed of a base material / negative electrode active material layer / solid electrolyte layer are prepared, and these are laminated to form the present invention. An all-solid-state secondary battery can also be obtained.
固体電解質層の形成において上記電子絶縁性材料を溶融させるための加熱は、上記無機固体電解質材料と上記電子絶縁性材料とを含有する組成物を用いて層を形成した後であれば、全固体二次電池の製造工程のどの段階で加熱してもよい。また、層形成自体(塗布工程自体)を上記電子絶縁性材料の溶融温以上の温度で行うこともでき、この場合は電子絶縁性材料を溶融させるための加熱工程を別途設ける必要はない。
また、少なくとも無機固体電解質材料を塗布して形成した層に、熱溶融状態にある硫黄及び/又は改質硫黄を含浸させ、次いで冷却して固体電解質層を形成することもできる。In the formation of the solid electrolyte layer, the heating for melting the electronically insulating material is all-solid as long as the layer is formed by using the composition containing the inorganic solid electrolyte material and the electronically insulating material. It may be heated at any stage in the manufacturing process of the secondary battery. Further, the layer formation itself (coating step itself) can be performed at a temperature equal to or higher than the melting temperature of the electronically insulating material, and in this case, it is not necessary to separately provide a heating step for melting the electronically insulating material.
It is also possible to impregnate a layer formed by applying at least an inorganic solid electrolyte material with sulfur and / or modified sulfur in a heat-melted state, and then cool the layer to form a solid electrolyte layer.
すなわち、本発明の全固体二次電池の製造方法の好ましい実施形態では、無機固体電解質材料と硫黄及び/又は改質硫黄とを含有する無機固体電解質組成物を用いて形成した層を加熱し、固体電解質層中の硫黄及び/又は改質硫黄を熱溶融させ、次いで冷却して固体電解質層を形成することを含むものである。本発明において電子絶縁性材料を溶融するために「層を加熱する」形態は、上記電子絶縁性材料を含む層を、この電子絶縁性材料の溶融温度以上の温度に曝すことを意味する。したがって、充填材の溶融温度以上の温度で製膜を行う場合、製膜後、さらに加熱する必要はないのであるが、本発明においては、製膜自体を溶融温度以上の高温で行い、その後に別途加熱処理を行わない形態も、「層を加熱する」形態に含むものとする。このことは、後述する本発明の固体電解質膜の製造においても同様である。 That is, in a preferred embodiment of the method for producing an all-solid-state secondary battery of the present invention, a layer formed by using an inorganic solid electrolyte material and an inorganic solid electrolyte composition containing sulfur and / or modified sulfur is heated. It involves thermally melting sulfur and / or modified sulfur in the solid electrolyte layer and then cooling to form the solid electrolyte layer. In the present invention, the form of "heating a layer" to melt an electronically insulating material means exposing the layer containing the electronically insulating material to a temperature equal to or higher than the melting temperature of the electronically insulating material. Therefore, when the film is formed at a temperature higher than the melting temperature of the filler, it is not necessary to further heat the film after the film is formed. However, in the present invention, the film forming itself is performed at a high temperature equal to or higher than the melting temperature, and then the film is formed. The form in which the heat treatment is not separately performed is also included in the form of "heating the layer". This also applies to the production of the solid electrolyte membrane of the present invention, which will be described later.
また、本発明の全固体二次電池の製造方法の別の好ましい実施形態は、無機固体電解質材料を用いて形成した層中に、熱溶融状態にある硫黄及び/又は改質硫黄を含浸させ、次いで冷却して固体電解質層を形成することを含むものである。 Further, another preferred embodiment of the method for producing an all-solid-state secondary battery of the present invention is to impregnate a layer formed by using an inorganic solid electrolyte material with sulfur and / or modified sulfur in a heat-melted state. It then involves cooling to form a solid electrolyte layer.
(各層の形成方法)
本発明の全固体二次電池の製造において、各層の形成方法は特に限定されず、適宜に選択できる。例えば、塗布(好ましくは湿式塗布)、スプレー塗布、スピンコート塗布、ディップコート、スリット塗布、ストライプ塗布およびバーコート塗布が挙げられる。
各層形成用の塗布液を塗布した後に乾燥処理を施してもよいし、重層塗布した後に乾燥処理をしてもよい。乾燥温度は特に限定されない。下限は30℃以上が好ましく、60℃以上がより好ましく、80℃以上がさらに好ましい。上限は、300℃以下が好ましく、250℃以下がより好ましく、200℃以下がさらに好ましい。このような温度範囲で加熱することで、(C)分散媒を除去し、固体状態にすることができる。また、温度を高くしすぎず、全固体二次電池の各部材を損傷せずに済むため好ましい。これにより、全固体二次電池において、優れた総合性能を示し、かつ良好な結着性を得ることができる。(Formation method of each layer)
In the production of the all-solid-state secondary battery of the present invention, the method for forming each layer is not particularly limited and can be appropriately selected. For example, coating (preferably wet coating), spray coating, spin coating coating, dip coating, slit coating, stripe coating and bar coating coating can be mentioned.
The coating liquid for forming each layer may be applied and then dried, or the layers may be applied and then dried. The drying temperature is not particularly limited. The lower limit is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 80 ° C. or higher. The upper limit is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 200 ° C. or lower. By heating in such a temperature range, the dispersion medium (C) can be removed and the solid state can be obtained. Further, it is preferable because the temperature is not raised too high and each member of the all-solid-state secondary battery is not damaged. As a result, in the all-solid-state secondary battery, excellent overall performance can be exhibited and good binding property can be obtained.
形成した固体電解質層、又は作製した全固体二次電池は、加圧することが好ましい。加圧方法としては油圧シリンダープレス機等が挙げられる。加圧力としては、特に限定されず、一般的には50〜1500MPaの範囲であることが好ましい。
また、塗布した固体電解質組成物は、加圧と同時に加熱することが好ましい。加熱温度としては、特に限定されず、一般的には30〜300℃の範囲である。無機固体電解質のガラス転移温度よりも高い温度でプレスすることもできる。
加圧は塗布溶媒又は分散媒をあらかじめ乾燥させた状態で行ってもよいし、溶媒又は分散媒が残存している状態で行ってもよい。It is preferable to pressurize the formed solid electrolyte layer or the produced all-solid secondary battery. Examples of the pressurizing method include a hydraulic cylinder press machine and the like. The pressing force is not particularly limited, and is generally preferably in the range of 50 to 1500 MPa.
Further, it is preferable that the applied solid electrolyte composition is heated at the same time as pressurization. The heating temperature is not particularly limited, and is generally in the range of 30 to 300 ° C. It can also be pressed at a temperature higher than the glass transition temperature of the inorganic solid electrolyte.
The pressurization may be performed in a state where the coating solvent or the dispersion medium is dried in advance, or may be performed in a state where the solvent or the dispersion medium remains.
加圧中の雰囲気としては、特に限定されず、大気下、乾燥空気下(露点−20℃以下)および不活性ガス中(例えばアルゴンガス中、ヘリウムガス中、窒素ガス中)などいずれでもよい。
プレス時間は短時間(例えば数時間以内)で高い圧力をかけてもよいし、長時間(1日以上)かけて中程度の圧力をかけてもよい。全固体二次電池用シート以外、例えば全固体二次電池の場合には、中程度の圧力をかけ続けるために、全固体二次電池の拘束具(ネジ締め圧等)を用いることもできる。
プレス圧はシート面等の被圧部に対して均一であっても異なる圧であってもよい。
プレス圧は被圧部の面積や膜厚に応じて変化させることができる。また同一部位を段階的に異なる圧力で変えることもできる。
プレス面は平滑であっても粗面化されていてもよい。The atmosphere during pressurization is not particularly limited, and may be any of air, dry air (dew point −20 ° C. or lower), inert gas (for example, argon gas, helium gas, nitrogen gas) and the like.
The pressing time may be short (for example, within several hours) and high pressure may be applied, or medium pressure may be applied for a long time (1 day or more). In the case of an all-solid-state secondary battery other than the all-solid-state secondary battery sheet, for example, in the case of an all-solid-state secondary battery, an all-solid-state secondary battery restraint (screw tightening pressure, etc.) can be used in order to continue applying a medium pressure.
The press pressure may be uniform or different with respect to the pressed portion such as the seat surface.
The press pressure can be changed according to the area and film thickness of the pressed portion. It is also possible to change the same part step by step with different pressures.
The pressed surface may be smooth or roughened.
また、電池をシート状に形成し、この電池シートを軸心の外周にロール状に巻いた状態とした円筒型とし、この円筒型電池の最外層から軸心方向に圧力をかける形態とすることもできる。 Further, the battery is formed in a sheet shape, and the battery sheet is wound around the outer circumference of the axis in a roll shape to form a cylindrical shape, and pressure is applied in the axial direction from the outermost layer of the cylindrical battery. You can also.
(初期化)
上記のようにして製造した全固体二次電池は、製造後又は使用前に初期化を行うことが好ましい。初期化の方法は特に限定されず、例えば、プレス圧を高めた状態で初充放電を行い、その後、全固体二次電池の一般使用圧力になるまで圧力を開放することにより行うことができる。(Initialize)
The all-solid-state secondary battery manufactured as described above is preferably initialized after manufacturing or before use. The initialization method is not particularly limited, and for example, the initial charge / discharge may be performed with the press pressure increased, and then the pressure may be released until the pressure reaches the general working pressure of the all-solid-state secondary battery.
<全固体二次電池の用途>
本発明の全固体二次電池は種々の用途に適用することができる。適用態様には特に限定はないが、例えば、電子機器に搭載する場合、ノートパソコン、ペン入力パソコン、モバイルパソコン、電子ブックプレーヤー、携帯電話、コードレスフォン子機、ページャー、ハンディーターミナル、携帯ファックス、携帯コピー、携帯プリンター、ヘッドフォンステレオ、ビデオムービー、液晶テレビ、ハンディークリーナー、ポータブルCD、ミニディスク、電気シェーバー、トランシーバー、電子手帳、電卓、メモリーカード、携帯テープレコーダー、ラジオ、バックアップ電源、メモリーカードなどが挙げられる。その他民生用として、自動車、電動車両、モーター、照明器具、玩具、ゲーム機器、ロードコンディショナー、時計、ストロボ、カメラ、医療機器(ペースメーカー、補聴器、肩もみ機など)などが挙げられる。更に、各種軍需用、宇宙用として用いることができる。また、太陽電池と組み合わせることもできる。<Use of all-solid-state secondary battery>
The all-solid-state secondary battery of the present invention can be applied to various applications. The application mode is not particularly limited, but for example, when it is mounted on an electronic device, it is a notebook computer, a pen input computer, a mobile computer, an electronic book player, a mobile phone, a cordless phone handset, a pager, a handy terminal, a mobile fax, or a mobile phone. Copies, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, mini discs, electric shavers, transceivers, electronic notebooks, calculators, memory cards, mobile tape recorders, radios, backup power supplies, memory cards, etc. Be done. Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.). Furthermore, it can be used for various munitions and space. It can also be combined with a solar cell.
なかでも、高容量かつ高レート放電特性が要求されるアプリケーションに適用することが好ましい。例えば、今後大容量化が予想される蓄電設備等においては高い安全性が必須となりさらに電池性能の両立が要求される。また、電気自動車などは高容量の二次電池を搭載し、家庭で日々充電が行われる用途が想定される。本発明によれば、このような使用形態に好適に対応してその優れた効果を発揮することができる。 Above all, it is preferable to apply it to an application that requires high capacity and high rate discharge characteristics. For example, high safety is indispensable for power storage equipment and the like whose capacity is expected to increase in the future, and further compatibility of battery performance is required. In addition, electric vehicles and the like are equipped with high-capacity secondary batteries and are expected to be used for daily charging at home. According to the present invention, it is possible to exert its excellent effect in a suitable manner corresponding to such a usage pattern.
[全固体二次電池用固体電解質膜]
本発明の全固体二次電池用固体電解質膜(以下、単に「本発明の電解質膜」という。)は、本発明の全固体二次電池の固体電解質層として好適に用いることができる。すなわち、本発明の電解質膜は、無機固体電解質材料に占有された電解質領域と、無機固体電解質材料の間を埋める充填材領域とを有し、この充填材領域を構成する上記電子絶縁性材料は、固体電解質膜形成時に熱溶融状態として充填されたもの(固体電解質膜形成時における熱溶融履歴を有するもの)である。
また、本発明の電解質膜は、無機固体電解質材料に占有された電解質領域と、無機固体電解質材料の間を埋める充填材領域とを有し、上記充填材領域のうち一辺が5μmの正方領域内に収まる充填材領域FRを平面視観察した場合に、FRの面積FAと、FRの外周長さFLとの比が、FL/FA≧0.81を満たすことが好ましい。
本発明の電解質膜の好ましい形態は、上述した本発明の全固体二次電池を構成する固体電解質層の好ましい形態と同じである。[Solid electrolyte membrane for all-solid secondary batteries]
The solid electrolyte membrane for an all-solid-state secondary battery of the present invention (hereinafter, simply referred to as “the electrolyte membrane of the present invention”) can be suitably used as the solid electrolyte layer of the all-solid-state secondary battery of the present invention. That is, the electrolyte membrane of the present invention has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that fills the space between the inorganic solid electrolyte materials, and the electronic insulating material constituting the filler region is , It is filled as a heat-melted state at the time of forming the solid electrolyte film (those having a history of heat-melting at the time of forming the solid electrolyte film).
Further, the electrolyte membrane of the present invention has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that fills the space between the inorganic solid electrolyte materials, and one side of the filler region is within a square region of 5 μm. When the filler region FR that fits in the above is observed in a plan view, it is preferable that the ratio of the area FA of the FR to the outer peripheral length FL of the FR satisfies FL / FA ≧ 0.81.
The preferred form of the electrolyte membrane of the present invention is the same as the preferred form of the solid electrolyte layer constituting the all-solid-state secondary battery of the present invention described above.
<全固体二次電池用固体電解質膜の製造>
本発明の電解質膜は、無機固体電解質材料と硫黄及び/又は改質硫黄とを含有する無機固体電解質組成物を用いて形成した膜を加熱し、この膜中の硫黄及び/又は改質硫黄を溶融させ、次いで冷却して硫黄及び/又は改質硫黄を固化することにより形成することができる。
また、本発明の電解質膜は、無機固体電解質材料を用いて形成した膜中に、熱溶融状態にある硫黄及び/又は改質硫黄を含浸させ、次いで冷却して硫黄及び/又は改質硫黄を固化することにより形成することができる。
本発明の電解質膜は、例えば、基材上に形成された状態で得ることができる。また、基材上に電解質膜を形成した後、基材を剥離して電解質膜単体としてもよい。<Manufacturing of solid electrolyte membranes for all-solid secondary batteries>
The electrolyte membrane of the present invention heats a membrane formed by using an inorganic solid electrolyte material and an inorganic solid electrolyte composition containing sulfur and / or modified sulfur, and removes sulfur and / or modified sulfur in the membrane. It can be formed by melting and then cooling to solidify sulfur and / or modified sulfur.
Further, in the electrolyte membrane of the present invention, a film formed by using an inorganic solid electrolyte material is impregnated with sulfur and / or modified sulfur in a heat-melted state, and then cooled to obtain sulfur and / or modified sulfur. It can be formed by solidifying.
The electrolyte membrane of the present invention can be obtained, for example, in a state of being formed on a base material. Further, after forming the electrolyte membrane on the base material, the base material may be peeled off to form a single electrolyte membrane.
本発明を実施例に基づきさらに詳細に説明するが、本発明はこれらの実施形態に限定されるものではない。 The present invention will be described in more detail based on examples, but the present invention is not limited to these embodiments.
[参考例1] 無機固体電解質の合成
アルゴン雰囲気下(露点−70℃)のグローブボックス内で、硫化リチウム(Li2S、Aldrich社製、純度>99.98%)4.84g、五硫化二リン(P2S5、Aldrich社製、純度>99%)7.80gをそれぞれ秤量し、メノウ製乳鉢に投入した。Li2S及びP2S5はモル比でLi2S:P2S5=75:25である。メノウ製乳鉢上において、メノウ製乳棒を用いて、5分間混合した。
ジルコニア製45mL容器(フリッチュ社製)に、直径5mmのジルコニアビーズを66個投入し、上記混合物全量を投入し、アルゴン雰囲気下で容器を完全に密閉した。フリッチュ社製遊星ボールミルP−7に容器をセットし、25℃で、回転数510rpmで20時間メカニカルミリングを行うことで黄色粉体の硫化物系無機固体電解質(Li/P/Sガラス、以下「LPS」ともいう。)12.4gを得た。
得られたLPSの体積平均粒子径を、レーザ回折/散乱式粒度分布測定装置LA−920(商品名、HORIBA社製)を用いて測定した結果、8μmであった。また、このLPSは、大粒径の粒子の粒子径と、それより小粒径の粒子の粒子径との関係が、[大粒径粒子の粒子径]>4×[小粒径粒子の粒子径]を満たす関係にある粒子を有するものであった。[Reference Example 1] Inorganic solid electrolyte argon atmosphere in a glove box (dew point -70 ° C.), lithium sulfide (Li 2 S, Aldrich Corp., purity> 99.98%) 4.84 g, pentasulfide phosphorus (P 2 S 5, Aldrich Co., purity> 99%) of 7.80g were weighed, were placed in an agate mortar. Li 2 S and P 2 S 5 have a molar ratio of Li 2 S: P 2 S 5 = 75: 25. On the agate mortar, the mixture was mixed for 5 minutes using an agate pestle.
66 zirconia beads having a diameter of 5 mm were put into a 45 mL container made of zirconia (manufactured by Fritsch), and the entire amount of the above mixture was put into the container, and the container was completely sealed under an argon atmosphere. A container is set in a planetary ball mill P-7 manufactured by Fritsch, and mechanical milling is performed at 25 ° C. at a rotation speed of 510 rpm for 20 hours to obtain a yellow powder sulfide-based inorganic solid electrolyte (Li / P / S glass, hereinafter "Li / P / S glass". Also referred to as "LPS") 12.4 g was obtained.
The volume average particle size of the obtained LPS was measured using a laser diffraction / scattering type particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA) and found to be 8 μm. Further, in this LPS, the relationship between the particle size of the particles having a large particle size and the particle size of the particles having a smaller particle size is [particle size of the large particle size particles]> 4 × [particle size of the small particle size particles]. It had particles having a relationship satisfying [Diameter].
[参考例2] 硫黄と無機固体電解質との混合物の調製
アルゴン雰囲気下(露点−70℃)のグローブボックス内で、硫黄(S、Aldrich社製、純度>99.98%)を0.8g、上記LPSを6.2g、それぞれ秤量し、メノウ製乳鉢に投入した。硫黄及びLPSは質量比でLPS:S=88:12、体積比でLPS:S=100:11である。メノウ製乳鉢上において、メノウ製乳棒を用いて、10分間混合した。[Reference Example 2] Preparation of a mixture of sulfur and an inorganic solid electrolyte 0.8 g of sulfur (S, manufactured by Aldrich, purity> 99.98%) in a glove box under an argon atmosphere (dew point -70 ° C), 6.2 g of each of the above LPSs was weighed and put into an agate mortar. Sulfur and LPS have a mass ratio of LPS: S = 88: 12 and a volume ratio of LPS: S = 100: 11. On the agate mortar, the mixture was mixed for 10 minutes using an agate pestle.
[参考例3] 硫黄とアルミナと無機固体電解質との混合物の調製
アルゴン雰囲気下(露点−70℃)のグローブボックス内で、硫黄(S、Aldrich社製、純度>99.98%)1.2g、酸化アルミニウムナノ粒子(Al2O3、純度>99%、粒子サイズ500nm、EMジャパン社製)0.6gをそれぞれ秤量し、メノウ製乳鉢に投入し、メノウ製乳棒を用いて10分間混合した。次いで、上記LPSを8.2g秤量し、上記乳鉢に投入して、メノウ製乳棒を用いて10分間混合した。LPS:アルミナ:硫黄は質量比で82:6:12、LPS:Sは体積比で100:11である。[Reference Example 3] Preparation of a mixture of sulfur, alumina and an inorganic solid electrolyte 1.2 g of sulfur (S, manufactured by Aldrich, purity> 99.98%) in a glove box under an argon atmosphere (dew point-70 ° C). , 0.6 g of aluminum oxide nanoparticles (Al 2 O 3 , purity> 99%, particle size 500 nm, manufactured by EM Japan) were weighed, placed in an agate mortar, and mixed for 10 minutes using an agate mortar. .. Next, 8.2 g of the LPS was weighed, put into the mortar, and mixed for 10 minutes using an agate pestle. LPS: Alumina: Sulfur has a mass ratio of 82: 6: 12, and LPS: S has a volume ratio of 100: 11.
[製造例] 全固体二次電池の製造
<全固体二次電池用正極シートの作製>
ジルコニア製45mL容器(フリッチュ社製)に、直径5mmのジルコニアビーズを180個投入し、上記で合成したLPS2.0gと、スチレンブタジエンゴム(商品コード182907、アルドリッチ社製)0.1gと、分散媒としてオクタン22gとを投入した。その後に、この容器をフリッチュ社製遊星ボールミルP−7にセットし、温度25℃で、回転数300rpmで2時間攪拌した。その後、正極活物質LiNi0.85Co0.10Al0.05O2(ニッケルコバルトアルミニウム酸リチウム)7.9gを容器に投入し、再びこの容器を遊星ボールミルP−7にセットし、温度25℃、回転数100rpmで15分間混合を続けた。このようにして、正極用組成物を得た。
次に、集電体となる厚み20μmのアルミ箔状に、上記で得られた正極用組成物をベーカー式アプリケーターにより塗布し、80℃2時間加熱して、正極用組成物を乾燥させた。その後、ヒートプレス機を用いて、所定の密度になるように乾燥させた正極層用組成物を加熱(120℃)しながら加圧(600MPa、1分)した。このようにして、膜厚110μmの正極活物質層を有する全固体二次電池用正極シートを作製した。[Manufacturing example] Manufacture of all-solid-state secondary battery <Manufacture of positive electrode sheet for all-solid-state secondary battery>
180 zirconia beads with a diameter of 5 mm were placed in a zirconia 45 mL container (Fritsch), 2.0 g of LPS synthesized above, 0.1 g of styrene-butadiene rubber (product code 182907, Aldrich), and a dispersion medium. As a result, 22 g of octane was added. After that, this container was set in a planetary ball mill P-7 manufactured by Fritsch, and stirred at a temperature of 25 ° C. and a rotation speed of 300 rpm for 2 hours. Then, 7.9 g of the positive electrode active material LiNi 0.85 Co 0.10 Al 0.05 O 2 (lithium nickel cobalt aluminate) was put into a container, and this container was set in the planetary ball mill P-7 again, and the temperature was 25. Mixing was continued for 15 minutes at ° C. and 100 rpm. In this way, a composition for a positive electrode was obtained.
Next, the positive electrode composition obtained above was applied to an aluminum foil having a thickness of 20 μm as a current collector with a baker-type applicator, and heated at 80 ° C. for 2 hours to dry the positive electrode composition. Then, using a heat press machine, the composition for the positive electrode layer dried to a predetermined density was pressurized (600 MPa, 1 minute) while heating (120 ° C.). In this way, a positive electrode sheet for an all-solid secondary battery having a positive electrode active material layer having a film thickness of 110 μm was produced.
<全固体二次電池の製造>
上記参考例2又は3で調製した混合物を、常温トルエン中で分散し固形分20質量%の塗布液を得た。この塗布液を、常温で上記の正極シート上にバーコート塗布し、120℃で乾燥して、膜厚100μmの固体電解質層を得た。
次いで、負極集電体となるSUS箔を固体電解質層の上に重ね、全固体二次電池用積層体を形成した。
この積層体に、拘束部材となる拘束板とネジを使い、トルクレンチでネジの締付力を調整し、所定の拘束圧を印加した。
その後、拘束圧のかかった状態の積層体を、ホットプレート上で150℃、1時間の加熱処理に付し、充填材である硫黄を熱溶融させた。
その後、自然冷却して、拘束圧を8MPaに調整して、実施例1の全固体二次電池とした。<Manufacturing of all-solid-state secondary batteries>
The mixture prepared in Reference Example 2 or 3 was dispersed in toluene at room temperature to obtain a coating liquid having a solid content of 20% by mass. This coating liquid was bar-coated on the above-mentioned positive electrode sheet at room temperature and dried at 120 ° C. to obtain a solid electrolyte layer having a film thickness of 100 μm.
Next, the SUS foil serving as the negative electrode current collector was laminated on the solid electrolyte layer to form a laminate for an all-solid secondary battery.
A restraining plate and a screw as a restraining member were used for this laminated body, and the tightening force of the screw was adjusted with a torque wrench, and a predetermined restraining pressure was applied.
Then, the laminated body under the restraining pressure was subjected to heat treatment at 150 ° C. for 1 hour on a hot plate to heat-melt sulfur as a filler.
Then, it was naturally cooled and the restraining pressure was adjusted to 8 MPa to obtain an all-solid-state secondary battery of Example 1.
下表に示す条件に変更したこと以外は、実施例1の全固体二次電池と同様にして実施例2、及び比較例1〜3の全固体二次電池を得た。 The all-solid-state secondary batteries of Example 2 and Comparative Examples 1 to 3 were obtained in the same manner as the all-solid-state secondary batteries of Example 1 except that the conditions shown in the table below were changed.
[試験例1] FL/FAの測定
上記の固体電解質層を、SEM−EDX装置を用い、クライオホルダーを用いることで凍結し、冷却した状態で測定を行った。
まず断面SEM像を倍率5000倍で撮影した。
次に、同じ断面のEDX像を元素Pと元素Sについて取得した。電解質領域と充填材領域(硫黄)の対応づけを、下記のようにP(リン)とS(硫黄)の有無で実施した。
電解質領域:P有り、S有り
充填材領域:P無し、S有り
断面SEM画像において、充填材領域として同定された各領域のうち、5μmの正方領域内(5μm×5μm)に収まる領域(充填材領域として同定された領域のうち、外周(電解質領域との境界)がすべて、5μmの正方領域内に収まる領域)を無作為に10領域選抜し、それらの領域のFL(周長)とFA(面積)を測定した。これらの測定値に基づき決定した各領域のFL/FAの平均(10領域のFL/FAの平均)を算出した。
なお、下表中、「SEM−EDX観察によるFRの状態」のカラムにおいて、「空隙」とは、断面SEM画像内に観察される、P無しかつS無しの領域を意味する。[Test Example 1] Measurement of FL / FA The above solid electrolyte layer was frozen by using a cryoholder using an SEM-EDX apparatus, and measured in a cooled state.
First, a cross-sectional SEM image was taken at a magnification of 5000 times.
Next, EDX images of the same cross section were obtained for element P and element S. The association between the electrolyte region and the filler region (sulfur) was carried out with or without P (phosphorus) and S (sulfur) as shown below.
Electrolyte region: with P, with S Filler region: without P, with S
In the cross-sectional SEM image, of each region identified as the filler region, a region within a 5 μm square region (5 μm × 5 μm) (outside the region identified as the filler region (boundary with the electrolyte region)). 10 regions were randomly selected (regions that fit within a square region of 5 μm), and FL (perimeter) and FA (area) of those regions were measured. The average of FL / FA of each region (average of FL / FA of 10 regions) determined based on these measured values was calculated.
In the table below, in the column of "FR state by SEM-EDX observation", "void" means a region without P and without S observed in the cross-sectional SEM image.
[試験例2] 充放電サイクル特性試験
上記で作製した各全固体二次電池を用いて、下記条件により充放電を行い、充放電サイクル特性試験を実施した。
(条件)
30℃、電流密度0.09mA/cm2(0.05Cに相当)、4.2V、一定電流条件で充放電[Test Example 2] Charge / discharge cycle characteristic test Using each of the all-solid-state secondary batteries produced above, charge / discharge was performed under the following conditions, and a charge / discharge cycle characteristic test was carried out.
(conditions)
Charge / discharge at 30 ° C., current density 0.09mA / cm 2 (equivalent to 0.05C), 4.2V, constant current conditions
内部短絡が生じた場合は充電が完了しないため、50時間で充電を終了させ、放電させた。内部短絡の有無は、充電時の急激な電圧降下の有無により判断した。
下記評価基準に基づき、充放電サイクル特性を評価した。
−充放電サイクル特性評価基準−
A:3サイクル以上でも短絡なし
B:2サイクル以上3サイクル未満で短絡
C:1サイクル以上2サイクル未満で短絡
D:1サイクル未満で短絡
結果を下表に示す。When an internal short circuit occurred, charging was not completed, so charging was completed and discharged in 50 hours. The presence or absence of an internal short circuit was determined by the presence or absence of a sudden voltage drop during charging.
The charge / discharge cycle characteristics were evaluated based on the following evaluation criteria.
-Charge / discharge cycle characteristic evaluation criteria-
A: No short circuit even in 3 cycles or more B: Short circuit in 2 cycles or more and less than 3 cycles C: Short circuit in 1 cycle or more and less than 2 cycles D: Short circuit in less than 1 cycle The results are shown in the table below.
上記表に示される通り、固体電解質層を構成する無機固体電解質の粒子間を、充填材により埋めることにより、短絡を効果的に抑制できることがわかる。 As shown in the above table, it can be seen that the short circuit can be effectively suppressed by filling the space between the particles of the inorganic solid electrolyte constituting the solid electrolyte layer with a filler.
本発明をその実施態様とともに説明したが、我々は特に指定しない限り我々の発明を説明のどの細部においても限定しようとするものではなく、添付の請求の範囲に示した発明の精神と範囲に反することなく幅広く解釈されるべきであると考える。 Although the present invention has been described with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified, and contrary to the spirit and scope of the invention set forth in the appended claims. I think that it should be widely interpreted without.
本願は、2017年3月7日に日本国で特許出願された特願2017−042634に基づく優先権を主張するものであり、これはここに参照してその内容を本明細書の記載の一部として取り込む。 The present application claims priority based on Japanese Patent Application No. 2017-042634, which was filed in Japan on March 7, 2017, which is referred to herein and is described herein. Incorporate as a part.
10 全固体二次電池
1 負極集電体
2 負極活物質層
3 固体電解質層
4 正極活物質層
5 正極集電体
6 作動部位
21a 固体電解質層
21b 正極集電体
21c 正極活物質層
21d 負極集電体
21e 負極活物質層
22 軸心
23 電池カバー10 All-solid secondary battery 1 Negative electrode
Claims (17)
該充填材領域が、100℃において固体でかつ200℃以下の温度領域で熱溶融する電子絶縁性材料の熱溶融物を用いて形成されたものであって、
前記固体電解質層が、前記無機固体電解質材料と前記電子絶縁性材料とを含む組成物の層であり、かつ、正極活物質層上に直接配されてなり、
前記固体電解質層中、前記無機固体電解質材料の含有量100体積%に対し、前記電子絶縁性材料の含有量が2体積%以上であり、
前記充填材領域が有機バインダーを含有する、全固体二次電池。 The solid electrolyte layer has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that closes the voids between the inorganic solid electrolyte materials.
The filler region is formed by using a thermal melt of an electronically insulating material that is solid at 100 ° C. and thermally melts in a temperature region of 200 ° C. or lower.
The solid electrolyte layer is a layer of a composition containing the inorganic solid electrolyte material and the electron insulating material, and is arranged directly on the positive electrode active material layer.
The solid electrolyte layer, with respect to content 100% by volume of the inorganic solid electrolyte material state, and are content more than 2% by volume of the electronically insulating material,
The filler area you containing an organic binder, all-solid secondary battery.
前記充填材領域が、100℃において固体でかつ200℃以下の温度領域で熱溶融する電子絶縁性材料を含み、
1辺が5μmの正方領域内に収まる充填材領域FRを平面視観察した場合に、FRの面積FAと、FRの外周長さFLとの比が、FL/FA≧0.81を満たし、
前記固体電解質層が、前記無機固体電解質材料と前記電子絶縁性材料とを含む組成物の層であり、かつ、正極活物質層上に直接配されてなり、
前記固体電解質層中、前記無機固体電解質材料の含有量100体積%に対し、前記電子絶縁性材料の含有量が2体積%以上であり、
前記充填材領域が有機バインダーを含有する、全固体二次電池。 The solid electrolyte layer has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that closes the voids between the inorganic solid electrolyte materials.
The filler region comprises an electronically insulating material that is solid at 100 ° C. and thermally melts in a temperature region of 200 ° C. or lower.
When the filler region FR that fits in the square region with one side of 5 μm is observed in a plan view, the ratio of the area FA of the FR to the outer peripheral length FL of the FR satisfies FL / FA ≧ 0.81.
The solid electrolyte layer is a layer of a composition containing the inorganic solid electrolyte material and the electron insulating material, and is arranged directly on the positive electrode active material layer.
The solid electrolyte layer, with respect to content 100% by volume of the inorganic solid electrolyte material state, and are content more than 2% by volume of the electronically insulating material,
The filler area you containing an organic binder, all-solid secondary battery.
該充填材領域が、100℃において固体でかつ200℃以下の温度領域で熱溶融する電子絶縁性材料の熱溶融物を用いて形成されたものであって、 The filler region is formed by using a thermal melt of an electronically insulating material that is solid at 100 ° C. and thermally melts in a temperature region of 200 ° C. or lower.
前記固体電解質層が、前記無機固体電解質材料と前記電子絶縁性材料とを含む組成物の層であり、かつ、正極活物質層上に直接配されてなり、The solid electrolyte layer is a layer of a composition containing the inorganic solid electrolyte material and the electron insulating material, and is arranged directly on the positive electrode active material layer.
前記固体電解質層中、前記無機固体電解質材料の含有量100体積%に対し、前記電子絶縁性材料の含有量が2体積%以上であり、In the solid electrolyte layer, the content of the electronically insulating material is 2% by volume or more with respect to the content of the inorganic solid electrolyte material of 100% by volume.
前記無機固体電解質材料が大粒径の粒子と小粒径の粒子とを有し、[大粒径粒子の粒子径]>4×[小粒径粒子の粒子径]を満たす粒度分布を有する、全固体二次電池。The inorganic solid electrolyte material has a large particle size particle and a small particle size particle, and has a particle size distribution satisfying [particle size of large particle size particles]> 4 × [particle size of small particle size particles]. All-solid secondary battery.
前記充填材領域が、100℃において固体でかつ200℃以下の温度領域で熱溶融する電子絶縁性材料を含み、The filler region comprises an electronically insulating material that is solid at 100 ° C. and thermally melts in a temperature region of 200 ° C. or lower.
1辺が5μmの正方領域内に収まる充填材領域FRを平面視観察した場合に、FRの面積FAと、FRの外周長さFLとの比が、FL/FA≧0.81を満たし、When the filler region FR that fits in the square region with one side of 5 μm is observed in a plan view, the ratio of the area FA of the FR to the outer peripheral length FL of the FR satisfies FL / FA ≧ 0.81.
前記固体電解質層が、前記無機固体電解質材料と前記電子絶縁性材料とを含む組成物の層であり、かつ、正極活物質層上に直接配されてなり、The solid electrolyte layer is a layer of a composition containing the inorganic solid electrolyte material and the electron insulating material, and is arranged directly on the positive electrode active material layer.
前記固体電解質層中、前記無機固体電解質材料の含有量100体積%に対し、前記電子絶縁性材料の含有量が2体積%以上であり、In the solid electrolyte layer, the content of the electronically insulating material is 2% by volume or more with respect to the content of the inorganic solid electrolyte material of 100% by volume.
前記無機固体電解質材料が大粒径の粒子と小粒径の粒子とを有し、[大粒径粒子の粒子径]>4×[小粒径粒子の粒子径]を満たす粒度分布を有する、全固体二次電池。The inorganic solid electrolyte material has a large particle size particle and a small particle size particle, and has a particle size distribution satisfying [particle size of large particle size particles]> 4 × [particle size of small particle size particles]. All-solid secondary battery.
該充填材領域は、100℃において固体でかつ200℃以下の温度領域で熱溶融する電子絶縁性材料の熱溶融物を用いて形成されたものである、全固体二次電池用固体電解質膜であって、
該全固体二次電池用固体電解質膜が、前記無機固体電解質材料と前記電子絶縁性材料とを含む組成物の膜であり、かつ、正極活物質層上に直接配して使用されるものであり、
前記全固体二次電池用固体電解質膜中、前記無機固体電解質材料の含有量100体積%に対し、前記電子絶縁性材料の含有量が2体積%以上であり、
前記無機固体電解質材料が大粒径の粒子と小粒径の粒子とを有し、[大粒径粒子の粒子径]>4×[小粒径粒子の粒子径]を満たす、全固体二次電池用固体電解質膜。 It has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that closes the voids between the inorganic solid electrolyte materials.
The filler region is a solid electrolyte membrane for an all-solid secondary battery, which is formed by using a thermal melt of an electronically insulating material that is solid at 100 ° C. and thermally melts in a temperature region of 200 ° C. or lower. There,
The solid electrolyte film for an all-solid secondary battery is a film of a composition containing the inorganic solid electrolyte material and the electronically insulating material, and is used by being directly arranged on the positive electrode active material layer. can be,
The all-solid secondary battery for a solid electrolyte membrane, to the content 100% by volume of the inorganic solid electrolyte material state, and are content more than 2% by volume of the electronically insulating material,
The inorganic solid electrolyte material has large particle size particles and small particle size particles, and satisfies [particle size of large particle size particles]> 4 × [particle size of small particle size particles]. Solid electrolyte membrane for batteries.
前記充填材領域が、100℃において固体でかつ200℃以下の温度領域で熱溶融する電子絶縁性材料を含み、
1辺が5μmの正方領域内に収まる充填材領域FRを平面視観察した場合に、FRの面積FAと、FRの外周長さFLとの比が、FL/FA≧0.81を満たす、全固体二次電池用固体電解質膜であって、
該全固体二次電池用固体電解質膜が、前記無機固体電解質材料と前記電子絶縁性材料とを含む組成物の膜であり、かつ、正極活物質層上に直接配して使用されるものであり、
前記全固体二次電池用固体電解質膜中、前記無機固体電解質材料の含有量100体積%に対し、前記電子絶縁性材料の含有量が2体積%以上であり、
前記無機固体電解質材料が大粒径の粒子と小粒径の粒子とを有し、[大粒径粒子の粒子径]>4×[小粒径粒子の粒子径]を満たす、全固体二次電池用固体電解質膜。 It has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that closes the voids between the inorganic solid electrolyte materials.
The filler region comprises an electronically insulating material that is solid at 100 ° C. and thermally melts in a temperature region of 200 ° C. or lower.
When the filler region FR that fits in the square region with one side of 5 μm is observed in a plan view, the ratio of the area FA of the FR to the outer peripheral length FL of the FR satisfies FL / FA ≧ 0.81. A solid electrolyte membrane for solid secondary batteries,
The solid electrolyte film for an all-solid secondary battery is a film of a composition containing the inorganic solid electrolyte material and the electronically insulating material, and is used by being directly arranged on the positive electrode active material layer. can be,
The all-solid secondary battery for a solid electrolyte membrane, to the content 100% by volume of the inorganic solid electrolyte material state, and are content more than 2% by volume of the electronically insulating material,
The inorganic solid electrolyte material has large particle size particles and small particle size particles, and satisfies [particle size of large particle size particles]> 4 × [particle size of small particle size particles]. Solid electrolyte membrane for batteries.
該固体電解質層が、前記無機固体電解質材料に占有された電解質領域と、該無機固体電解質材料間の空隙を塞ぐ充填材領域とを有し、
該充填材領域が、前記硫黄及び/又は前記改質硫黄の熱溶融物を用いて形成されたものであり、
前記固体電解質層中、前記無機固体電解質材料の含有量100体積%に対し、前記硫黄及び前記改質硫黄の含有量の合計が2体積%以上である、全固体二次電池の製造方法。 This includes impregnating a layer formed using an inorganic solid electrolyte material from the outside to the inside of the layer with sulfur and / or modified sulfur in a heat-melted state, and then cooling to form a solid electrolyte layer. , A method of manufacturing an all-solid-state secondary battery,
The solid electrolyte layer has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that closes the voids between the inorganic solid electrolyte materials.
The filler region is formed by using the hot melt of the sulfur and / or the modified sulfur.
A method for producing an all-solid secondary battery, wherein the total content of the sulfur and the modified sulfur in the solid electrolyte layer is 2% by volume or more with respect to 100% by volume of the content of the inorganic solid electrolyte material.
該固体電解質膜が、前記無機固体電解質材料に占有された電解質領域と、該無機固体電解質材料間の空隙を塞ぐ充填材領域とを有し、
該充填材領域が、前記硫黄及び/又は前記改質硫黄の熱溶融物を用いて形成されたものであり、
前記固体電解質膜中、前記無機固体電解質材料の含有量100体積%に対し、前記硫黄及び前記改質硫黄の含有量の合計が2体積%以上である、全固体二次電池用固体電解質膜の製造方法。
For all-solid-state secondary batteries, including impregnating hot-melted sulfur and / or modified sulfur from the outside of a film formed using an inorganic solid electrolyte material toward the inside of the film, and then cooling. A method for producing a solid electrolyte membrane.
The solid electrolyte membrane has an electrolyte region occupied by the inorganic solid electrolyte material and a filler region that closes the voids between the inorganic solid electrolyte materials.
The filler region is formed by using the hot melt of the sulfur and / or the modified sulfur.
The solid electrolyte membrane for an all-solid secondary battery in which the total content of the sulfur and the modified sulfur is 2% by volume or more with respect to 100% by volume of the content of the inorganic solid electrolyte material in the solid electrolyte membrane. Production method.
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