JP2019204800A - Solid electrolyte for all-solid secondary battery, manufacturing method thereof, and all-solid secondary battery - Google Patents

Solid electrolyte for all-solid secondary battery, manufacturing method thereof, and all-solid secondary battery Download PDF

Info

Publication number
JP2019204800A
JP2019204800A JP2019161035A JP2019161035A JP2019204800A JP 2019204800 A JP2019204800 A JP 2019204800A JP 2019161035 A JP2019161035 A JP 2019161035A JP 2019161035 A JP2019161035 A JP 2019161035A JP 2019204800 A JP2019204800 A JP 2019204800A
Authority
JP
Japan
Prior art keywords
solid electrolyte
solid
secondary battery
particles
state secondary
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2019161035A
Other languages
Japanese (ja)
Other versions
JP7061100B2 (en
Inventor
弘樹 山下
Hiroki Yamashita
弘樹 山下
大神　剛章
Takeaki Ogami
剛章 大神
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiheiyo Cement Corp
Original Assignee
Taiheiyo Cement Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiheiyo Cement Corp filed Critical Taiheiyo Cement Corp
Publication of JP2019204800A publication Critical patent/JP2019204800A/en
Application granted granted Critical
Publication of JP7061100B2 publication Critical patent/JP7061100B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

To provide a solid electrolyte for an all-solid secondary battery, a manufacturing method thereof, and an all-solid secondary battery in which interfacial resistance with an electrode active material is effectively reduced even when a secondary battery is continuously used.SOLUTION: In a solid electrolyte for an all-solid secondary battery, a solid electrolyte nanoparticle aggregate (b) in which a plurality of solid electrolyte nanoparticles (a) are linearly carried on a carbon chain derived from cellulose nanofibers having an average fiber diameter of 50 nm or less is carried on the surface of a solid electrolyte particle (A).SELECTED DRAWING: Figure 1

Description

本発明は、電極活物質との界面抵抗が低減された全固体二次電池用固体電解質、特に全固体リチウムイオン二次電池用固体電解質、及びそれらの製造方法、並びにそれらを用いた全固体二次電池ないし全固体リチウムイオン二次電池に関する。   The present invention relates to a solid electrolyte for an all-solid-state secondary battery having reduced interface resistance with an electrode active material, in particular, a solid electrolyte for an all-solid-state lithium ion secondary battery, a production method thereof, and an all-solid-state secondary battery using the same. The present invention relates to a secondary battery or an all solid lithium ion secondary battery.

現在市販されているリチウムイオン二次電池等の二次電池は、電解液に可燃性の有機溶媒が使用されているため、短絡防止のための構造や、短絡が生じた場合の温度上昇を抑える安全装置が必要となる。これに対し、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２などの酸化物系の固体電解質や、７５Ｌｉ２Ｓ・２５Ｐ２Ｓ５などの硫化物系の固体電解質を備えた全固体リチウムイオン二次電池は、エネルギー密度の高さと共に、可燃物を用いないことから安全装置の簡素化を図ることができ、製造コストや生産性にも優れるリチウムイオン二次電池として期待されている。 Secondary batteries such as lithium-ion secondary batteries currently on the market use a flammable organic solvent in the electrolyte solution, so they prevent structures from short-circuiting and prevent temperature rises when short-circuiting occurs. A safety device is required. On the other hand, an all-solid-state lithium ion secondary battery including an oxide-based solid electrolyte such as Li 7 La 3 Zr 2 O 12 or a sulfide-based solid electrolyte such as 75Li 2 S · 25P 2 S 5 is It is expected to be a lithium ion secondary battery that has high energy density and simplifies the safety device because it does not use combustible materials, and is excellent in manufacturing cost and productivity.

全固体リチウムイオン二次電池は、アルミ箔等の正極集電体、正極活物質、固体電解質、負極活物質、及び銅箔等の負極集電体といった、構成材料のすべてが固体物質で構成されている。上記全固体リチウムイオン二次電池の製造では、一般的に、これらの構成材料を積層してプレスする工程が含まれるが、これは、固体材料間の固−固界面の接触を改良して界面抵抗を低減し、得られるリチウムイオン二次電池の性能を向上させるためである。   All solid-state lithium ion secondary batteries are composed of solid materials such as a positive electrode current collector such as aluminum foil, a positive electrode active material, a solid electrolyte, a negative electrode active material, and a negative electrode current collector such as copper foil. ing. The production of the all-solid-state lithium ion secondary battery generally includes a step of laminating and pressing these constituent materials, which improves the solid-solid interface contact between the solid materials. This is for reducing the resistance and improving the performance of the obtained lithium ion secondary battery.

また、非特許文献１には、１７５℃で５時間の加熱処理を行うことによって、固体電解質Ｌｉ７−ｘＬａ３Ｚｒ２−ｘＴａｘＯ１２（ＬＬＺＴ）と金属リチウムからなる負極材料とが良好な接合界面を形成し、界面抵抗が効果的に低減できることが開示されている。 Further, Non-Patent Document 1, by performing heat treatment for 5 hours at 175 ° C., a solid electrolyte Li 7-x La 3 Zr 2 -x Ta x O 12 and (LLZT) a negative electrode material made of metallic lithium It is disclosed that a good bonding interface can be formed and the interface resistance can be effectively reduced.

稲田亮史外；第５８回電池討論会講演要旨、１Ｃ０７、２０１７Ryo Inada; Abstract of the 58th Battery Discussion Meeting, 1C07, 2017

しかしながら、上述のようにプレスして製造された全固体リチウムイオン二次電池等では、充放電によって繰り返される電極活物質の膨張、収縮や、使用中の振動等によって、二次電池内の材料の積層構造の破壊が生じ、正極活物質と負極活物質とが接触して電池が内部短絡する恐れがある。また、非特許文献１の方法では、金属リチウム以外の電極活物質への適用が困難という問題がある。   However, in an all-solid-state lithium ion secondary battery or the like manufactured by pressing as described above, the material in the secondary battery may be affected by expansion and contraction of the electrode active material that is repeatedly charged and discharged, vibration during use, and the like. The laminated structure may be destroyed, and the positive electrode active material and the negative electrode active material may come into contact with each other and the battery may be internally short-circuited. Further, the method of Non-Patent Document 1 has a problem that it is difficult to apply to electrode active materials other than metallic lithium.

したがって、本発明の課題は、継続的な二次電池の使用においても電極活物質との界面抵抗が有効に低減される、全固体二次電池用固体電解質、特に全固体リチウムイオン二次電池用固体電解質、及びその製造方法、並びにそれらを用いた全固体二次電池を提供することにある。   Accordingly, an object of the present invention is to provide a solid electrolyte for an all-solid secondary battery, particularly an all-solid lithium ion secondary battery, in which the interface resistance with the electrode active material is effectively reduced even in continuous use of the secondary battery. An object of the present invention is to provide a solid electrolyte, a manufacturing method thereof, and an all-solid secondary battery using the same.

本発明者らは、上記課題を解決するため鋭意検討した結果、以下に示す全固体二次電池用固体電解質、及びその製造方法、並びにそれらを用いた全固体二次電池により、上記目的を達成できることを見出して、本発明を完成するに至った。   As a result of intensive studies to solve the above problems, the present inventors have achieved the above object by using the solid electrolyte for an all-solid-state secondary battery shown below, a manufacturing method thereof, and an all-solid-state secondary battery using the same. The present invention was completed by finding out what can be done.

すなわち、本発明の全固体二次電池用固体電解質は、平均繊維径が５０ｎｍ以下のセルロースナノファイバー由来の炭素鎖に複数の固体電解質ナノ粒子（ａ）が線状に担持してなる固体電解質ナノ粒子集合体（ｂ）が、固体電解質粒子（Ａ）の表面に担持されてなることを特徴とする。   That is, the solid electrolyte for an all-solid-state secondary battery according to the present invention is a solid electrolyte nanoparticle in which a plurality of solid electrolyte nanoparticles (a) are linearly supported on a carbon chain derived from cellulose nanofibers having an average fiber diameter of 50 nm or less. The particle aggregate (b) is supported on the surface of the solid electrolyte particle (A).

また、本発明の他の全固体二次電池用固体電解質は、平均繊維径が５０ｎｍ以下のセルロースナノファイバーに誘導されて固体電解質ナノ粒子（ａ）が線状に連続して配列した固体電解質ナノ粒子列（ｃ）が、固体電解質粒子（Ａ）の表面に担持されてなることを特徴とする。   Another solid electrolyte for an all-solid-state secondary battery of the present invention is a solid electrolyte nanoparticle in which solid electrolyte nanoparticles (a) are linearly arrayed by being induced by cellulose nanofibers having an average fiber diameter of 50 nm or less. The particle row (c) is supported on the surface of the solid electrolyte particle (A).

本発明の全固体二次電池用固体電解質によると、上述のように、セルロースナノファイバー由来の炭素鎖を軸又は基材として、これに特定の固体電解質のナノ粒子が複数連なって担持又は配列してなる特異な形状を呈する固体電解質ナノ粒子集合体（ｂ）、又は固体電解質のナノ粒子を用いて得られる線状に配列した複数の固体電解質のナノ粒子列（ｃ）を、たとえば、電極活物質層と固体電解質の界面部に存在させることによって、電極活物質と固体電解質との有効な接合が十分に確保されて界面抵抗が低減され、さらには、電極活物質が充放電による膨張、収縮を繰り返しても電極活物質と固体電解質との有効な接合が継続され得ることが可能となる。   According to the solid electrolyte for an all-solid-state secondary battery of the present invention, as described above, a carbon chain derived from cellulose nanofibers is used as a shaft or a base material, and a plurality of specific solid electrolyte nanoparticles are supported or arranged in series on this. The solid electrolyte nanoparticle aggregate (b) having a unique shape or a plurality of solid electrolyte nanoparticle arrays (c) arranged in a linear shape obtained by using the solid electrolyte nanoparticles, for example, By being present at the interface between the material layer and the solid electrolyte, an effective bonding between the electrode active material and the solid electrolyte is sufficiently ensured, the interface resistance is reduced, and further, the electrode active material expands and contracts due to charge and discharge. Even if the process is repeated, it is possible to continue the effective bonding between the electrode active material and the solid electrolyte.

また、本発明の全固体二次電池用固体電解質において、上記固体電解質粒子（Ａ）の平均粒子径が、１０ｎｍ〜５０μｍとすることができる。上記構成とすることにより、電極活物質（粒子）や電解質（粒子）等との空隙率の小さい良好なパッキング状態を構成することができ、全固体二次電池用固体電解質としてより好適なものとなりうる。   In the solid electrolyte for an all-solid secondary battery of the present invention, the average particle size of the solid electrolyte particles (A) can be 10 nm to 50 μm. By adopting the above configuration, a good packing state with a small porosity with the electrode active material (particles), the electrolyte (particles), etc. can be configured, and it becomes more suitable as a solid electrolyte for an all-solid-state secondary battery. sell.

また、本発明の全固体二次電池用固体電解質において、上記固体電解質ナノ粒子（ａ）の平均粒子径が、０．５ｎｍ〜１００ｎｍとすることができる。上記構成とすることにより、電極活物質（粒子）や電解質（粒子）等と空隙率の小さい良好なパッキング状態を構成することができ、全固体二次電池用固体電解質としてより好適なものとなりうる。   Moreover, in the solid electrolyte for an all-solid-state secondary battery of the present invention, the average particle diameter of the solid electrolyte nanoparticles (a) may be 0.5 nm to 100 nm. By adopting the above-described configuration, a good packing state with a small porosity can be formed with the electrode active material (particles), the electrolyte (particles), and the like, which can be more suitable as a solid electrolyte for an all-solid-state secondary battery. .

また、本発明の全固体二次電池用固体電解質において、上記固体電解質粒子（Ａ）と、上記固体電解質ナノ粒子集合体（ｂ）、上記固体電解質ナノ粒子列（ｃ）、又はその両方を含む場合にはその合計量、との質量割合（（Ａ）：固体電解質ナノ粒子集合体（ｂ）＋固体電解質ナノ粒子列（ｃ）（ただし、固体電解質ナノ粒子集合体（ｂ）と固体電解質ナノ粒子列（ｃ）は、いずれか一方しか含まない場合は、その一方のみ。））が、９９．９：０．１〜７０：３０とすることができる。上記構成とすることにより、全固体二次電池用固体電解質としてより好適なものとなりうる。   The solid electrolyte for an all-solid-state secondary battery of the present invention includes the solid electrolyte particle (A), the solid electrolyte nanoparticle aggregate (b), the solid electrolyte nanoparticle array (c), or both. In the case, the total amount, and the mass ratio ((A): solid electrolyte nanoparticle aggregate (b) + solid electrolyte nanoparticle array (c) (however, solid electrolyte nanoparticle aggregate (b) and solid electrolyte nanoparticle In the case where only one of the particle rows (c) is included, only one of them can be set to 99.9: 0.1 to 70:30. By setting it as the said structure, it can become a more suitable thing as a solid electrolyte for all-solid-state secondary batteries.

また、本発明の全固体二次電池用固体電解質において、上記固体電解質粒子（Ａ）が、Ｌｉ３ＰＯ４‐Ｌｉ４ＳｉＯ４、Ｌｉ７−ｘＬａ３Ｚｒ２−ｘＴａｘＯ１２、Ｌａ０．５１Ｌｉ０．３４ＴｉＯ２．９４、Ｌｉ１．３Ａｌ０．３Ｔｉ１．７（ＰＯ４）３、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２、及び５０Ｌｉ４ＳｉＯ４・５０Ｌｉ３ＢＯ３からなる群のうち少なくとも１種以上を含むものであっても構わない。上記構成とすることにより、全固体二次電池用固体電解質、特に全固体リチウムイオン二次電池用固体電解質としてより好適なものとなりうる。 In the solid electrolyte for an all-solid-state secondary battery of the present invention, the solid electrolyte particles (A) are Li 3 PO 4 -Li 4 SiO 4 , Li 7-x La 3 Zr 2-x Ta x O 12 , La From 0.51 Li 0.34 TiO 2.94 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 7 La 3 Zr 2 O 12 , and 50Li 4 SiO 4 .50Li 3 BO 3 You may include at least 1 sort (s) among the group which consists of. By setting it as the said structure, it can become more suitable as a solid electrolyte for all-solid-state secondary batteries, especially a solid electrolyte for all-solid-state lithium ion secondary batteries.

また、本発明の全固体二次電池用固体電解質において、上記固体電解質ナノ粒子（ａ）が、Ｌｉ３ＰＯ４‐Ｌｉ４ＳｉＯ４、Ｌｉ７−ｘＬａ３Ｚｒ２−ｘＴａｘＯ１２、Ｌａ０．５１Ｌｉ０．３４ＴｉＯ２．９４、Ｌｉ１．３Ａｌ０．３Ｔｉ１．７（ＰＯ４）３、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２、及び５０Ｌｉ４ＳｉＯ４・５０Ｌｉ３ＢＯ３からなる群のうち少なくとも１種以上を含むものであっても構わない。上記構成とすることにより、全固体二次電池用固体電解質、特に全固体リチウムイオン二次電池用固体電解質としてより好適なものとなりうる。 In the solid electrolyte for an all-solid-state secondary battery of the present invention, the solid electrolyte nanoparticles (a) are Li 3 PO 4 -Li 4 SiO 4 , Li 7-x La 3 Zr 2 -x Ta x O 12 , La 0.51 Li 0.34 TiO 2.94 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 7 La 3 Zr 2 O 12 , and 50Li 4 SiO 4 .50Li 3 BO 3 It may contain at least one or more of the group consisting of By setting it as the said structure, it can become more suitable as a solid electrolyte for all-solid-state secondary batteries, especially a solid electrolyte for all-solid-state lithium ion secondary batteries.

また、本発明の全固体二次電池用固体電解質において、上記線状が、直線状、又は略直線状であるとすることができる。上記構成とすることにより、全固体二次電池用固体電解質として好適なものとなりうる。   In the solid electrolyte for an all-solid secondary battery of the present invention, the linear shape may be a linear shape or a substantially linear shape. By setting it as the said structure, it can become a suitable thing as a solid electrolyte for all-solid-state secondary batteries.

また、本発明の全固体二次電池用固体電解質において、上記全固体リチウムイオン二次電池用であるとすることができる。本発明の全固体二次電池用固体電解質は、上記特徴を有しているため、特に全固体リチウムイオン二次電池用として用いられることが好ましい。   Moreover, the solid electrolyte for an all-solid secondary battery of the present invention can be used for the all-solid lithium ion secondary battery. Since the solid electrolyte for an all-solid-state secondary battery of the present invention has the above characteristics, it is particularly preferable to be used for an all-solid-state lithium ion secondary battery.

一方、本発明の全固体二次電池用固体電解質の製造方法は、
次の工程（ＩＩ）〜（ＩＩＩ）：
少なくとも１種の固体電解質の原料化合物、アルカリ溶液、及び原料となるセルロースナノファイバー（以下、「ＣＮＦ」と称することもある。）を含有するスラリーを、温度が１００℃以上、圧力が０．３ＭＰａ〜０．９ＭＰａの水熱反応に付して、原料ＣＮＦの一部、又は全部を内包する固体電解質ナノ粒子集合体（ｄ）、原料ＣＮＦの一部、又は全部を内包する上記固体電解質の前駆体からなるナノ粒子集合体（ｅ）、又はその両方、を製造する工程（ＩＩ）、及び、
少なくとも、工程（ＩＩ）で得られた上記原料ＣＮＦの一部、又は全部を内包する固体電解質ナノ粒子集合体（ｄ）、原料ＣＮＦの一部、又は全部を内包する上記固体電解質の前駆体からなるナノ粒子集合体（ｅ）及び上記原料ＣＮＦの一部、又は全部を内包する上記固体電解質の前駆体からなるナノ粒子集合体（ｅ）と反応して固体電解質ナノ粒子集合体（ｂ）若しくは固体電解質ナノ粒子列（ｃ）を生成するための残余の原料化合物、又はその両方を焼成する工程（ＩＩＩ）、
を含むことを特徴とする。 On the other hand, the method for producing a solid electrolyte for an all-solid-state secondary battery of the present invention is as follows.
Next steps (II) to (III):
A slurry containing at least one solid electrolyte raw material compound, an alkaline solution, and cellulose nanofibers (hereinafter also referred to as “CNF”) as a raw material has a temperature of 100 ° C. or higher and a pressure of 0.3 MPa. The solid electrolyte nanoparticle aggregate (d) enclosing part or all of the raw material CNF by subjecting it to a hydrothermal reaction of ˜0.9 MPa, and the precursor of the solid electrolyte enclosing part or all of the raw material CNF A step (II) of producing a nanoparticle assembly (e) consisting of a body, or both, and
At least from the solid electrolyte nanoparticle aggregate (d) enclosing part or all of the raw material CNF obtained in step (II), the precursor of the solid electrolyte encapsulating part or all of the raw material CNF A solid electrolyte nanoparticle aggregate (b) which reacts with the nanoparticle aggregate (e) and the nanoparticle aggregate (e) comprising the precursor of the solid electrolyte encapsulating part or all of the raw material CNF Step (III) of firing the remaining raw material compounds for producing the solid electrolyte nanoparticle array (c), or both,
It is characterized by including.

また、他の本発明の全固体二次電池用固体電解質の製造方法は、
次の工程（ＩＩ）〜（ＩＩＩ’）：
少なくとも１種の固体電解質の原料化合物、アルカリ溶液、及び原料となるセルロースナノファイバーを含有するスラリーを、温度が１００℃以上、圧力が０．３ＭＰａ〜０．９ＭＰａの水熱反応に付して、原料ＣＮＦの一部、又は全部を内包する固体電解質ナノ粒子集合体（ｄ）、原料ＣＮＦの一部、又は全部を内包する上記固体電解質の前駆体からなるナノ粒子集合体（ｅ）、又はその両方、を製造する工程（ＩＩ）、及び、
少なくとも、工程（ＩＩ）で得られた上記原料ＣＮＦの一部、又は全部を内包する固体電解質ナノ粒子集合体（ｄ）、原料ＣＮＦの一部、又は全部を内包する上記固体電解質の前駆体からなるナノ粒子集合体（ｅ）及び上記原料ＣＮＦの一部、又は全部を内包する上記固体電解質の前駆体からなるナノ粒子集合体（ｅ）と反応して固体電解質ナノ粒子集合体（ｂ）を生成するための残余の原料化合物、又はその両方を、還元雰囲気下で焼成する工程（ＩＩＩ’）、
を含むことを特徴とする。 In addition, another method for producing a solid electrolyte for an all-solid-state secondary battery of the present invention,
Next steps (II) to (III ′):
A slurry containing at least one raw material compound of a solid electrolyte, an alkali solution, and cellulose nanofibers as a raw material is subjected to a hydrothermal reaction at a temperature of 100 ° C. or higher and a pressure of 0.3 MPa to 0.9 MPa, Solid electrolyte nanoparticle aggregate (d) encapsulating part or all of the raw material CNF, nanoparticle aggregate (e) comprising the solid electrolyte precursor encapsulating part or all of the raw material CNF, or Steps (II) for producing both, and
At least from the solid electrolyte nanoparticle aggregate (d) enclosing part or all of the raw material CNF obtained in step (II), the precursor of the solid electrolyte encapsulating part or all of the raw material CNF The solid electrolyte nanoparticle aggregate (b) reacts with the nanoparticle aggregate (e) comprising the nanoparticle aggregate (e) and the solid electrolyte precursor containing part or all of the raw material CNF. A step (III ′) of calcining the remaining raw material compounds to be produced, or both in a reducing atmosphere;
It is characterized by including.

また、他の本発明の全固体二次電池用固体電解質の製造方法は、
次の工程（ＩＩ）〜（ＩＩＩ’’）：
少なくとも１種の固体電解質の原料化合物、アルカリ溶液、及び原料となるセルロースナノファイバーを含有するスラリーを、温度が１００℃以上、圧力が０．３ＭＰａ〜０．９ＭＰａの水熱反応に付して、原料ＣＮＦの一部、又は全部を内包する固体電解質ナノ粒子集合体（ｄ）、原料ＣＮＦの一部、又は全部を内包する上記固体電解質の前駆体からなるナノ粒子集合体（ｅ）、又はその両方、を製造する工程（ＩＩ）、及び、
少なくとも、工程（ＩＩ）で得られた上記原料ＣＮＦの一部、又は全部を内包する固体電解質ナノ粒子集合体（ｄ）、原料ＣＮＦの一部、又は全部を内包する上記固体電解質の前駆体からなるナノ粒子集合体（ｅ）及び上記原料ＣＮＦの一部、又は全部を内包する上記固体電解質の前駆体からなるナノ粒子集合体（ｅ）と反応して固体電解質ナノ粒子列（ｃ）を生成するための残余の原料化合物、又はその両方を、酸化雰囲気下で焼成する工程（ＩＩＩ’’）、
を含むことを特徴とする。 In addition, another method for producing a solid electrolyte for an all-solid-state secondary battery of the present invention,
Next steps (II) to (III ″):
A slurry containing at least one raw material compound of a solid electrolyte, an alkali solution, and cellulose nanofibers as a raw material is subjected to a hydrothermal reaction at a temperature of 100 ° C. or higher and a pressure of 0.3 MPa to 0.9 MPa, Solid electrolyte nanoparticle aggregate (d) encapsulating part or all of the raw material CNF, nanoparticle aggregate (e) comprising the solid electrolyte precursor encapsulating part or all of the raw material CNF, or Steps (II) for producing both, and
At least from the solid electrolyte nanoparticle aggregate (d) enclosing part or all of the raw material CNF obtained in step (II), the precursor of the solid electrolyte encapsulating part or all of the raw material CNF Reacting with the nanoparticle aggregate (e) and the nanoparticle aggregate (e) comprising the precursor of the solid electrolyte encapsulating part or all of the raw material CNF to produce a solid electrolyte nanoparticle array (c) A step (III ″) of firing the remaining raw material compounds to be used, or both in an oxidizing atmosphere,
It is characterized by including.

本発明の全固体二次電池用固体電解質の製造方法は、上記構成を有することにより、上述の全固体二次電池用固体電解質をより簡便に製造することが可能となる。さらには、上述のように、工程（ＩＩＩ’）、又は工程（ＩＩＩ’’）を有することにより、セルロースナノファイバー由来の炭素鎖に複数の固体電解質ナノ粒子（ａ）が線状に担持してなる上記固体電解質ナノ粒子集合体（ｂ）を備える固体電解質、及びセルロースナノファイバーに誘導されて固体電解質ナノ粒子（ａ）が線状に連続して配列した上記固体電解質ナノ粒子列（ｃ）を備える固体電解質について、各々所望のものを簡便に得ることが可能となる。   The method for producing a solid electrolyte for an all-solid-state secondary battery of the present invention can produce the above-described solid electrolyte for an all-solid-state secondary battery more simply by having the above-described configuration. Furthermore, as described above, by having the step (III ′) or the step (III ″), a plurality of solid electrolyte nanoparticles (a) are linearly supported on the carbon chains derived from cellulose nanofibers. A solid electrolyte comprising the solid electrolyte nanoparticle aggregate (b), and the solid electrolyte nanoparticle array (c) in which the solid electrolyte nanoparticles (a) are linearly arranged continuously by being induced by cellulose nanofibers. Regarding the solid electrolyte provided, it is possible to easily obtain each desired one.

また、本発明の全固体二次電池用固体電解質の製造方法において、工程（ＩＩＩ）、（ＩＩＩ’）、又は（ＩＩＩ’’）において、焼成する際に、さらに固体電解質粒子（Ａ）を含むことができる。たとえば、焼成前の原料混合物に、事前に、固体電解質粒子（Ａ）を含めておくことで、上記固体電解質ナノ粒子集合体（ｂ）、又は固体電解質ナノ粒子列（ｃ）のいずれか一方を、固体電解質粒子（Ａ）の表面に担持した全固体二次電池用固体電解質をより簡便に得ることが可能となりうる。   Moreover, in the manufacturing method of the solid electrolyte for all-solid-state secondary batteries of this invention, when baking in process (III), (III '), or (III' '), a solid electrolyte particle (A) is further included. be able to. For example, by including the solid electrolyte particles (A) in advance in the raw material mixture before firing, either the solid electrolyte nanoparticle aggregate (b) or the solid electrolyte nanoparticle array (c) is added. It may be possible to more easily obtain a solid electrolyte for an all-solid-state secondary battery supported on the surface of the solid electrolyte particles (A).

また、本発明の全固体二次電池用固体電解質の製造方法において、さらに、工程（ＩＩＩ）、（ＩＩＩ’）、又は（ＩＩＩ’’）に先立ち、上記固体電解質粒子（Ａ）を製造する工程（Ｉ）、を含むことができる。   In the method for producing a solid electrolyte for an all-solid-state secondary battery of the present invention, the step of producing the solid electrolyte particles (A) prior to the step (III), (III ′) or (III ″). (I) can be included.

また、本発明の全固体二次電池用固体電解質の製造方法において、工程（ＩＩ）のスラリー中におけるセルロースナノファイバーの含有量が、スラリー中の水１００質量部に対し、炭素原子換算量で０．０１質量部〜１０質量部であるとすることができる。上記構成とすることにより、より確実に、原料ＣＮＦの一部、又は全部を内包する固体電解質ナノ粒子集合体（ｄ）、原料ＣＮＦの一部、又は全部を内包する上記固体電解質の前駆体からなるナノ粒子集合体（ｅ）、又はその両方へと変換させ、上記全固体二次電池用固体電解質を得ることができうる。   Moreover, in the manufacturing method of the solid electrolyte for all-solid-state secondary batteries of this invention, content of the cellulose nanofiber in the slurry of process (II) is 0 in carbon atom conversion amount with respect to 100 mass parts of water in slurry. .01 parts by mass to 10 parts by mass. By adopting the above-described configuration, the solid electrolyte nanoparticle aggregate (d) enclosing part or all of the raw material CNF is more reliably obtained from the precursor of the solid electrolyte including part or all of the raw material CNF. It is possible to obtain the above solid electrolyte for an all-solid-state secondary battery by converting into the nanoparticle aggregate (e) or both.

また、本発明の全固体二次電池用固体電解質の製造方法において、工程（ＩＩ）における水熱反応が、温度が１００℃以上、圧力が０．３ＭＰａ〜０．９ＭＰａ、反応時間が０．５時間〜２４時間であるとすることができる。上記構成とすることにより、より確実に、原料ＣＮＦの一部、又は全部を内包する固体電解質ナノ粒子集合体（ｄ）、原料ＣＮＦの一部、又は全部を内包する上記固体電解質の前駆体からなるナノ粒子集合体（ｅ）、又はその両方へと変換させ、上記全固体二次電池用固体電解質を得ることができうる。   In the method for producing a solid electrolyte for an all-solid secondary battery of the present invention, the hydrothermal reaction in the step (II) is performed at a temperature of 100 ° C. or higher, a pressure of 0.3 MPa to 0.9 MPa, and a reaction time of 0.5. It may be from 24 hours to 24 hours. By adopting the above-described configuration, the solid electrolyte nanoparticle aggregate (d) enclosing part or all of the raw material CNF is more reliably obtained from the precursor of the solid electrolyte including part or all of the raw material CNF. It is possible to obtain the above solid electrolyte for an all-solid-state secondary battery by converting into the nanoparticle aggregate (e) or both.

また、本発明の全固体二次電池用固体電解質の製造方法において、工程（ＩＩＩ）、（ＩＩＩ’）、又は（ＩＩＩ’’）における焼成の温度が、５００℃〜１２００℃であるとすることができる。上記構成とすることにより、より確実に、上記セルロースナノファイバーを炭化または焼失させるとともに、原料ＣＮＦの一部、又は全部を内包する上記固体電解質の前駆体からなるナノ粒子集合体（ｅ）が含まれる場合にはそれを固体電解質ナノ粒子集合体（ｂ）、又は固体電解質ナノ粒子列（ｃ）へと変換させ、上記全固体二次電池用固体電解質を得ることができうる。   Moreover, in the manufacturing method of the solid electrolyte for all-solid-state secondary batteries of this invention, the calcination temperature in process (III), (III '), or (III' ') shall be 500 to 1200 degreeC. Can do. By the above configuration, the nanoparticle aggregate (e) composed of the precursor of the solid electrolyte encapsulating part or all of the raw material CNF while carbonizing or burning out the cellulose nanofibers more reliably is included. If it is, it can be converted into a solid electrolyte nanoparticle aggregate (b) or a solid electrolyte nanoparticle array (c) to obtain the solid electrolyte for an all-solid-state secondary battery.

他方、本発明の全固体二次電池は、上記全固体二次電池用固体電解質を備えることを特徴とする。   On the other hand, the all-solid-state secondary battery of the present invention includes the above-described solid electrolyte for all-solid-state secondary battery.

上記全固体二次電池は、上記特性を有する全固体二次電池用固体電解質を構成要素として備えるため、充放電容量や充放電の繰り返しに伴う耐久性等をより一層高めうることができる。   Since the all-solid-state secondary battery includes the solid electrolyte for an all-solid-state secondary battery having the above characteristics as a constituent element, the charge / discharge capacity, durability associated with repeated charge / discharge, and the like can be further improved.

また、本発明の全固体二次電池は、全固体リチウムイオン二次電池であることが好ましい。上記特性を備えるため、充放電容量や充放電の繰り返しに伴う耐久性等をより一層高めた全固体リチウムイオン二次電池となりうる。   Moreover, it is preferable that the all-solid-state secondary battery of this invention is an all-solid-state lithium ion secondary battery. Since it has the above characteristics, it can be an all-solid-state lithium ion secondary battery having further enhanced durability and the like accompanying repeated charge / discharge capacity and charge / discharge.

本発明の全固体二次電池用固体電解質によれば、固体電解質粒子（Ａ）の表面に固体電解質ナノ粒子集合体（ｂ）、又は固体電解質粒子のナノ粒子列（ｃ）が担持されているため、それを用いた全固体二次電池、特に全固体リチウムイオン二次電池における電極活物質粒子と上記固体電解質粒子間の界面抵抗が十分に低減され、上記二次電池の充放電容量をより一層高めることができうる。   According to the solid electrolyte for an all-solid-state secondary battery of the present invention, the solid electrolyte nanoparticle aggregate (b) or the solid electrolyte particle nanoparticle array (c) is supported on the surface of the solid electrolyte particles (A). Therefore, the interfacial resistance between the electrode active material particles and the solid electrolyte particles in an all-solid secondary battery using the same, particularly an all-solid lithium ion secondary battery is sufficiently reduced, and the charge / discharge capacity of the secondary battery is further increased. It can be further enhanced.

また、本発明の全固体二次電池用固体電解質の製造方法によれば、上述の固体電解質粒子（Ａ）の表面に固体電解質ナノ粒子集合体（ｂ）、又は固体電解質粒子のナノ粒子列（ｃ）が担持されている所望の各固体電解質を簡便に得ることが可能となる。   Moreover, according to the manufacturing method of the solid electrolyte for all-solid-state secondary batteries of this invention, the solid electrolyte nanoparticle aggregate | assembly (b) or the nanoparticle row | line | column of a solid electrolyte particle (b) on the surface of the above-mentioned solid electrolyte particle (A) ( It becomes possible to easily obtain each desired solid electrolyte carrying c).

また、本発明の全固体二次電池、ないし全固体リチウムイオン二次電池によれば、上記特性を有する全固体二次電池用固体電解質を備えるため、電極活物質粒子と上記固体電解質粒子間の界面抵抗が十分に低減され、上記二次電池の充放電容量や充放電の繰り返しに伴う耐久性をより一層高めた全固体二次電池、ないし全固体リチウムイオン二次電池とすることができうる。   In addition, according to the all solid secondary battery or the all solid lithium ion secondary battery of the present invention, since the solid electrolyte for the all solid secondary battery having the above characteristics is provided, between the electrode active material particles and the solid electrolyte particles. Interfacial resistance is sufficiently reduced, and the secondary battery can be made into an all-solid secondary battery or an all-solid lithium ion secondary battery with further enhanced durability associated with repeated charge / discharge capacity and charge / discharge. .

実施例１で得られた固体電解質粒子の表面構造を示すＴＥＭ写真である。2 is a TEM photograph showing the surface structure of solid electrolyte particles obtained in Example 1. FIG.

以下、本発明について詳細に説明する。   Hereinafter, the present invention will be described in detail.

〔全固体二次電池用固体電解質〕
本発明の全固体リチウムイオン二次電池用固体電解質は、平均粒子径が１０ｎｍ〜５０μｍの固体電解質粒子（Ａ）の表面に、平均繊維径が５０ｎｍ以下のセルロースナノファイバー由来の炭素鎖に、平均粒径が０．５ｎｍ〜１００ｎｍの複数の固体電解質ナノ粒子（ａ）が線状に担持してなる固体電解質ナノ粒子集合体（ｂ）（以後、「固体電解質ナノアレイ（ｂ）」と称することもある。）か、又は上記セルロースナノファイバーに誘導されて固体電解質ナノ粒子（ａ）が線状に連続して配列した固体電解質ナノ粒子列（ｃ）が、固体電解質粒子（Ａ）の表面に担持されてなる。 [Solid electrolyte for all-solid-state secondary batteries]
The solid electrolyte for an all-solid-state lithium ion secondary battery of the present invention has an average particle diameter on the surface of solid electrolyte particles (A) having an average particle diameter of 10 nm to 50 μm and carbon chains derived from cellulose nanofibers having an average fiber diameter of 50 nm or less Solid electrolyte nanoparticle aggregate (b) in which a plurality of solid electrolyte nanoparticles (a) having a particle size of 0.5 nm to 100 nm are linearly supported (hereinafter also referred to as “solid electrolyte nanoarray (b)”) Or a solid electrolyte nanoparticle array (c) in which the solid electrolyte nanoparticles (a) are linearly arrayed by being induced by the cellulose nanofibers are supported on the surface of the solid electrolyte particles (A). Being done.

ここで、本発明における固体電解質ナノ粒子集合体（ｂ）とは、ナノスケールの構造体である平均繊維径が５０ｎｍ以下のセルロースナノファイバー由来の炭素鎖に、もう一方のナノスケールの構造体である平均粒径が０．５ｎｍ〜１００ｎｍの複数の固体電解質ナノ粒子が線状に、連続して、又は断続的に、担持してなる、特異な形状を呈している。そして、上記固体電解質ナノ粒子集合体（ｂ）は、構成材料の分離が生じ難いため、上記特異な形状を保持しつつ、固体電解質粒子（Ａ）の表面に担持することが可能である。   Here, the solid electrolyte nanoparticle aggregate (b) in the present invention is the other nanoscale structure on a carbon chain derived from cellulose nanofibers having an average fiber diameter of 50 nm or less, which is a nanoscale structure. A plurality of solid electrolyte nanoparticles having an average particle diameter of 0.5 nm to 100 nm have a unique shape in which they are supported linearly, continuously or intermittently. And since the said solid electrolyte nanoparticle aggregate | assembly (b) does not produce separation of a constituent material easily, it can carry | support on the surface of a solid electrolyte particle (A), hold | maintaining the said specific shape.

本発明における固体電解質ナノアレイ（ｂ）、又は固体電解質ナノ粒子列（ｃ）が表面に担持された全固体二次電池用固体電解質、特に全固体リチウムイオン二次電池用固体電解質は、本発明の範囲が当該推測のメカニズムに限定されるものではないが、その表面の固体電解質ナノアレイ（ｂ）、又は固体電解質ナノ粒子列（ｃ）の担持による微小な凹凸構造によって、たとえば、充放電によって電極活物質の膨張、収縮が繰り返し生じた場合であっても、電極活物質粒子と固体電解質粒子との間に常に多量の有効な接合点が存在しうる状態を保持できることにより、これらを用いて得られる全固体二次電池、特に全固体リチウムイオン二次電池は、電極活物質粒子と固体電解質粒子間の界面抵抗が十分に低減されて、良好な充放電容量を発現しうると推測している。   The solid electrolyte nanoarray (b) in the present invention, or the solid electrolyte for an all solid state secondary battery having the solid electrolyte nanoparticle array (c) supported on the surface thereof, particularly the solid electrolyte for an all solid state lithium ion secondary battery, Although the range is not limited to the speculated mechanism, the electrode is activated by charging / discharging by, for example, charging / discharging due to the minute uneven structure supported by the solid electrolyte nanoarray (b) or the solid electrolyte nanoparticle array (c) on the surface. Even when the material is repeatedly expanded and contracted, it can be obtained by using a state in which a large amount of effective bonding points can always be maintained between the electrode active material particles and the solid electrolyte particles. All-solid-state secondary batteries, especially all-solid-state lithium ion secondary batteries, have a sufficiently reduced interfacial resistance between electrode active material particles and solid electrolyte particles, resulting in good charge / discharge capacity. Speculate that may be.

なお、上記固体電解質粒子（Ａ）の表面上の上記固体電解質ナノアレイ（ｂ）、又は上記固体電解質粒子（Ａ）の表面上の上記固体電解質ナノ粒子列（ｃ）の担持状態は、必ずしも物理的、又は化学的に強固である必要はない。なぜなら、たとえば、全固体リチウムイオン二次電池の製造では、正極活物質層、固体電解質層、及び負極活物質層の積層構造をプレスして電池とするため、かかる圧縮力によって固体電解質ナノアレイ（ｂ）を介して固体電解質粒子（Ａ）と電極活物質粒子との間、又は固体電解質ナノ粒子列（ｃ）を介して固体電解質粒子（Ａ）と電極活物質粒子との間には、良好な接触状態が形成されうるからである。   The supported state of the solid electrolyte nanoarray (b) on the surface of the solid electrolyte particle (A) or the solid electrolyte nanoparticle array (c) on the surface of the solid electrolyte particle (A) is not necessarily a physical state. Or need not be chemically strong. This is because, for example, in the production of an all-solid-state lithium ion secondary battery, since the laminated structure of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is pressed to form a battery, the solid electrolyte nanoarray (b ) Between the solid electrolyte particles (A) and the electrode active material particles, or between the solid electrolyte particles (A) and the electrode active material particles via the solid electrolyte nanoparticle array (c). This is because a contact state can be formed.

また、本発明に用いる固体電解質粒子（Ａ）は、全固体二次電池、特に全固体リチウムイオン二次電池に用いることができるものであって、かつ、後述する製造方法における焼成工程において熱分解を生じ難いものであれば、その種類に制限はない。具体的には、酸化物系固体電解質等を用いることができ、たとえば、Ｌｉ３ＰＯ４‐Ｌｉ４ＳｉＯ４、Ｌｉ７−ｘＬａ３Ｚｒ２−ｘＴａｘＯ１２、Ｌａ０．５１Ｌｉ０．３４ＴｉＯ２．９４、Ｌｉ１．３Ａｌ０．３Ｔｉ１．７（ＰＯ４）３、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２、５０Ｌｉ４ＳｉＯ４・５０Ｌｉ３ＢＯ３等をあげることができる。また、本発明の固体電解質粒子（Ａ）は、Ｌｉ３ＰＯ４‐Ｌｉ４ＳｉＯ４、Ｌｉ７−ｘＬａ３Ｚｒ２−ｘＴａｘＯ１２、Ｌａ０．５１Ｌｉ０．３４ＴｉＯ２．９４、Ｌｉ１．３Ａｌ０．３Ｔｉ１．７（ＰＯ４）３、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２、及び５０Ｌｉ４ＳｉＯ４・５０Ｌｉ３ＢＯ３からなる群のうち少なくとも１種以上を含むものであってもよい。 Further, the solid electrolyte particles (A) used in the present invention can be used for all-solid secondary batteries, particularly all-solid lithium ion secondary batteries, and are thermally decomposed in the firing step in the production method described later. As long as it is difficult to produce, there is no restriction on the type. Specifically, an oxide-based solid electrolyte or the like can be used. For example, Li 3 PO 4 -Li 4 SiO 4 , Li 7-x La 3 Zr 2 -x Ta x O 12 , La 0.51 Li 0 .34 TiO 2.94 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 7 La 3 Zr 2 O 12 , 50Li 4 SiO 4 .50Li 3 BO 3 and the like. Further, the solid electrolyte particles (A) of the present invention are Li 3 PO 4 -Li 4 SiO 4 , Li 7-x La 3 Zr 2-x Ta x O 12 , La 0.51 Li 0.34 TiO 2.94. Including at least one selected from the group consisting of Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 7 La 3 Zr 2 O 12 , and 50Li 4 SiO 4 .50Li 3 BO 3 It may be.

上記固体電解質粒子（Ａ）の平均粒径は、好ましくは１０ｎｍ〜５０μｍであり、より好ましくは１０ｎｍ〜２５μｍである。固体電解質粒子（Ａ）の平均粒径が上記範囲とすることにより、得られる全固体二次電池の内部において電極活物質粒子と空隙率の小さい良好なパッキング状態を構成することができうる。   The average particle diameter of the solid electrolyte particles (A) is preferably 10 nm to 50 μm, more preferably 10 nm to 25 μm. By setting the average particle size of the solid electrolyte particles (A) within the above range, it is possible to form a good packing state having a small porosity with the electrode active material particles inside the obtained all-solid-state secondary battery.

ここで、本発明における平均粒径とは、ＳＥＭ、又はＴＥＭの電子顕微鏡を用いた観察における、数十個の粒子の粒径（長軸の長さ）の測定値の平均値を意味する。また、上記平均値の算出は、たとえば、１０個の粒子の測定値を用いて行う。   Here, the average particle diameter in the present invention means an average value of measured values of particle diameters (lengths of major axes) of several tens of particles in observation using an SEM or TEM electron microscope. The average value is calculated using, for example, measured values of 10 particles.

本発明の固体電解質ナノアレイ（ｂ）を構成するセルロースナノファイバー由来の炭素鎖の原料となるセルロースナノファイバーとは、全ての植物細胞壁の約５割を占める骨格成分であって、上記細胞壁を構成する植物繊維をナノサイズまで解繊等することにより得ることができる軽量高強度繊維であり、水への良好な分散性も有している。また、セルロースナノファイバーを構成するセルロース分子鎖は、炭素による周期的構造が形成されていることから、還元条件下での焼成などして得られるセルロースナノファイバーが炭化されて形成される鎖状の炭素は、良好な導電パスとして、固体電解質粒子（Ａ）の表面に担持される固体電解質ナノアレイ（ｂ）中に一部または全部が内包されうる。   Cellulose nanofibers, which are raw materials for carbon chains derived from cellulose nanofibers constituting the solid electrolyte nanoarray (b) of the present invention, are skeletal components that occupy about 50% of all plant cell walls, and constitute the cell walls. It is a lightweight, high-strength fiber that can be obtained by defibrating plant fibers to the nano size and has good dispersibility in water. In addition, since the cellulose molecular chain constituting the cellulose nanofiber has a periodic structure formed of carbon, the cellulose nanofiber obtained by baking under reducing conditions is carbonized to form a chain shape. Carbon can be partly or wholly included in the solid electrolyte nanoarray (b) supported on the surface of the solid electrolyte particles (A) as a good conductive path.

また、当然のことながら、酸素雰囲気下の焼成においては、上記セルロースナノファイバーは二酸化炭素ならびに水となって焼失するので、原料ＣＮＦの一部、又は全部を内包する固体電解質ナノ粒子集合体（ｄ）（以後、「ＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）」と称す場合もある。）、又は原料ＣＮＦの一部、又は全部を内包する上記固体電解質の前駆体からなるナノ粒子集合体（ｅ）（以後、「ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）」と称す場合もある。）を酸素雰囲気焼成することによって、ＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）、又はＣＮＦ内包前駆体ナノ粒子集合体（ｅ）からセルロースナノファイバーが除去されて得られるナノアレイでの整列状態を保持した固体電解質ナノ粒子列（ｃ）のみを、固体電解質粒子（Ａ）の表面に担持させることが可能である。   In addition, as a matter of course, in the firing in an oxygen atmosphere, the cellulose nanofibers are burnt down as carbon dioxide and water, and therefore, a solid electrolyte nanoparticle aggregate (d) containing a part or all of the raw material CNF ) (Hereinafter also referred to as “CNF-encapsulated solid electrolyte nanoparticle aggregate (d)”), or a nanoparticle aggregate composed of a precursor of the solid electrolyte encapsulating part or all of the raw material CNF ( e) CNF-encapsulated solid electrolyte nanoparticle aggregate (d), or CNF-encapsulated precursor by firing an oxygen atmosphere (hereinafter also referred to as “CNF-encapsulated precursor nanoparticle aggregate (e)”) Only the solid electrolyte nanoparticle array (c) retaining the aligned state in the nanoarray obtained by removing the cellulose nanofibers from the nanoparticle aggregate (e) It is possible to be supported on the surface of (A).

なお、本発明において、「内包」とは、対象物の一部、又は全部を、断片的に、又は連続的に、覆っている状態を意味する。本発明においては、たとえば、上記ＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）とは、原料ＣＮＦの一部、又は全部を、少なくとも固体電解質ナノ粒子（ａ）が線状、又は塊状に、連続して、又は断続的に覆っている状態にあり、また、上記ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）とは、原料ＣＮＦの一部、又は全部を、少なくとも上記固体電解質の前駆体からなるナノ粒子が線状、又は塊状に、連続して、又は断続的に覆っている状態にある。   In the present invention, the “inclusive” means a state in which a part or the whole of an object is covered in a fragmentary manner or continuously. In the present invention, for example, the CNF-encapsulated solid electrolyte nanoparticle aggregate (d) refers to a part or all of the raw material CNF, and at least the solid electrolyte nanoparticles (a) are continuously linear or massive. In addition, the CNF-encapsulating precursor nanoparticle aggregate (e) is a nanoparticle composed of at least a part of the raw material CNF and a precursor of the solid electrolyte. The particles are covered linearly or in a lump, continuously or intermittently.

本発明に用いるセルロースナノファイバーの平均長さは、固体電解質ナノ粒子（ａ）が線状に、連続して、又は断続的な、担持されることを可能としつつ、固体電解質粒子（Ａ）との良好な担持を確保する観点から、好ましくは５０ｎｍ〜２００μｍであり、より好ましくは５０ｎｍ〜１５０μｍであり、さらに好ましくは５０ｎｍ〜１００μｍである。また、同様の観点から、用いるセルロースナノファイバーの平均繊維径は、好ましくは５ｎｍ〜５０ｎｍ、より好ましくは５ｎｍ〜３０ｎｍであり、さらに好ましくは５ｎｍ〜２０ｎｍである。   The average length of the cellulose nanofibers used in the present invention is such that the solid electrolyte nanoparticles (a) and the solid electrolyte particles (A) can be supported linearly, continuously or intermittently. From the viewpoint of ensuring good loading, the thickness is preferably 50 nm to 200 μm, more preferably 50 nm to 150 μm, and still more preferably 50 nm to 100 μm. From the same viewpoint, the average fiber diameter of the cellulose nanofiber used is preferably 5 nm to 50 nm, more preferably 5 nm to 30 nm, and further preferably 5 nm to 20 nm.

また、上記セルロースナノファイバーが炭化されてなる、セルロースナノファイバー由来の炭素鎖の平均長さは、固体電解質ナノ粒子（ａ）が線状に、連続して、又は断続的な、担持されることを可能としつつ、効果的に充放電容量を高め得る形状を呈するのを確保する観点から、好ましくは５０ｎｍ〜１０μｍであり、より好ましくは５０ｎｍ〜５μｍであり、さらに好ましくは５０ｎｍ〜１μｍである。   Moreover, the average length of the carbon chain derived from the cellulose nanofiber obtained by carbonizing the cellulose nanofiber is such that the solid electrolyte nanoparticle (a) is supported linearly, continuously, or intermittently. From the viewpoint of ensuring a shape that can effectively increase the charge / discharge capacity while enabling the above-mentioned, it is preferably 50 nm to 10 μm, more preferably 50 nm to 5 μm, and still more preferably 50 nm to 1 μm.

また、上記セルロースナノファイバー由来の炭素鎖の平均繊維径は、５０ｎｍ以下であって、好ましくは４０ｎｍ以下であり、より好ましくは３０ｎｍ以下である。セルロースナノファイバー由来の炭素鎖の平均繊維径の下限値については特に制限はないが、通常、５ｎｍ以上である。   Moreover, the average fiber diameter of the carbon chain derived from the cellulose nanofiber is 50 nm or less, preferably 40 nm or less, and more preferably 30 nm or less. Although there is no restriction | limiting in particular about the lower limit of the average fiber diameter of the carbon chain derived from a cellulose nanofiber, Usually, it is 5 nm or more.

本発明の、固体電解質ナノアレイ（ｂ）、又は固体電解質ナノ粒子列（ｃ）を構成する固体電解質ナノ粒子（ａ）は、全固体二次電池、特に全固体リチウムイオン二次電池に用いることができるものであり、かつ、後述する製造方法における焼成工程において熱分解を生じ難いものであれば、その種類に制限はない。さらに、担持の基材となる固体電解質粒子（Ａ）と必ずしも同じである必要はない。具体的には、酸化物系固体電解質を用いることができ、たとえば、Ｌｉ３ＰＯ４‐Ｌｉ４ＳｉＯ４、Ｌｉ７−ｘＬａ３Ｚｒ２−ｘＴａｘＯ１２、Ｌａ０．５１Ｌｉ０．３４ＴｉＯ２．９４、Ｌｉ１．３Ａｌ０．３Ｔｉ１．７（ＰＯ４）３、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２、５０Ｌｉ４ＳｉＯ４・５０Ｌｉ３ＢＯ３等をあげることができる。また、本発明における固体電解質ナノアレイ（ｂ）、又は固体電解質ナノ粒子列（ｃ）を構成する固体電解質として、Ｌｉ３ＰＯ４‐Ｌｉ４ＳｉＯ４、Ｌｉ７−ｘＬａ３Ｚｒ２−ｘＴａｘＯ１２、Ｌａ０．５１Ｌｉ０．３４ＴｉＯ２．９４、Ｌｉ１．３Ａｌ０．３Ｔｉ１．７（ＰＯ４）３、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２、及び５０Ｌｉ４ＳｉＯ４・５０Ｌｉ３ＢＯ３からなる群のうち少なくとも１種以上を含むものであってもよい。 The solid electrolyte nanoarray (b) or the solid electrolyte nanoparticle (a) constituting the solid electrolyte nanoparticle array (c) of the present invention may be used for an all-solid secondary battery, particularly an all-solid lithium ion secondary battery. There is no limitation on the type of the material as long as it can be produced and hardly undergoes thermal decomposition in the firing step in the production method described later. Furthermore, it is not necessarily the same as the solid electrolyte particles (A) serving as the supporting substrate. Specifically, it is possible to use an oxide-based solid electrolyte, for example, Li 3 PO 4 -Li 4 SiO 4, Li 7-x La 3 Zr 2-x Ta x O 12, La 0.51 Li 0. 34 TiO 2.94 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 7 La 3 Zr 2 O 12 , 50Li 4 SiO 4 .50Li 3 BO 3 and the like can be mentioned. Further, as the solid electrolyte constituting the solid electrolyte Nanoarrays in the present invention (b), or a solid electrolyte nanoparticles column (c), Li 3 PO 4 -Li 4 SiO 4, Li 7-x La 3 Zr 2-x Ta x O 12 , La 0.51 Li 0.34 TiO 2.94 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 7 La 3 Zr 2 O 12 , and 50Li 4 SiO 4 .50Li It may contain at least one or more of the group consisting of 3 BO 3 .

上記固体電解質ナノアレイ（ｂ）、又は固体電解質ナノ粒子列（ｃ）を構成する固体電解質ナノ粒子（ａ）の平均粒径は、電極活物質等との良好な界面を形成する観点、及びセルロースナノファイバー由来の炭素鎖に良好に担持する観点から、０．５ｎｍ〜１００ｎｍが好ましく、１ｎｍ〜８０ｎｍがより好ましく、１ｎｍ〜５０ｎｍが特に好ましい。   The average particle diameter of the solid electrolyte nanoarray (b) or the solid electrolyte nanoparticle (a) constituting the solid electrolyte nanoparticle array (c) has a viewpoint of forming a good interface with the electrode active material, etc. From the viewpoint of favorably supporting the carbon chain derived from the fiber, 0.5 nm to 100 nm is preferable, 1 nm to 80 nm is more preferable, and 1 nm to 50 nm is particularly preferable.

また、上記固体電解質ナノアレイ（ｂ）、又は固体電解質ナノ粒子列（ｃ）を構成する固体電解質のナノ粒子の形状（晶癖）としては、特に限定されないが、板状、針状、立方体、直方体、六角柱状等をあげることができる。なかでも、セルロースナノファイバー由来の炭素鎖への担持をより強固にする観点からは、上記炭素鎖の軸長方向に伸延した直方体粒子が好ましい。   Moreover, the shape (crystal habit) of the solid electrolyte nanoparticles constituting the solid electrolyte nanoarray (b) or the solid electrolyte nanoparticle array (c) is not particularly limited, but is a plate, needle, cube, cuboid And hexagonal columnar shape. Among these, from the viewpoint of further strengthening the support to the carbon chains derived from cellulose nanofibers, the cuboid particles extending in the axial length direction of the carbon chains are preferable.

上記セルロースナノファイバー由来の炭素鎖と上記固体電解質ナノ粒子（ａ）から構成される固体電解質ナノアレイ（ｂ）の平均長さは、特異な形状を呈することによる充放電容量の効果的な向上を確保する観点から、好ましくは５０ｎｍ〜１０μｍであり、より好ましくは５０ｎｍ〜５μｍであり、さらに好ましくは５０ｎｍ〜１μｍである。   The average length of the solid electrolyte nanoarray (b) composed of the carbon chains derived from the cellulose nanofibers and the solid electrolyte nanoparticles (a) ensures effective improvement of the charge / discharge capacity by exhibiting a unique shape. In view of the above, it is preferably 50 nm to 10 μm, more preferably 50 nm to 5 μm, and still more preferably 50 nm to 1 μm.

本発明の全固体二次電池用固体電解質における、上記固体電解質粒子（Ａ）と、上記固体電解質ナノ粒子集合体（ｂ）、上記固体電解質ナノ粒子列（ｃ）、又はその両方を含む場合にはその合計量、との質量割合は、全固体二次電池内で電極活物質粒子と固体電解質粒子とのパッキング構造において界面抵抗が十分に低減された良好な界面を形成する観点、及び全固体二次電池のエネルギー密度を高める観点から、固体電解質粒子：（固体電解質ナノアレイ（ｂ）＋固体電解質ナノ粒子列（ｃ）（ただし、固体電解質ナノアレイ（ｂ）と固体電解質ナノ粒子列（ｃ）は、いずれか一方しか含まない場合は、その一方のみ。））（質量比）＝９９．９：０．１〜７０：３０であるのが好ましく、９９：１〜８０：２０であるのがより好ましい。   In the solid electrolyte for an all-solid-state secondary battery of the present invention, the solid electrolyte particles (A), the solid electrolyte nanoparticle aggregate (b), the solid electrolyte nanoparticle array (c), or both are included. Is the total amount, and the mass proportion of the all-solid-state secondary battery is to form a good interface in which the interface resistance is sufficiently reduced in the packing structure of the electrode active material particles and the solid electrolyte particles, and the total solid From the viewpoint of increasing the energy density of the secondary battery, solid electrolyte particles: (solid electrolyte nanoarray (b) + solid electrolyte nanoparticle array (c) (however, solid electrolyte nanoarray (b) and solid electrolyte nanoparticle array (c) are In the case where only one of them is included, only one of them is included.)) (Mass ratio) = preferably 99.9: 0.1 to 70:30, more preferably 99: 1 to 80:20. preferable.

また、本発明の全固体二次電池用固体電解質において、上記線状とは、直線状、又は略直線状であるとすることができる。なお、線状とは、細長く線形のものをいい、直線的なもののみならず、曲線状や鎖状のものも含む。また、直線状とは、上記固体電解質ナノ粒子（ａ）の集合体（ｂ）又は列（ｃ）の（概）長軸方向において、直線部分が長さ比で概ね７０％以上であるものであってもよく、８０％以上であるものであってもよく、９０％以上であるものであってもよい。また、略直線状とは、上記固体電解質ナノ粒子（ａ）の集合体（ｂ）又は列（ｃ）の（概）軸長方向において、多少の湾曲や近似計算上の誤差のある線状を含む。   In the solid electrolyte for an all-solid-state secondary battery of the present invention, the linear shape may be a linear shape or a substantially linear shape. The linear shape means an elongated and linear shape and includes not only a linear shape but also a curved shape or a chain shape. In addition, the term “linear” means that the straight portion has a length ratio of approximately 70% or more in the (approximately) major axis direction of the aggregate (b) or row (c) of the solid electrolyte nanoparticles (a). It may be 80% or more, or 90% or more. Further, the substantially linear shape means a linear shape having a slight curvature or an error in approximate calculation in the (approximately) axial length direction of the aggregate (b) or the row (c) of the solid electrolyte nanoparticles (a). Including.

また、本発明の全固体二次電池用固体電解質において、上記全固体リチウムイオン二次電池用であるとすることができる。また、本明細書中における全固体二次電池用固体電解質に関する各構成成分や固体電解質等は、特にリチウムイオンに関する特記をしていないものでも、適宜、全固体リチウムイオン二次電池用として用いられうる。   Moreover, the solid electrolyte for an all-solid secondary battery of the present invention can be used for the all-solid lithium ion secondary battery. In addition, each component, solid electrolyte, and the like related to the solid electrolyte for an all-solid-state secondary battery in this specification are appropriately used for an all-solid-state lithium-ion secondary battery, even if not specifically mentioned for lithium ions. sell.

〔全固体二次電池用固体電解質の製造方法〕
一方、本発明の全固体二次電池用固体電解質は、次の工程（ＩＩ）〜（ＩＩＩ）：
少なくとも１種の固体電解質の原料化合物、アルカリ溶液、及びセルロースナノファイバーを含有するスラリーを、温度が１００℃以上、圧力が０．３ＭＰａ〜０．９ＭＰａの水熱反応に付して、ＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）、ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）、又はその両方、を製造する工程（ＩＩ）、並びに、
少なくとも、工程（ＩＩ）で得られた上記ＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）、上記ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）及び上記ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）と反応して固体電解質ナノ粒子集合体（ｂ）若しくは固体電解質ナノ粒子列（ｃ）を生成するための残余の原料化合物、又はその両方を焼成する工程（ＩＩＩ）、
を含む製造方法により、得ることができうる。 [Method for producing solid electrolyte for all-solid-state secondary battery]
On the other hand, the solid electrolyte for an all-solid secondary battery of the present invention includes the following steps (II) to (III):
A slurry containing at least one solid electrolyte raw material compound, an alkaline solution, and cellulose nanofibers is subjected to a hydrothermal reaction at a temperature of 100 ° C. or higher and a pressure of 0.3 MPa to 0.9 MPa to obtain a CNF-encapsulated solid. A step (II) of producing an electrolyte nanoparticle aggregate (d), a CNF-encapsulated precursor nanoparticle aggregate (e), or both, and
Reaction with at least the CNF-encapsulated solid electrolyte nanoparticle aggregate (d), the CNF-encapsulated precursor nanoparticle aggregate (e), and the CNF-encapsulated precursor nanoparticle aggregate (e) obtained in step (II) And firing the remaining raw material compound for producing the solid electrolyte nanoparticle aggregate (b) or the solid electrolyte nanoparticle array (c), or both (III),
Can be obtained by a production method comprising

また、他の本発明の全固体二次電池用固体電解質の製造方法として、
次の工程（ＩＩ）〜（ＩＩＩ’）：
少なくとも１種の固体電解質の原料化合物、アルカリ溶液、及びセルロースナノファイバーを含有するスラリーを、温度が１００℃以上、圧力が０．３ＭＰａ〜０．９ＭＰａの水熱反応に付して、ＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）、ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）、又はその両方、を製造する工程（ＩＩ）、並びに、
少なくとも、工程（ＩＩ）で得られた上記ＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）、上記ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）及び上記ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）と反応して固体電解質ナノ粒子集合体（ｂ）を生成するための残余の原料化合物、又はその両方を、還元雰囲気下で焼成する工程（ＩＩＩ’）、
を含む製造方法を適宜用いることができうる。 In addition, as another method for producing a solid electrolyte for an all-solid-state secondary battery of the present invention,
Next steps (II) to (III ′):
A slurry containing at least one solid electrolyte raw material compound, an alkaline solution, and cellulose nanofibers is subjected to a hydrothermal reaction at a temperature of 100 ° C. or higher and a pressure of 0.3 MPa to 0.9 MPa to obtain a CNF-encapsulated solid. A step (II) of producing an electrolyte nanoparticle aggregate (d), a CNF-encapsulated precursor nanoparticle aggregate (e), or both, and
Reaction with at least the CNF-encapsulated solid electrolyte nanoparticle aggregate (d), the CNF-encapsulated precursor nanoparticle aggregate (e), and the CNF-encapsulated precursor nanoparticle aggregate (e) obtained in step (II) Step (III ′) of firing the remaining raw material compound for producing the solid electrolyte nanoparticle aggregate (b), or both in a reducing atmosphere,
Can be used as appropriate.

さらに、他の本発明の全固体二次電池用固体電解質の製造方法として、
次の工程（ＩＩ）〜（ＩＩＩ’’）：
少なくとも１種の固体電解質の原料化合物、アルカリ溶液、及びセルロースナノファイバーを含有するスラリーを、温度が１００℃以上、圧力が０．３ＭＰａ〜０．９ＭＰａの水熱反応に付して、ＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）、ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）、又はその両方、を製造する工程（ＩＩ）、並びに、
少なくとも、工程（ＩＩ）で得られた上記ＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）、上記ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）及び上記ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）と反応して固体電解質ナノ粒子列（ｃ）を生成するための残余の原料化合物、又はその両方を、酸化雰囲気下で焼成する工程（ＩＩＩ’’）、
を含む製造方法を適宜用いることができうる。 Furthermore, as another method for producing a solid electrolyte for an all-solid-state secondary battery of the present invention,
Next steps (II) to (III ″):
A slurry containing at least one solid electrolyte raw material compound, an alkaline solution, and cellulose nanofibers is subjected to a hydrothermal reaction at a temperature of 100 ° C. or higher and a pressure of 0.3 MPa to 0.9 MPa to obtain a CNF-encapsulated solid. A step (II) of producing an electrolyte nanoparticle aggregate (d), a CNF-encapsulated precursor nanoparticle aggregate (e), or both, and
Reaction with at least the CNF-encapsulated solid electrolyte nanoparticle aggregate (d), the CNF-encapsulated precursor nanoparticle aggregate (e), and the CNF-encapsulated precursor nanoparticle aggregate (e) obtained in step (II) Step (III ″) of firing the remaining raw material compounds for producing the solid electrolyte nanoparticle array (c), or both in an oxidizing atmosphere,
Can be used as appropriate.

また、本発明の全固体二次電池用固体電解質の製造方法において、
さらに、工程（ＩＩＩ）、（ＩＩＩ’）、又は（ＩＩＩ’’）に先立ち、上記固体電解質粒子（Ａ）を製造する工程（Ｉ）、を含む製造方法を適宜用いることができうる。 Further, in the method for producing a solid electrolyte for an all-solid secondary battery of the present invention,
Furthermore, prior to the step (III), (III ′), or (III ″), a production method including the step (I) for producing the solid electrolyte particles (A) can be appropriately used.

工程（Ｉ）は、全固体二次電池用固体電解質粒子（Ａ）を得る工程である。上記固体電解質粒子（Ａ）について、得られる固体電解質粒子（Ａ）の平均粒径が５０ｎｍ〜５０μｍとなるような、既存の、任意の製造方法を用いて製造すればよい。   Step (I) is a step of obtaining solid electrolyte particles (A) for all-solid-state secondary batteries. What is necessary is just to manufacture about the said solid electrolyte particle (A) using the existing arbitrary manufacturing methods that the average particle diameter of the obtained solid electrolyte particle (A) will be 50 nm-50 micrometers.

工程（ＩＩ）は、少なくとも１種の固体電解質の原料化合物、アルカリ溶液、及びセルロースナノファイバーを含有するスラリーを、温度が１００℃以上、圧力が０．３ＭＰａ〜０．９ＭＰａの水熱反応に付して、固体電解質ナノ粒子集合体（ｄ）、又は固体電解質の前駆体からなるナノ粒子集合体（ｅ）、又はその両方、を製造する工程である。   In step (II), a slurry containing at least one solid electrolyte raw material compound, an alkali solution, and cellulose nanofibers is subjected to a hydrothermal reaction at a temperature of 100 ° C. or higher and a pressure of 0.3 MPa to 0.9 MPa. Then, the solid electrolyte nanoparticle aggregate (d), the nanoparticle aggregate (e) composed of the precursor of the solid electrolyte, or both are produced.

この工程（ＩＩ）で得られる水熱反応物は、製造対象とする固体電解質によってＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）、ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）、又はその両方であったりする。具体的には、たとえば、上記固体電解質において、Ｌｉ３ＰＯ４‐Ｌｉ４ＳｉＯ４及び５０Ｌｉ４ＳｉＯ４・５０Ｌｉ３ＢＯ３は、工程（ＩＩ）の１回の水熱反応によってＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）を得ることができるが、一方、Ｌｉ７−ｘＬａ３Ｚｒ２−ｘＴａｘＯ１２、Ｌａ０．５１Ｌｉ０．３４ＴｉＯ２．９４、Ｌｉ１．３Ａｌ０．３Ｔｉ１．７（ＰＯ４）３、及びＬｉ７Ｌａ３Ｚｒ２Ｏ１２は１回の水熱反応でＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）を得ることが困難なので、工程（ＩＩ）の水熱反応ではＣＮＦ内包前駆体ナノ粒子集合体（ｅ）を得うる。 The hydrothermal reactant obtained in this step (II) is CNF-encapsulated solid electrolyte nanoparticle aggregate (d), CNF-encapsulated precursor nanoparticle aggregate (e), or both depending on the solid electrolyte to be produced. Or Specifically, for example, in a solid-state electrolyte, Li 3 PO 4 -Li 4 SiO 4 and 50Li 4 SiO 4 · 50Li 3 BO 3 is, CNF containing solid electrolyte nano by one hydrothermal reaction step (II) Although it is possible to obtain particles aggregates (d), whereas, Li 7-x La 3 Zr 2-x Ta x O 12, La 0.51 Li 0.34 TiO 2.94, Li 1.3 Al 0. 3 Ti 1.7 (PO 4 ) 3 and Li 7 La 3 Zr 2 O 12 are difficult to obtain a CNF-encapsulated solid electrolyte nanoparticle aggregate (d) by one hydrothermal reaction, and therefore, step (II) In the hydrothermal reaction, a CNF-encapsulated precursor nanoparticle aggregate (e) can be obtained.

ここで、固体電解質の前駆体とは、たとえば、Ｌｉ７−ｘＬａ３Ｚｒ２−ｘＴａｘＯ１２では、ＬｉＴａＯ３、Ｌａ０．５１Ｌｉ０．３４ＴｉＯ２．９４では、ＴｉＯ２、Ｌｉ１．３Ａｌ０．３Ｔｉ１．７（ＰＯ４）３では、Ｌｉ３ＰＯ４、また、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２では、ＺｒＯ２である。これらは単独で使用してもよく、また２種以上を混合して使用してもよい。 Here, the precursor of the solid electrolyte is, for example, Li 7-x La 3 Zr 2-x Ta x O 12 , LiTaO 3 , La 0.51 Li 0.34 TiO 2.94 , TiO 2 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 is Li 3 PO 4 , and Li 7 La 3 Zr 2 O 12 is ZrO 2 . These may be used singly or in combination of two or more.

工程（ＩＩ）における、少なくとも１種の固体電解質の原料化合物の使用量は、製造対象とする固体電解質、又は固体電解質の前駆体に応じて所定割合の原料化合物を準備することができる。   In the step (II), the amount of the raw material compound of at least one solid electrolyte used can prepare a predetermined proportion of the raw material compound depending on the solid electrolyte to be produced or the precursor of the solid electrolyte.

この固体電解質の原料化合物としては、具体的には、たとえば、ジルコニウム化合物、チタン化合物、アルミニウム化合物、ケイ素化合物等をあげることができる。なかでも、これら元素の硫酸塩、硝酸塩、炭酸塩、酢酸塩、シュウ酸塩、酸化物、水酸化物、ハロゲン化物等を好適に使用することができる。これらは単独で使用してもよく、また２種以上を混合して使用してもよい。   Specific examples of the solid electrolyte raw material compound include a zirconium compound, a titanium compound, an aluminum compound, and a silicon compound. Of these, sulfates, nitrates, carbonates, acetates, oxalates, oxides, hydroxides, halides, and the like of these elements can be preferably used. These may be used singly or in combination of two or more.

上記原料化合物、及びセルロースナノファイバーを混合してスラリーを調製する際、通常、水を用いる。上記水の使用量は、各原料化合物の溶解性、又は分散性、撹拌の容易性、及び水熱反応の効率等の点から、上記原料化合物の金属元素１モルに対して、１０モル〜３００モルであることが好ましく、さらに５０モル〜２００モルであることが好ましい。   When preparing the slurry by mixing the raw material compound and cellulose nanofiber, water is usually used. The amount of water used is from 10 mol to 300 mol with respect to 1 mol of the metal element of the raw material compound from the viewpoints of solubility or dispersibility of each raw material compound, easiness of stirring, efficiency of hydrothermal reaction, and the like. It is preferable that it is mol, and it is further preferable that it is 50 mol-200 mol.

工程（ＩＩ）で用いられるアルカリ溶液としては、たとえば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、アンモニア等の水溶液をあげることができる。なかでも、水熱反応の効率を高める観点、及び得られるＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）、又はＣＮＦ内包前駆体ナノ粒子集合体（ｅ）を微小にする観点から、水酸化ナトリウム、炭酸ナトリウム又はそれらの混合溶液を用いるのが好ましい。また、スラリーへのアルカリ溶液の使用量は、上記スラリーのｐＨを７〜１２に保持するのに充分な量を滴下する量を用いればよい。また、これらは単独で使用してもよく、また２種以上を混合して使用してもよい。   Examples of the alkaline solution used in step (II) include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and the like. Among these, from the viewpoint of increasing the efficiency of the hydrothermal reaction, and from the viewpoint of making the resulting CNF-encapsulated solid electrolyte nanoparticle aggregate (d) or CNF-encapsulated precursor nanoparticle aggregate (e) fine, sodium hydroxide, It is preferable to use sodium carbonate or a mixed solution thereof. Moreover, what is necessary is just to use the quantity which dripped the quantity sufficient to hold | maintain the pH of the said slurry to 7-12 as the usage-amount of the alkaline solution to a slurry. These may be used alone or in combination of two or more.

また、スラリー中におけるセルロースナノファイバーの含有量は、スラリー中の水１００質量部に対し、炭素原子換算量で、好ましくは０．０１質量部〜１０質量部であり、より好ましくは０．０５質量部〜８質量部である。   Moreover, content of the cellulose nanofiber in a slurry is a carbon atom conversion amount with respect to 100 mass parts of water in a slurry, Preferably it is 0.01 mass part-10 mass parts, More preferably, it is 0.05 mass. Part to 8 parts by mass.

これらの原料の添加順序は、特に限定されない。添加した後、混合する時間は、好ましくは１分間〜１２時間であり、より好ましくは５分間〜６時間である。また、混合する温度は、好ましくは５℃〜６０℃であり、より好ましくは５℃〜５０℃である。   The order of adding these raw materials is not particularly limited. After the addition, the mixing time is preferably 1 minute to 12 hours, more preferably 5 minutes to 6 hours. Moreover, the temperature to mix becomes like this. Preferably it is 5 to 60 degreeC, More preferably, it is 5 to 50 degreeC.

なお、上記スラリーの混合では、セルロースナノファイバーを充分に分散させる観点から、分散機（ホモジナイザー）を用いた処理により、凝集しているセルロースナノファイバーを解砕することが好ましい。上記分散機としては、たとえば、離解機、叩解機、低圧ホモジナイザー、高圧ホモジナイザー、グラインダー、カッターミル、ボールミル、ジェットミル、短軸押出機、２軸押出機、超音波攪拌機、家庭用ジューサーミキサー等をあげることができる。なかでも、分散効率の観点から、超音波攪拌機が好ましい。得られたスラリーの分散均一性の程度は、たとえば、ＵＶ・可視光分光装置を使用した光線透過率や、Ｅ型粘度計を使用した粘度で定量的に評価することもでき、また目視によって白濁度が均一であることを確認することによっても、簡便に評価することができる。分散機で処理する時間は、好ましくは３０秒間〜６分間であり、より好ましくは２分間〜５分間である。   In the mixing of the slurry, from the viewpoint of sufficiently dispersing the cellulose nanofibers, it is preferable to crush the aggregated cellulose nanofibers by a treatment using a disperser (homogenizer). Examples of the disperser include a disaggregator, a beater, a low pressure homogenizer, a high pressure homogenizer, a grinder, a cutter mill, a ball mill, a jet mill, a short shaft extruder, a twin screw extruder, an ultrasonic stirrer, and a home juicer mixer. I can give you. Among these, an ultrasonic stirrer is preferable from the viewpoint of dispersion efficiency. The degree of dispersion uniformity of the obtained slurry can be quantitatively evaluated by, for example, light transmittance using a UV / visible light spectroscope or viscosity using an E-type viscometer. It can also be easily evaluated by confirming that the degree is uniform. The processing time with the disperser is preferably 30 seconds to 6 minutes, more preferably 2 minutes to 5 minutes.

上記スラリーは、未だ凝集状態にあるセルロースナノファイバーを有効に取り除く観点から、さらに、湿式分級することが好ましい。湿式分級には、篩や市販の湿式分級機を使用することができる。篩の目開きは、用いるセルロースナノファイバーの繊維長により変動し得るが、作業効率の観点から、２５μｍ〜１６０μｍであるのが好ましい。   The slurry is preferably further subjected to wet classification from the viewpoint of effectively removing cellulose nanofibers that are still in an aggregated state. A sieve or a commercially available wet classifier can be used for wet classification. The opening of the sieve may vary depending on the fiber length of the cellulose nanofiber to be used, but is preferably 25 μm to 160 μm from the viewpoint of work efficiency.

次に、得られたスラリーを、水熱反応に付す。水熱反応は、１００℃以上であればよく、１３０℃〜１８０℃が好ましい。水熱反応は耐圧容器中で行うのが好ましく、１３０℃〜１８０℃で反応を行う場合、この時の圧力は０．３ＭＰａ〜０．９ＭＰａであるのが好ましく、１４０℃〜１６０℃で反応を行う場合の圧力は０．３ＭＰａ〜０．６ＭＰａであるのが好ましい。水熱反応時間は０．５時間〜２４時間が好ましく、さらに０．５時間〜１５時間が好ましい。   Next, the obtained slurry is subjected to a hydrothermal reaction. Hydrothermal reaction should just be 100 degreeC or more, and 130 to 180 degreeC is preferable. The hydrothermal reaction is preferably performed in a pressure vessel. When the reaction is performed at 130 ° C to 180 ° C, the pressure at this time is preferably 0.3 MPa to 0.9 MPa, and the reaction is performed at 140 ° C to 160 ° C. The pressure in carrying out is preferably 0.3 MPa to 0.6 MPa. The hydrothermal reaction time is preferably 0.5 hours to 24 hours, more preferably 0.5 hours to 15 hours.

得られた水熱反応物は、セルロースナノファイバーと固体電解質、又はセルロースナノファイバーと固体電解質の前駆体からなる複合体であり、ろ過後、水で洗浄し、リパルプ（再懸濁）する。なお、ろ過手段には、減圧ろ過、加圧ろ過、遠心ろ過等を用いることができるが、操作の簡便性等からフィルタープレス等の加圧ろ過が好ましい。   The obtained hydrothermal reaction product is a composite composed of cellulose nanofibers and a solid electrolyte, or a cellulose nanofiber and a solid electrolyte precursor, and after filtration, washed with water and repulped (resuspended). The filtration means may be vacuum filtration, pressure filtration, centrifugal filtration or the like, but pressure filtration such as a filter press is preferred from the viewpoint of simplicity of operation.

ろ過後の複合体を水で洗浄する際、複合体１質量部に対し、水を５質量部〜１００質量部用いるのが好ましい。   When the complex after filtration is washed with water, it is preferable to use 5 to 100 parts by mass of water with respect to 1 part by mass of the complex.

次に、水洗された複合体をリパルプする。次工程の工程（ＩＩＩ）、（ＩＩＩ’）、又は（ＩＩＩ’’）で均一な固体電解質ナノ粒子からなる固体電解質ナノアレイ（ｂ）、又は固体電解質ナノ粒子列（ｃ）を生成させる観点から、リパルプして得られるスラリー中の複合体の含有率は０．５質量％〜２０質量％であることが好ましく、より好ましくは１質量％〜１５質量％であり、さらに好ましくは１．５質量％〜１２質量％である。   Next, the washed composite is repulped. From the viewpoint of generating a solid electrolyte nanoarray (b) or a solid electrolyte nanoparticle array (c) consisting of uniform solid electrolyte nanoparticles in the next step (III), (III ′) or (III ″), The content of the composite in the slurry obtained by repulping is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and even more preferably 1.5% by mass. ˜12% by mass.

工程（ＩＩＩ）、（ＩＩＩ’）、及び（ＩＩＩ’’）は、各々、固体電解質粒子（Ａ）（工程（Ｉ）を含む場合には工程（Ｉ）で得られた固体電解質粒子（Ａ））、上記ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）、及び上記ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）と反応して固体電解質ナノ粒子集合体（ｂ）若しくは固体電解質ナノ粒子列（ｃ）を生成するための残余の原料化合物、又はその両方、を所定量混合して焼成する工程である。   Steps (III), (III ′), and (III ″) are each a solid electrolyte particle (A) (if the step (I) is included, the solid electrolyte particle (A) obtained in step (I) ), The CNF inclusion precursor nanoparticle aggregate (e), and the CNF inclusion precursor nanoparticle aggregate (e) to react with the solid electrolyte nanoparticle aggregate (b) or the solid electrolyte nanoparticle array (c) Is a step of mixing a predetermined amount of the remaining raw material compound or both of them in order to produce baked.

上記工程（ＩＩＩ）、（ＩＩＩ’）、又は（ＩＩＩ’’）により、上記固体電解質ナノアレイ（ｂ）、又は直線的に配列した複数の固体電解質のナノ粒子列（ｃ）が、上記全固体二次電池用固体電解質粒子（Ａ）の表面に担持されることとなる。さらに、この焼成により、全固体二次電池用固体電解質粒子（ｂ）、及び固体電解質のナノ粒子列（ｃ）の双方の結晶性を向上させることができるため、得られる全固体二次電池用固体電解質における充放電特性を有効に高めることができる。   By the step (III), (III ′), or (III ″), the solid electrolyte nanoarray (b) or the nanoparticle array (c) of a plurality of linearly arranged solid electrolytes is converted into the all solid state It will carry | support on the surface of the solid electrolyte particle (A) for secondary batteries. Furthermore, since the crystallinity of both the solid electrolyte particles (b) for an all-solid secondary battery and the nanoparticle array (c) of the solid electrolyte can be improved by this firing, the obtained all-solid-state secondary battery use The charge / discharge characteristics in the solid electrolyte can be effectively enhanced.

ここで、上記全固体二次電池用固体電解質粒子（Ａ）の表面に担持される固体電解質が、セルロースナノファイバー由来の炭素鎖を軸又は基材として、これに特定の固体電解質ナノ粒子（ａ）が複数連なって線状に担持又は配列してなる特異な形状を呈する固体電解質ナノ粒子集合体（固体電解質ナノアレイ）（ｂ）であるか、又は線状に連続して配列した複数の固体電解質ナノ粒子列（ｃ）であるかは、上記焼成における焼成雰囲気で決まる。不活性雰囲気下や還元雰囲気下で焼成される場合には、工程（ＩＩ）で得られたＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）又はＣＮＦ内包前駆体ナノ粒子集合体（ｅ）が担持するセルロースナノファイバーが、炭化してセルロースナノファイバー由来の炭素鎖となって固体電解質ナノアレイ（ｂ）が得られうる。これに対し、酸素雰囲気下で焼成される場合には、上記セルロースナノファイバーが焼失して特異な配列をした複数の固体電解質ナノ粒子列（ｃ）が得られうる。なお、本発明の固体電解質として、得られた固体電解質ナノ粒子集合体（固体電解質ナノアレイ）（ｂ）と固体電解質ナノ粒子列（ｃ）とを適宜組み合わせて用いてもよい。   Here, the solid electrolyte supported on the surface of the solid electrolyte particle (A) for the all-solid-state secondary battery is a specific solid electrolyte nanoparticle (a ) Is a solid electrolyte nanoparticle aggregate (solid electrolyte nanoarray) (b) having a unique shape formed by being supported or arranged in a line in a line, or a plurality of solid electrolytes arranged in a line continuously Whether it is a nanoparticle row | line | column (c) is determined by the baking atmosphere in the said baking. When firing in an inert atmosphere or a reducing atmosphere, the CNF-encapsulated solid electrolyte nanoparticle aggregate (d) or CNF-encapsulated precursor nanoparticle aggregate (e) obtained in step (II) is supported. The cellulose nanofiber is carbonized to become a carbon chain derived from the cellulose nanofiber, and the solid electrolyte nanoarray (b) can be obtained. In contrast, when firing in an oxygen atmosphere, a plurality of solid electrolyte nanoparticle arrays (c) in which the cellulose nanofibers are burned out and have a unique arrangement can be obtained. As the solid electrolyte of the present invention, the obtained solid electrolyte nanoparticle aggregate (solid electrolyte nanoarray) (b) and solid electrolyte nanoparticle array (c) may be used in appropriate combination.

上記焼成における雰囲気は、本発明の全固体二次電池用固体電解質として酸化物系固体電解質を用いる限り制限はなく、必要に応じて使い分ければよい。具体的には、たとえば、電子伝導性に乏しいオリビン系正極活物質を含む全固体リチウムイオン二次電池に本発明の全固体二次電池用固体電解質を使用する場合は、不活性雰囲気焼成による固体電解質ナノアレイ（ｂ）を担持した電子伝導性に優れた固体電解質が好ましく、電子伝導性に問題を有しない電極活物質を含む全固体リチウムイオン二次電池の場合は、簡便な焼成方法である酸素雰囲気焼成を用いた固体電解質のナノ粒子列（ｃ）を担持した固体電解質が好ましい。   There is no restriction | limiting in the atmosphere in the said baking as long as an oxide type solid electrolyte is used as a solid electrolyte for all-solid-state secondary batteries of this invention, What is necessary is just to use properly as needed. Specifically, for example, when the solid electrolyte for an all-solid secondary battery of the present invention is used for an all-solid lithium ion secondary battery containing an olivine-based positive electrode active material having poor electron conductivity, A solid electrolyte excellent in electronic conductivity carrying the electrolyte nanoarray (b) is preferable, and in the case of an all-solid lithium ion secondary battery containing an electrode active material having no problem in electronic conductivity, oxygen is a simple firing method. A solid electrolyte carrying a solid electrolyte nanoparticle array (c) using atmospheric firing is preferred.

工程（ＩＩＩ）は、より詳細には、次の工程（ＩＩＩ−１）〜（ＩＩＩ−３）：
上記固体電解質粒子（Ａ）（工程（Ｉ）を含む場合には工程（Ｉ）で得られた固体電解質粒子（Ａ））、及び工程（ＩＩ）で得られたＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）を混合するか、
上記固体電解質粒子（Ａ）（工程（Ｉ）を含む場合には工程（Ｉ）で得られた固体電解質粒子（Ａ））、工程（ＩＩ）で得られたＣＮＦ内包前駆体ナノ粒子集合体（ｅ）を含むスラリー及び固体電解質の残りの原料化合物を混合するか、又は、
上記固体電解質粒子（Ａ）（工程（Ｉ）を含む場合には工程（Ｉ）で得られた固体電解質粒子（Ａ））、並びに、工程（ＩＩ）で得られたＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）、ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）を含むスラリー及び固体電解質の残りの原料化合物を混合して、スラリーとする工程（ＩＩＩ−１）、
工程（ＩＩＩ−１）で得られたスラリーを乾燥して、全固体二次電池用固体電解質粒子（Ａ）及びＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）からなる混合物か、
全固体二次電池用固体電解質粒子（Ａ）、ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）及び固体電解質の残りの原料化合物からなる混合物か、又は、
全固体二次電池用固体電解質粒子（Ａ）、ＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）、並びにＣＮＦ内包前駆体ナノ粒子集合体（ｅ）及び固体電解質の残りの原料化合物からなる混合物を得る工程（ＩＩＩ−２）、並びに、
工程（ＩＩＩ−２）で得られた混合物を焼成して、全固体二次電池用固体電解質を得る工程（ＩＩＩ−３）、を含む。 More specifically, the step (III) includes the following steps (III-1) to (III-3):
Solid electrolyte particles (A) (in the case of including step (I), solid electrolyte particles (A) obtained in step (I)), and CNF-encapsulated solid electrolyte nanoparticle aggregates obtained in step (II) (D) is mixed,
The solid electrolyte particles (A) (in the case where the step (I) is included, the solid electrolyte particles (A) obtained in the step (I)), the CNF inclusion precursor nanoparticle aggregate obtained in the step (II) ( e) mixing the slurry containing and the remaining raw material compound of the solid electrolyte, or
Solid electrolyte particles (A) (in the case of including step (I), solid electrolyte particles (A) obtained in step (I)), and CNF-encapsulated solid electrolyte nanoparticles obtained in step (II) (D), a slurry containing the CNF-encapsulating precursor nanoparticle aggregate (e) and the remaining raw material compound of the solid electrolyte are mixed to form a slurry (III-1),
The slurry obtained in the step (III-1) is dried, and is a mixture comprising the solid electrolyte particles (A) for all-solid-state secondary batteries and the CNF-encapsulated solid electrolyte nanoparticle aggregate (d),
A mixture comprising solid electrolyte particles (A) for all-solid-state secondary batteries, CNF-encapsulated precursor nanoparticle aggregates (e) and the remaining raw material compounds of the solid electrolyte, or
A solid electrolyte particle (A) for an all-solid-state secondary battery, a CNF-encapsulated solid electrolyte nanoparticle aggregate (d), and a mixture comprising the CNF-encapsulated precursor nanoparticle aggregate (e) and the remaining raw material compound of the solid electrolyte are obtained. Step (III-2), and
Calcination of the mixture obtained in step (III-2) to obtain a solid electrolyte for an all-solid-state secondary battery (III-3).

工程（ＩＩＩ−１）は、具体的には、工程（ＩＩ）で得られたスラリーに、固体電解質粒子（Ａ）（工程（Ｉ）を含む場合には工程（Ｉ）で得られた固体電解質粒子（Ａ））を、又はさらに固体電解質の残りの原料化合物を混合して、スラリーとすればよい。また、上記スラリーには固体電解質粒子（Ａ）を含む場合の全固体二次電池用固体電解質の製造方法例が記載されているが、固体電解質粒子（Ａ）以外の成分で、固体電解質ナノアレイ（ｂ）、又は固体電解質ナノ粒子列（ｃ）を製造した上で、適宜、公知の手法を組み合わせて、それらのいずれか一方、又は両方、を固体電解質粒子（Ａ）の表面に担持して全固体二次電池用固体電解質を得てもよい。   Specifically, in the step (III-1), the solid electrolyte particles (A) (in the case where the step (I) is included, the solid electrolyte obtained in the step (I) is included in the slurry obtained in the step (II). The particles (A)) or the remaining raw material compound of the solid electrolyte may be mixed to form a slurry. Moreover, although the example of the manufacturing method of the solid electrolyte for all-solid-state secondary batteries in case the solid electrolyte particle (A) is included in the said slurry is described, solid electrolyte nanoarray ( b), or after producing the solid electrolyte nanoparticle array (c), by appropriately combining known methods, either or both of them are supported on the surface of the solid electrolyte particles (A) A solid electrolyte for a solid secondary battery may be obtained.

また、工程（ＩＩ）で得られたスラリーと全固体二次電池用固体電解質粒子（Ａ）の混合割合は、最終的に得られる全固体二次電池用固体電解質中の固体電解質粒子（Ａ）と、上記固体電解質ナノ粒子集合体（ｂ）、上記固体電解質ナノ粒子列（ｃ）、又はその両方を含む場合にはその合計量、との質量割合（固体電解質粒子（Ａ）：固体電解質ナノ粒子集合体（ｂ）＋固体電解質ナノ粒子列（ｃ）（ただし、固体電解質ナノ粒子集合体（ｂ）と固体電解質ナノ粒子列（ｃ）は、いずれか一方しか含まない場合は、その一方のみ。））が、９９．９：０．１〜７０：３０であるようにすることが好ましい。   Moreover, the mixing ratio of the slurry obtained in the step (II) and the solid electrolyte particles (A) for all-solid-state secondary batteries is determined by the solid electrolyte particles (A) in the solid electrolyte for all-solid-state secondary batteries finally obtained. And the solid electrolyte nanoparticle aggregate (b), the solid electrolyte nanoparticle array (c), or the total amount thereof when both are included (solid electrolyte particles (A): solid electrolyte nano Particle aggregate (b) + solid electrolyte nanoparticle array (c) (however, when either one of solid electrolyte nanoparticle aggregate (b) and solid electrolyte nanoparticle array (c) is included, only one of them is included. .)) Is preferably 99.9: 0.1 to 70:30.

上記ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）と共に工程（ＩＩ）で得られたスラリーに混合される固体電解質の残りの原料化合物は、所定の元素の硝酸塩、炭酸塩、酢酸塩、シュウ酸塩、酸化物、水酸化物等を好適に使用することができる。これらは単独で使用してもよく、また２種以上を混合して使用してもよい。   The remaining raw material compound of the solid electrolyte mixed with the slurry obtained in the step (II) together with the CNF inclusion precursor nanoparticle aggregate (e) is nitrate, carbonate, acetate, oxalate of a predetermined element Oxides, hydroxides and the like can be preferably used. These may be used singly or in combination of two or more.

これらの原料の工程（ＩＩ）で得られたスラリーへの添加順序は、特に限定されない。添加した後、混合する時間は、好ましくは１分間〜１２時間であり、より好ましくは５分間〜６時間である。また、混合する温度は、好ましくは５℃〜６０℃であり、より好ましくは５℃〜５０℃である。   The order of adding these raw materials to the slurry obtained in step (II) is not particularly limited. After the addition, the mixing time is preferably 1 minute to 12 hours, more preferably 5 minutes to 6 hours. Moreover, the temperature to mix becomes like this. Preferably it is 5 to 60 degreeC, More preferably, it is 5 to 50 degreeC.

続く工程（ＩＩＩ−２）では、工程（ＩＩＩ−１）で得られたスラリーを、乾燥して、全固体二次電池用固体電解質粒子（Ａ）及びＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）からなる混合物か、
全固体二次電池用固体電解質粒子（Ａ）、ＣＮＦ内包前駆体ナノ粒子集合体（ｅ）及び固体電解質の残りの原料化合物からなる混合物か、又は、
全固体二次電池用固体電解質粒子（Ａ）、ＣＮＦ内包固体電解質ナノ粒子集合体（ｄ）、並びにＣＮＦ内包前駆体ナノ粒子集合体（ｅ）及び固体電解質の残りの原料化合物からなる混合物を得る。 In the subsequent step (III-2), the slurry obtained in the step (III-1) is dried, and the solid electrolyte particles for all-solid-state secondary battery (A) and the CNF-encapsulated solid electrolyte nanoparticle aggregate (d) A mixture consisting of
A mixture comprising solid electrolyte particles (A) for all-solid-state secondary batteries, CNF-encapsulated precursor nanoparticle aggregates (e) and the remaining raw material compounds of the solid electrolyte, or
A solid electrolyte particle (A) for an all-solid-state secondary battery, a CNF-encapsulated solid electrolyte nanoparticle aggregate (d), and a mixture comprising the CNF-encapsulated precursor nanoparticle aggregate (e) and the remaining raw material compound of the solid electrolyte are obtained. .

乾燥により得られる混合物の粒径は、レーザー回折・散乱法に基づく粒度分布におけるＤ５０値で、好ましくは５ｎｍ〜５０μｍであり、より好ましくは５０ｎｍ〜２５μｍである。ここで、粒度分布測定におけるＤ５０値とは、レーザー回折・散乱法に基づく体積基準の粒度分布により得られる値であり、Ｄ５０値は累積５０％での粒径（メジアン径）を意味する。 The particle size of the mixture obtained by drying is a D 50 value in the particle size distribution based on the laser diffraction / scattering method, preferably 5 nm to 50 μm, more preferably 50 nm to 25 μm. Here, the D 50 value in the particle size distribution measurement is a value obtained by a volume-based particle size distribution based on the laser diffraction / scattering method, and the D 50 value means a particle size (median diameter) at a cumulative 50%. .

乾燥方法としては、噴霧乾燥、箱型乾燥、流動床乾燥、外熱式乾燥、媒体流動乾燥、凍結乾燥、真空乾燥等をあげることができる。なかでも、得られる混合物の粒子が必要以上に増大するのを有効に制御して微細化を図る観点から、凍結乾燥、凍結乾燥、又は噴霧乾燥が好ましい。   Examples of the drying method include spray drying, box drying, fluidized bed drying, external heat drying, medium fluidized drying, freeze drying, and vacuum drying. Of these, freeze-drying, freeze-drying, or spray-drying is preferred from the viewpoint of effectively controlling the increase in the particles of the resulting mixture more than necessary to achieve finer particles.

続く工程（ＩＩＩ−３）では、工程（ＩＩＩ−２）で得られた混合物を焼成して、全固体二次電池用固体電解質を得る。この焼成により、複合体に含まれるセルロースナノファーバーを炭化させるか焼失させると共に、複合体にＣＮＦ内包前駆体ナノ粒子集合体（ｅ）及び固体電解質の残りの原料化合物を含む場合には、固体電解質ナノ粒子（ａ）を生成する固相反応も生じて、固体電解質ナノアレイ（ｂ）、又は固体電解質ナノ粒子列（ｃ）が表面に担持された全固体二次電池用固体電解質を得ることができる。   In the subsequent step (III-3), the mixture obtained in the step (III-2) is baked to obtain a solid electrolyte for an all-solid-state secondary battery. By this firing, the cellulose nanofabric contained in the composite is carbonized or burned out, and when the composite contains the CNF-encapsulated precursor nanoparticle aggregate (e) and the remaining raw material compound of the solid electrolyte, the solid electrolyte A solid-phase reaction that generates nanoparticles (a) also occurs, and a solid electrolyte for an all-solid-state secondary battery on which the solid electrolyte nanoarray (b) or the solid electrolyte nanoparticle array (c) is supported can be obtained. .

焼成は、任意の焼成雰囲気下で行われ、焼成温度は、好ましくは５００℃〜１２００℃であり、より好ましくは６００℃〜１１００℃である。また焼成時間は、好ましくは１０分間〜１２時間であり、より好ましくは３０分間〜８時間である。   Firing is performed under any firing atmosphere, and the firing temperature is preferably 500 ° C to 1200 ° C, more preferably 600 ° C to 1100 ° C. The firing time is preferably 10 minutes to 12 hours, more preferably 30 minutes to 8 hours.

また、工程（ＩＩＩ’）、及び工程（ＩＩＩ’’）についても、上述の工程（ＩＩＩ）を適宜読み替えて行うことができうる。   Further, the step (III ′) and the step (III ″) can be performed by appropriately replacing the above-described step (III).

〔全固体二次電池〕
本発明の全固体二次電池ないし全固体リチウムイオン二次電池は、上記全固体二次電池用固体電解質を備える。 [All-solid secondary battery]
An all solid state secondary battery or an all solid state lithium ion secondary battery of the present invention includes the solid electrolyte for an all solid state secondary battery.

本発明の全固体二次電池ないし全固体リチウムイオン二次電池においては、上述の全固体二次電池用固体電解質を適宜適用できる。また、本発明の全固体二次電池ないし全固体リチウムイオン二次電池の構成、及び製造方法は、本発明の全固体二次電池用固体電解質を用いる他は、公知の手法を適宜組み合わせることができる。また、本発明の全固体二次電池用固体電解質を適宜適用できる全固体二次電池としては、正極と負極と固体電解質を必須構成とするものであって、正極活物質層、固体電解質層、及び負極活物質層の順に積層配置された積層体が形成されるものであれば特に限定されない。   In the all-solid secondary battery or all-solid lithium ion secondary battery of the present invention, the above-described solid electrolyte for an all-solid secondary battery can be appropriately applied. In addition, the configuration and manufacturing method of the all-solid secondary battery or all-solid lithium ion secondary battery of the present invention can be appropriately combined with known methods, except that the solid electrolyte for the all-solid secondary battery of the present invention is used. it can. Moreover, as an all-solid secondary battery to which the solid electrolyte for an all-solid secondary battery of the present invention can be appropriately applied, a positive electrode, a negative electrode, and a solid electrolyte are essential components, and a positive electrode active material layer, a solid electrolyte layer, And a negative electrode active material layer are not particularly limited as long as a laminate in which the layers are arranged in this order is formed.

この正極活物質層、固体電解質層、及び負極活物質層の順に積層配置された積層体の製造においては、たとえば、特開２０１７−１０８１６号公報に記載されるように、正極活物質層、及び負極活物質層に内包される固体電解質粒子として、本発明の全固体二次電池用固体電解質を用い、固体電解質層には本発明以外の固体電解質を用いてもよい。   In the production of a laminate in which the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer are arranged in this order, for example, as described in JP 2017-10816 A, a positive electrode active material layer, and As the solid electrolyte particles included in the negative electrode active material layer, the solid electrolyte for an all-solid secondary battery of the present invention may be used, and a solid electrolyte other than the present invention may be used for the solid electrolyte layer.

上記の構成を有する全固体二次電池、特に全固体リチウムイオン二次電池の形状としては、特に制限を受けるものではなく、コイン型、円筒型，角型等種々の形状や、ラミネート外装体に封入した不定形状であってもよい。   The shape of the all-solid-state secondary battery having the above-described configuration, particularly the all-solid-state lithium ion secondary battery, is not particularly limited, and various shapes such as a coin shape, a cylindrical shape, and a square shape, and a laminate exterior body can be used. The enclosed irregular shape may be sufficient.

以下、本発明について、実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。   EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

［製造例１］（ＬｉＣｏＰＯ４正極活物質粒子の製造）
水酸化リチウム一水和物１２．７２ｇ、及び水４０ｍＬを混合して、スラリーＡ１を得た。得られたスラリーＡ１を、２５℃の温度に保持しながら３分間撹拌しつつ８５％のリン酸水溶液１１．５３ｇを３５ｍＬ／分で滴下し、撹拌速度４００ｒｐｍで１時間撹拌することによりＬｉ３ＰＯ４スラリーＢ１を得た。次に、得られたＬｉ３ＰＯ４スラリーＢ１全量に対し、硫酸コバルト七水和物２１．０８ｇを添加して、スラリーＣ１とした後、スラリーＣ１をオートクレーブに投入し、１７０℃で１時間の水熱反応を行った。オートクレーブ内の圧力は、０．８ＭＰａであった。生成した水熱反応物をろ過し、次いで、水熱反応物１質量部に対し、１２質量部の水により洗浄した。洗浄した水熱反応物を−５０℃で１２時間凍結乾燥してＬｉＣｏＰＯ４正極活物質粒子（粒子径１００ｎｍ）を得た。 [Production Example 1] (Production of LiCoPO 4 positive electrode active material particles)
12.72 g of lithium hydroxide monohydrate and 40 mL of water were mixed to obtain slurry A1. While the obtained slurry A1 was stirred for 3 minutes while maintaining a temperature of 25 ° C., 11.53 g of 85% phosphoric acid aqueous solution was added dropwise at 35 mL / min, and the mixture was stirred at a stirring speed of 400 rpm for 1 hour to obtain Li 3 PO. 4 slurry B1 was obtained. Next, 21.08 g of cobalt sulfate heptahydrate was added to the total amount of the obtained Li 3 PO 4 slurry B1 to make a slurry C1, and then the slurry C1 was put into an autoclave, and heated at 170 ° C. for 1 hour. Hydrothermal reaction was performed. The pressure in the autoclave was 0.8 MPa. The produced hydrothermal reactant was filtered, and then washed with 12 parts by mass of water with respect to 1 part by mass of the hydrothermal reactant. The washed hydrothermal reaction product was freeze-dried at −50 ° C. for 12 hours to obtain LiCoPO 4 positive electrode active material particles (particle diameter: 100 nm).

［製造例２］（Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２固体電解質粒子の製造）
炭酸リチウム５．１７ｇ、水酸化ランタン１１．４０ｇ、及び酸化ジルコニウム４．９３ｇを、遊星ボールミルで２００ｒｐｍで２時間粉砕混合して混合物Ａ２を得た。得られた混合物Ａ２をペレットに成形した後、空気雰囲気下で９００℃で１２時間焼成した後、乳鉢で解砕して、ＬＬＺ（Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２）固体電解質粒子を得た。（ＬＬＺ固体電解質粒子の平均粒径：１μｍ） [Production Example 2] (Production of Li 7 La 3 Zr 2 O 12 solid electrolyte particles)
Lithium carbonate 5.17 g, lanthanum hydroxide 11.40 g, and zirconium oxide 4.93 g were pulverized and mixed at 200 rpm for 2 hours in a planetary ball mill to obtain a mixture A2. The obtained mixture A2 was formed into pellets, calcined at 900 ° C. for 12 hours in an air atmosphere, and then crushed in a mortar to obtain LLZ (Li 7 La 3 Zr 2 O 12 ) solid electrolyte particles. (Average particle size of LLZ solid electrolyte particles: 1 μm)

［実施例１］（ＬＬＺナノアレイを担持したＬＬＺ固体電解質粒子）
硫酸ジルコニウム四水和物１．８１ｇ、セルロースナノファイバー１９．２９ｇ（スギノマシン社製、ＴＭａ−１０００２、含水量９８質量％）、及び水５５ｍＬを６０分間混合してスラリーＡ３を作製した。得られたスラリーＡ３に、１０質量％濃度のＮａＯＨ水溶液１２．０ｇを添加し、５分間混合してスラリーＢ３を作製した。得られたスラリーＢ３をオートクレーブに投入し、１４０℃で１時間水熱反応を行った。得られた水熱反応生成物Ｃ３を放冷した後、ろ過、水洗、水でリパルプして、セルロースナノファイバーに複数のＺｒＯ２ナノ粒子が直線的に担持されたＺｒＯ２ナノアレイを１０質量％含有したスラリーＤ３を得た。 [Example 1] (LLZ solid electrolyte particles supporting an LLZ nanoarray)
A slurry A3 was prepared by mixing 1.81 g of zirconium sulfate tetrahydrate, 19.29 g of cellulose nanofiber (manufactured by Sugino Machine, TMa-1202, water content 98 mass%), and 55 mL of water for 60 minutes. To the obtained slurry A3, 12.0 g of a 10 mass% NaOH aqueous solution was added and mixed for 5 minutes to prepare a slurry B3. The obtained slurry B3 was put into an autoclave and subjected to a hydrothermal reaction at 140 ° C. for 1 hour. The obtained hydrothermal reaction product C3 is allowed to cool, then filtered, washed with water, repulped with water, and contains 10% by mass of ZrO 2 nanoarrays in which a plurality of ZrO 2 nanoparticles are linearly supported on cellulose nanofibers. A slurry D3 was obtained.

得られたスラリーＤ３全量に、硝酸リチウム１．２１ｇ、硝酸ランタン六水和物３．２５ｇ、及び製造例１で得られたＬＬＺ固体電解質粒子３９．７ｇを混合し、スラリーＥ３を得た。得られたスラリーＥ３を凍結乾燥して、原料混合粉末Ｆ３を得た。原料混合粉末Ｆ３を窒素ガスをパージした電気炉を用い、１１００℃で１時間焼成することにより、ＬＬＺ固体電解質粒子の表面にＬＬＺ固体電解質ナノアレイが担持してなる全固体リチウムイオン二次電池用電極活物質Ａを得た。得られた全固体リチウムイオン二次電池用電極活物質Ａ１００質量％中のＬＬＺ固体電解質ナノアレイの含有率は、５質量％であった。   Lithium nitrate 1.21 g, lanthanum nitrate hexahydrate 3.25 g, and 39.7 g of LLZ solid electrolyte particles obtained in Production Example 1 were mixed with the total amount of the obtained slurry D3 to obtain slurry E3. The obtained slurry E3 was freeze-dried to obtain a raw material mixed powder F3. An electrode for an all-solid-state lithium ion secondary battery in which the LLZ solid electrolyte nanoarray is supported on the surface of the LLZ solid electrolyte particles by firing the raw material mixed powder F3 at 1100 ° C. for 1 hour using an electric furnace purged with nitrogen gas Active material A was obtained. The content of the LLZ solid electrolyte nanoarray in 100% by mass of the obtained electrode active material A for an all solid lithium ion secondary battery was 5% by mass.

得られた全固体リチウムイオン二次電池用電極活物質Ａの、表面部のＴＥＭ写真を図１に示す。なお、使用したＴＥＭは、日本電子株式会社製ＪＥＭ−ＡＲＭ２００Ｆであった。   FIG. 1 shows a TEM photograph of the surface portion of the obtained electrode active material A for an all solid lithium ion secondary battery. The TEM used was JEM-ARM200F manufactured by JEOL Ltd.

［比較例１］（ＬＬＺ固体電解質粒子）
製造例２で得たＬＬＺ固体電解質粒子を、そのまま全固体リチウムイオン二次電池用固体電解質として用いた。 [Comparative Example 1] (LLZ solid electrolyte particles)
The LLZ solid electrolyte particles obtained in Production Example 2 were used as they were as a solid electrolyte for an all solid lithium ion secondary battery.

≪全固体リチウムイオン二次電池における放電容量の評価≫
製造例１で得られたＬｉＣｏＰＯ４正極活物質粒子と、実施例１又は比較例１で得られた固体電解質粒子を用い、全固体リチウムイオン電池用正極を作製した。より具体的には、正極活物質：固体電解質（質量比）を７５：２５の配合割合で混合後、プレス用冶具に投入して正極活物質層とし、その上に固体電解質粒子のみをさらに投入して固体電解質層として積層させた後、ハンドプレスを用いて１６ＭＰａで２分間プレスして、φ１４ｍｍの円盤状の正極を得た。次いで、負極としてリチウム箔を固体電解質層側に取り付けることで、全固体リチウムイオン二次電池を作製した。 ≪Evaluation of discharge capacity in all solid-state lithium ion secondary battery≫
Using the LiCoPO 4 positive electrode active material particles obtained in Production Example 1 and the solid electrolyte particles obtained in Example 1 or Comparative Example 1, a positive electrode for an all solid lithium ion battery was produced. More specifically, after mixing positive electrode active material: solid electrolyte (mass ratio) at a mixing ratio of 75:25, it is put into a pressing jig to form a positive electrode active material layer, and only solid electrolyte particles are further put thereon. After being laminated as a solid electrolyte layer, it was pressed at 16 MPa for 2 minutes using a hand press to obtain a disk-shaped positive electrode having a diameter of 14 mm. Next, an all-solid lithium ion secondary battery was fabricated by attaching a lithium foil as the negative electrode to the solid electrolyte layer side.

作製した全固体リチウムイオン二次電池を用いて、充電条件を１６ｍＡ／ｇ、電圧５．０Ｖの定電流充電、放電条件を１６ｍＡ／ｇ、終止電圧３．５Ｖの定電流放電とした場合の、１６ｍＡ／ｇにおける放電容量を求めた。なお、充放電試験は全て４５℃で行った。   Using the produced all-solid lithium ion secondary battery, the charging condition is 16 mA / g, the voltage is 5.0 V constant current charging, the discharging condition is 16 mA / g, the final voltage is 3.5 V constant current discharging, The discharge capacity at 16 mA / g was determined. All charge / discharge tests were conducted at 45 ° C.

上記評価の結果を表１に示す。   The results of the evaluation are shown in Table 1.

表１から明らかなように、実施例１の、粒子表面に固体電解質ナノ粒子が担持された固体電解質を使用した全固体リチウムイオン二次電池は、比較例１の、固体電解質ナノ粒子を担持していない一般的な固体電解質を使用した全固体リチウムイオン二次電池と比べ、放電容量が非常に大きくなっていることがわかる。   As is clear from Table 1, the all-solid-state lithium ion secondary battery using the solid electrolyte in which the solid electrolyte nanoparticles are supported on the particle surface of Example 1 carries the solid electrolyte nanoparticles in Comparative Example 1. It can be seen that the discharge capacity is very large compared to an all-solid lithium ion secondary battery using a general solid electrolyte that is not.

Claims (11)

平均繊維径が５０ｎｍ以下のセルロースナノファイバー由来の炭素鎖に複数の固体電解質ナノ粒子（ａ）が線状に担持してなる固体電解質ナノ粒子集合体（ｂ）が、固体電解質粒子（Ａ）の表面に担持されてなる、全固体二次電池用固体電解質。   A solid electrolyte nanoparticle aggregate (b) in which a plurality of solid electrolyte nanoparticles (a) are linearly supported on a carbon chain derived from cellulose nanofibers having an average fiber diameter of 50 nm or less is a solid electrolyte particle (A). A solid electrolyte for an all-solid-state secondary battery supported on a surface. 平均繊維径が５０ｎｍ以下のセルロースナノファイバーに誘導されて固体電解質ナノ粒子（ａ）が線状に連続して配列した固体電解質ナノ粒子列（ｃ）が、固体電解質粒子（Ａ）の表面に担持されてなる、全固体二次電池用固体電解質。   A solid electrolyte nanoparticle array (c) in which the solid electrolyte nanoparticles (a) are linearly arranged in a linear manner and are guided by cellulose nanofibers having an average fiber diameter of 50 nm or less is supported on the surface of the solid electrolyte particles (A). A solid electrolyte for an all-solid-state secondary battery. 前記固体電解質粒子（Ａ）の平均粒子径が、１０ｎｍ〜５０μｍである、請求項１又は２に記載の全固体二次電池用固体電解質。   The solid electrolyte for an all-solid-state secondary battery according to claim 1 or 2, wherein an average particle size of the solid electrolyte particles (A) is 10 nm to 50 µm. 前記固体電解質ナノ粒子（ａ）の平均粒子径が、０．５ｎｍ〜１００ｎｍである請求項１〜３のいずれか１項に記載の全固体二次電池用固体電解質。   The solid electrolyte for an all-solid-state secondary battery according to any one of claims 1 to 3, wherein an average particle size of the solid electrolyte nanoparticles (a) is 0.5 nm to 100 nm. 前記固体電解質粒子（Ａ）と、前記固体電解質ナノ粒子集合体（ｂ）、前記固体電解質ナノ粒子列（ｃ）、又はその両方を含む場合にはその合計量、との質量割合が、９９．９：０．１〜７０：３０である請求項１〜４のいずれか１項に記載の全固体二次電池用固体電解質。   When the solid electrolyte particles (A) and the solid electrolyte nanoparticle aggregate (b), the solid electrolyte nanoparticle array (c), or both are included, the mass ratio thereof is 99.99. It is 9: 0.1-70: 30, The solid electrolyte for all-solid-state secondary batteries of any one of Claims 1-4. 前記固体電解質粒子（Ａ）が、Ｌｉ３ＰＯ４‐Ｌｉ４ＳｉＯ４、Ｌｉ７−ｘＬａ３Ｚｒ２−ｘＴａｘＯ１２、Ｌａ０．５１Ｌｉ０．３４ＴｉＯ２．９４、Ｌｉ１．３Ａｌ０．３Ｔｉ１．７（ＰＯ４）３、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２、及び５０Ｌｉ４ＳｉＯ４・５０Ｌｉ３ＢＯ３からなる群のうち少なくとも１種以上を含む、請求項１〜５のいずれか１項に記載の全固体二次電池用固体電解質。 The solid electrolyte particles (A) is, Li 3 PO 4 -Li 4 SiO 4, Li 7-x La 3 Zr 2-x Ta x O 12, La 0.51 Li 0.34 TiO 2.94, Li 1. 3 Al 0.3 Ti 1.7 (PO 4 ) 3, Li 7 La 3 Zr 2 O 12, and 50Li 4 including SiO 4 · 50Li 3 BO 3 at least one or more of the group consisting of, claim 1 6. The solid electrolyte for an all-solid-state secondary battery according to any one of 5 above. 前記固体電解質ナノ粒子（ａ）が、Ｌｉ３ＰＯ４‐Ｌｉ４ＳｉＯ４、Ｌｉ７−ｘＬａ３Ｚｒ２−ｘＴａｘＯ１２、Ｌａ０．５１Ｌｉ０．３４ＴｉＯ２．９４、Ｌｉ１．３Ａｌ０．３Ｔｉ１．７（ＰＯ４）３、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２、及び５０Ｌｉ４ＳｉＯ４・５０Ｌｉ３ＢＯ３からなる群のうち少なくとも１種以上を含む、請求項１〜６のいずれか１項に記載の全固体二次電池用固体電解質。 The solid electrolyte nanoparticles (a) is, Li 3 PO 4 -Li 4 SiO 4, Li 7-x La 3 Zr 2-x Ta x O 12, La 0.51 Li 0.34 TiO 2.94, Li 1 .3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 7 La 3 Zr 2 O 12 , and 50Li 4 SiO 4 .50Li 3 BO 3. The solid electrolyte for all-solid-state secondary batteries of any one of -6. 前記線状が、直線状、又は略直線状である、請求項１〜７のいずれか１項に記載の全固体二次電池用固体電解質。   The solid electrolyte for an all-solid-state secondary battery according to claim 1, wherein the linear shape is linear or substantially linear. 全固体リチウムイオン二次電池用である、請求項１〜８のいずれか１項に記載の全固体二次電池用固体電解質。   The solid electrolyte for an all solid state secondary battery according to any one of claims 1 to 8, which is used for an all solid state lithium ion secondary battery. 請求項１〜９のいずれか１項に記載の全固体二次電池用固体電解質を備える、全固体二次電池。   An all-solid-state secondary battery comprising the solid electrolyte for an all-solid-state secondary battery according to claim 1. 前記二次電池が、全固体リチウムイオン二次電池である、請求項１０に記載の全固体二次電池。   The all-solid-state secondary battery of Claim 10 whose said secondary battery is an all-solid-state lithium ion secondary battery.
JP2019161035A 2017-03-16 2019-09-04 Solid electrolytes for all-solid-state secondary batteries, their manufacturing methods, and all-solid-state secondary batteries Active JP7061100B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017051281 2017-03-16
JP2017051281 2017-03-16

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP2018047660A Division JP6622838B2 (en) 2017-03-16 2018-03-15 Solid electrolyte for all solid state secondary battery, method for producing the same, and all solid state secondary battery

Publications (2)

Publication Number Publication Date
JP2019204800A true JP2019204800A (en) 2019-11-28
JP7061100B2 JP7061100B2 (en) 2022-04-27

Family

ID=63715695

Family Applications (12)

Application Number Title Priority Date Filing Date
JP2017157812A Active JP6442574B2 (en) 2017-03-16 2017-08-18 Nanoparticle aggregate, nanoparticle fired product, and production method thereof
JP2017181024A Active JP6505181B2 (en) 2017-03-16 2017-09-21 Catalyst for purifying automobile exhaust gas and method for producing the same
JP2018037045A Active JP6527258B2 (en) 2017-03-16 2018-03-02 Method of manufacturing positive electrode active material for nano-array like lithium ion secondary battery
JP2018042464A Active JP6646092B2 (en) 2017-03-16 2018-03-09 Oxide semiconductor nanoparticle aggregate for resistance type oxygen sensor and method for producing the same
JP2018044275A Active JP6590967B2 (en) 2017-03-16 2018-03-12 Oxide semiconductor for carbon monoxide gas sensor and method for producing the same
JP2018044694A Active JP6595028B2 (en) 2017-03-16 2018-03-12 Method for producing exhaust gas purification catalyst
JP2018044274A Active JP6602908B2 (en) 2017-03-16 2018-03-12 Zirconia slurry for thin film formation and manufacturing method thereof
JP2018044276A Active JP6590968B2 (en) 2017-03-16 2018-03-12 Oxide semiconductor for ammonia gas sensor and manufacturing method thereof
JP2018047662A Active JP6625153B2 (en) 2017-03-16 2018-03-15 Electrode active material for all-solid secondary battery, method for producing the same, and all-solid secondary battery
JP2018047660A Active JP6622838B2 (en) 2017-03-16 2018-03-15 Solid electrolyte for all solid state secondary battery, method for producing the same, and all solid state secondary battery
JP2019161173A Active JP7061101B2 (en) 2017-03-16 2019-09-04 Electrode active material for all-solid-state secondary battery, its manufacturing method, and all-solid-state secondary battery
JP2019161035A Active JP7061100B2 (en) 2017-03-16 2019-09-04 Solid electrolytes for all-solid-state secondary batteries, their manufacturing methods, and all-solid-state secondary batteries

Family Applications Before (11)

Application Number Title Priority Date Filing Date
JP2017157812A Active JP6442574B2 (en) 2017-03-16 2017-08-18 Nanoparticle aggregate, nanoparticle fired product, and production method thereof
JP2017181024A Active JP6505181B2 (en) 2017-03-16 2017-09-21 Catalyst for purifying automobile exhaust gas and method for producing the same
JP2018037045A Active JP6527258B2 (en) 2017-03-16 2018-03-02 Method of manufacturing positive electrode active material for nano-array like lithium ion secondary battery
JP2018042464A Active JP6646092B2 (en) 2017-03-16 2018-03-09 Oxide semiconductor nanoparticle aggregate for resistance type oxygen sensor and method for producing the same
JP2018044275A Active JP6590967B2 (en) 2017-03-16 2018-03-12 Oxide semiconductor for carbon monoxide gas sensor and method for producing the same
JP2018044694A Active JP6595028B2 (en) 2017-03-16 2018-03-12 Method for producing exhaust gas purification catalyst
JP2018044274A Active JP6602908B2 (en) 2017-03-16 2018-03-12 Zirconia slurry for thin film formation and manufacturing method thereof
JP2018044276A Active JP6590968B2 (en) 2017-03-16 2018-03-12 Oxide semiconductor for ammonia gas sensor and manufacturing method thereof
JP2018047662A Active JP6625153B2 (en) 2017-03-16 2018-03-15 Electrode active material for all-solid secondary battery, method for producing the same, and all-solid secondary battery
JP2018047660A Active JP6622838B2 (en) 2017-03-16 2018-03-15 Solid electrolyte for all solid state secondary battery, method for producing the same, and all solid state secondary battery
JP2019161173A Active JP7061101B2 (en) 2017-03-16 2019-09-04 Electrode active material for all-solid-state secondary battery, its manufacturing method, and all-solid-state secondary battery

Country Status (1)

Country Link
JP (12) JP6442574B2 (en)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3602661A4 (en) * 2017-03-31 2021-01-13 The Regents of The University of Michigan System and method for the formation of facile lithium metal anode interface with a solid state electrolyte
WO2019065066A1 (en) * 2017-09-28 2019-04-04 富士フイルム株式会社 Solid electrolyte composition, solid electrolyte-containing sheet, all-solid-state secondary battery, method for producing solid electrolyte-containing sheet, and method for producing all-solid-state secondary battery
JP6962883B2 (en) * 2018-08-24 2021-11-05 株式会社三共 Pachinko machine
JP2020028577A (en) * 2018-08-24 2020-02-27 株式会社三共 Game machine
JP7165569B2 (en) * 2018-12-03 2022-11-04 太平洋セメント株式会社 Positive electrode paste for lithium ion secondary battery and method for producing the same
JP7152945B2 (en) * 2018-12-10 2022-10-13 太平洋セメント株式会社 Method for producing nanoparticle aggregate for negative electrode active material of lithium ion secondary battery
JP7189006B2 (en) * 2018-12-21 2022-12-13 太平洋セメント株式会社 Method for producing NASICON-type oxide particles for solid electrolyte of lithium-ion secondary battery
JP7165048B2 (en) * 2018-12-21 2022-11-02 太平洋セメント株式会社 METHOD FOR MANUFACTURING LISICON-TYPE CRYSTAL PARTICLES FOR SOLID ELECTROLYTE FOR LITHIUM-ION SECONDARY BATTERY
JP7224170B2 (en) * 2018-12-21 2023-02-17 太平洋セメント株式会社 LISICON type crystal particles for solid electrolyte of lithium ion secondary battery and method for producing the same
JP7224171B2 (en) * 2018-12-21 2023-02-17 太平洋セメント株式会社 Method for producing LISICON type crystal particles for solid electrolyte of lithium ion secondary battery
WO2020166429A1 (en) * 2019-02-13 2020-08-20 Ｓｅｍｉｔｅｃ株式会社 Gas detection device and gas detection method
JP7165608B2 (en) * 2019-03-19 2022-11-04 太平洋セメント株式会社 Positive electrode active material composite for lithium ion secondary battery and method for producing the same
WO2020195237A1 (en) * 2019-03-26 2020-10-01 サクラ工業株式会社 Catalyst layer forming material, catalyst device constituent material, catalyst device, and production methods thereof
JP7385859B2 (en) 2019-08-26 2023-11-24 国立大学法人東京工業大学 Gas sensor with nanogap electrode and manufacturing method thereof
JP7340995B2 (en) * 2019-09-02 2023-09-08 太平洋セメント株式会社 Method for producing chain-like lithium lanthanum titanate crystal particle aggregate for solid electrolyte
JP7403289B2 (en) 2019-11-27 2023-12-22 太平洋セメント株式会社 Positive electrode active material composite for lithium ion secondary battery and method for manufacturing the same
JP7351736B2 (en) 2019-12-11 2023-09-27 太平洋セメント株式会社 Method for producing lithium lanthanum zirconium oxide crystal particle aggregate for solid electrolyte
US11532813B2 (en) 2020-02-20 2022-12-20 Samsung Electronics Co., Ltd. Composite cathode active material, preparation method thereof, cathode layer including the same, and all-solid secondary battery including the cathode layer
CN111977658B (en) * 2020-08-26 2021-03-02 成都新柯力化工科技有限公司 Method for continuously producing silicon-carbon negative electrode material of lithium battery
CN112499678B (en) * 2020-11-23 2021-12-28 山东国瓷功能材料股份有限公司 Nano zirconium oxide powder, preparation method thereof, dispersion liquid obtained by preparation method and optical film

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004319186A (en) * 2003-04-14 2004-11-11 Sony Corp Nonaqueous electrolyte battery
JP2014026809A (en) * 2012-07-26 2014-02-06 Toyota Motor Corp Fibrous oxide solid electrolyte, all solid battery, and method for manufacturing the same
JP2015153460A (en) * 2014-02-10 2015-08-24 古河機械金属株式会社 Solid electrolyte sheet, all-solid lithium ion battery, and method of manufacturing solid electrolyte sheet
JP2016058277A (en) * 2014-09-10 2016-04-21 トヨタ自動車株式会社 Positive electrode mixture, positive electrode, solid battery and manufacturing methods thereof
US20160248118A1 (en) * 2013-09-11 2016-08-25 Candace Chan Nanowire-based solid electrolytes and lithium-ion batteries including the same
JP2016184569A (en) * 2015-03-26 2016-10-20 太平洋セメント株式会社 Positive electrode active material for secondary battery and manufacturing method of the same
JP2016207418A (en) * 2015-04-21 2016-12-08 トヨタ自動車株式会社 Electrode mixture
WO2016199805A1 (en) * 2015-06-08 2016-12-15 富士フイルム株式会社 Solid electrolyte composition, electrode sheet for all-solid-state secondary batteries, all-solid-state secondary battery, method for producing electrode sheet for all-solid-state secondary batteries, and method for producing all-solid-state secondary battery

Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3903181B2 (en) * 2002-06-27 2007-04-11 独立行政法人産業技術総合研究所 Resistance oxygen sensor, oxygen sensor device using the same, and air-fuel ratio control system
KR100534708B1 (en) * 2003-10-15 2005-12-07 현대자동차주식회사 Oxygen sensor heating control method of vehicle
JP2007139669A (en) * 2005-11-21 2007-06-07 Ngk Spark Plug Co Ltd Gas sensor
KR100812357B1 (en) * 2005-12-23 2008-03-11 한국과학기술연구원 Ultra-sensitive metal oxide gas sensor and fbrication method thereof
JP2007229640A (en) * 2006-03-01 2007-09-13 Nissan Motor Co Ltd Catalyst for purification of exhaust gas and its manufacturing method
EP2022562B1 (en) * 2006-04-03 2021-06-09 Nissan Motor Company Limited Exhaust gas purifying catalyst
CA2669438C (en) * 2006-04-24 2015-06-16 Axcelon Biopolymers Corporation Nanosilver coated bacterial cellulose
JP2008121127A (en) * 2006-11-08 2008-05-29 Ehime Prefecture Method for producing pulp
JP5551329B2 (en) * 2006-11-14 2014-07-16 日産自動車株式会社 Exhaust gas purification catalyst and method for producing the same
JP5661989B2 (en) * 2007-04-20 2015-01-28 日産自動車株式会社 High heat resistant catalyst and process for producing the same
JP2009014610A (en) * 2007-07-06 2009-01-22 Yamaha Motor Co Ltd Resistance oxygen sensor, air-fuel ratio controller, and transport machine
CA2638410A1 (en) * 2008-07-28 2010-01-28 Hydro-Quebec Composite electrode material
JP5272738B2 (en) * 2009-01-05 2013-08-28 コニカミノルタ株式会社 Polymer film with cellulose coating film
WO2010095574A1 (en) * 2009-02-18 2010-08-26 国立大学法人 九州大学 Complex comprising cellulose nanofibers and metal nanoparticles, and process for producing same
JP6057893B2 (en) * 2011-04-28 2017-01-11 昭和電工株式会社 Positive electrode material for lithium secondary battery and method for producing the same
SE536780C2 (en) * 2011-10-26 2014-08-05 Stora Enso Oyj Process for preparing a dispersion comprising nanoparticles and a dispersion prepared according to the process
JP6345122B2 (en) * 2012-02-10 2018-06-20 セルテック・アクチボラゲットＣｅｌｌｕｔｅｃｈ Ａｂ Cellulose nanofibrils modified with magnetic nanoparticles
JP5895600B2 (en) * 2012-03-01 2016-03-30 日産自動車株式会社 Exhaust gas purification catalyst and method for producing the same
JP2013209779A (en) * 2012-03-30 2013-10-10 Toppan Printing Co Ltd Formed body and method for producing the same
JP5921960B2 (en) * 2012-06-04 2016-05-24 第一工業製薬株式会社 Composition containing inorganic fine particles and film using the same
US9604198B2 (en) * 2012-09-19 2017-03-28 Shin-Etsu Chemical Co., Ltd. Visible light-responsive photocatalytic nanoparticle dispersion liquid, method for producing same, and member having photocatalytic thin film on surface
JP6224311B2 (en) * 2012-11-06 2017-11-01 Ｎｉｓｓｈａ株式会社 Semiconductor gas sensor element
JP6345925B2 (en) * 2013-10-03 2018-06-20 中越パルプ工業株式会社 Nanocomposite and method for producing nanocomposite
JP5802811B1 (en) * 2014-08-27 2015-11-04 株式会社ジーエル・マテリアルズホールディングス Method for producing nanoparticles
JP6913307B2 (en) * 2014-09-17 2021-08-04 国立大学法人東海国立大学機構 Conductive composition and its manufacturing method
KR101610354B1 (en) * 2014-09-18 2016-04-11 재단법인대구경북과학기술원 Production method of a metal oxide supported carbon nano fiber electrode using electro deposition method, and an energy storage device and a filter using the same
KR101992614B1 (en) * 2014-09-26 2019-06-25 다이헤이요 세멘토 가부시키가이샤 Positive-electrode active material for secondary cell, and method for manufacturing same
JP2016069616A (en) * 2014-09-28 2016-05-09 第一工業製薬株式会社 Inorganic fine particle-containing composition and coating using the same
JP6243372B2 (en) * 2015-03-27 2017-12-06 トヨタ自動車株式会社 Exhaust gas purification catalyst
KR101745128B1 (en) * 2015-09-01 2017-06-08 현대자동차주식회사 Chemochromic nanoparticles, method for manufacturing the same, and hydrogen sensor comprising the same
JP6910026B2 (en) * 2016-10-03 2021-07-28 国立研究開発法人産業技術総合研究所 Composite materials and their manufacturing methods and thermally conductive materials

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004319186A (en) * 2003-04-14 2004-11-11 Sony Corp Nonaqueous electrolyte battery
JP2014026809A (en) * 2012-07-26 2014-02-06 Toyota Motor Corp Fibrous oxide solid electrolyte, all solid battery, and method for manufacturing the same
US20160248118A1 (en) * 2013-09-11 2016-08-25 Candace Chan Nanowire-based solid electrolytes and lithium-ion batteries including the same
JP2015153460A (en) * 2014-02-10 2015-08-24 古河機械金属株式会社 Solid electrolyte sheet, all-solid lithium ion battery, and method of manufacturing solid electrolyte sheet
JP2016058277A (en) * 2014-09-10 2016-04-21 トヨタ自動車株式会社 Positive electrode mixture, positive electrode, solid battery and manufacturing methods thereof
JP2016184569A (en) * 2015-03-26 2016-10-20 太平洋セメント株式会社 Positive electrode active material for secondary battery and manufacturing method of the same
JP2016207418A (en) * 2015-04-21 2016-12-08 トヨタ自動車株式会社 Electrode mixture
WO2016199805A1 (en) * 2015-06-08 2016-12-15 富士フイルム株式会社 Solid electrolyte composition, electrode sheet for all-solid-state secondary batteries, all-solid-state secondary battery, method for producing electrode sheet for all-solid-state secondary batteries, and method for producing all-solid-state secondary battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIBO DENG, ET AL.: "Carbon nanofibres produced from electrospun cellulose nanofibres", CARBON, vol. 58, JPN6019005163, 2013, pages 66 - 75, XP028579257, ISSN: 0004725167, DOI: 10.1016/j.carbon.2013.02.032 *

Also Published As

Publication number Publication date
JP2018155748A (en) 2018-10-04
JP6505181B2 (en) 2019-04-24
JP2018154545A (en) 2018-10-04
JP6527258B2 (en) 2019-06-05
JP6595028B2 (en) 2019-10-23
JP6602908B2 (en) 2019-11-06
JP6625153B2 (en) 2019-12-25
JP6590967B2 (en) 2019-10-16
JP6442574B2 (en) 2018-12-19
JP2018156941A (en) 2018-10-04
JP7061101B2 (en) 2022-04-27
JP2018156935A (en) 2018-10-04
JP6646092B2 (en) 2020-02-14
JP2019212637A (en) 2019-12-12
JP2018153794A (en) 2018-10-04
JP2018156940A (en) 2018-10-04
JP6590968B2 (en) 2019-10-16
JP2018155749A (en) 2018-10-04
JP2018155746A (en) 2018-10-04
JP7061100B2 (en) 2022-04-27
JP2018153803A (en) 2018-10-04
JP2018154550A (en) 2018-10-04
JP6622838B2 (en) 2019-12-18

Similar Documents

Publication Publication Date Title
JP6622838B2 (en) Solid electrolyte for all solid state secondary battery, method for producing the same, and all solid state secondary battery
JP6026997B2 (en) Positive electrode active material for lithium secondary battery and lithium secondary battery
JP6230540B2 (en) Positive electrode active material for lithium secondary battery and positive electrode using the same
EP2509143A2 (en) Anode active material precursor and active material for a rechargeable lithium battery comprising hollow nanofibrous carbon, and a production method therefor
TW201628239A (en) Positive electrode active material and preparation method thereof
JP2013528907A (en) Negative electrode active material for lithium secondary battery, method for producing the same, and lithium secondary battery including the same
CN112786827A (en) Cobalt-free cathode material and preparation method thereof
JP2014067546A (en) Positive electrode active material of lithium secondary battery, and lithium secondary battery
JP6088923B2 (en) Method for producing positive electrode active material for lithium secondary battery or precursor thereof
JP5670104B2 (en) Positive electrode active material and lithium secondary battery
CN105358485A (en) Process for the preparation of lithium titanium spinel and its use
JP7158269B2 (en) Positive electrode active material for secondary battery and method for producing the same
JP2014049407A (en) Method of manufacturing cathode active material for lithium secondary battery
JP3160147B2 (en) Method and apparatus for producing fine composite ceramic powder, solid oxide fuel cell using said ceramic powder and said ceramic powder as electrode material
JP7121734B2 (en) Method for Producing High Performance Lithium Titanate Anode Materials for Lithium Ion Battery Applications
JP5604217B2 (en) Method for producing lithium vanadium phosphate carbon composite
JP7351736B2 (en) Method for producing lithium lanthanum zirconium oxide crystal particle aggregate for solid electrolyte
JP7473828B2 (en) Positive electrode for non-aqueous electrolyte secondary battery and method for producing same
JP6486518B2 (en) Method for producing negative electrode active material for lithium ion secondary battery
CN115954445A (en) Nano sodium oxalate composite positive active material and application thereof
JP6178554B2 (en) Method for producing composite material of metal oxide and conductive carbon
KR20220127517A (en) Method of manufacturing cathode active material for lithium secondary battery
JP2020155225A (en) Manufacturing method of composite positive electrode active material particles for all-solid lithium ion secondary battery
JP7152945B2 (en) Method for producing nanoparticle aggregate for negative electrode active material of lithium ion secondary battery
Julien et al. Fabrication of Li4Ti5O12 (LTO) as Anode Material for Li-Ion Batteries

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20200819

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20210817

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20211014

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20220311

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20220323

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20220413

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20220415

R150 Certificate of patent or registration of utility model

Ref document number: 7061100

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150