TW202332113A - Solid electrolyte, production method for solid electrolyte, and battery - Google Patents

Solid electrolyte, production method for solid electrolyte, and battery Download PDF

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TW202332113A
TW202332113A TW111135708A TW111135708A TW202332113A TW 202332113 A TW202332113 A TW 202332113A TW 111135708 A TW111135708 A TW 111135708A TW 111135708 A TW111135708 A TW 111135708A TW 202332113 A TW202332113 A TW 202332113A
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solid electrolyte
meth
lithium
carbonate
compound
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橋本紗英
森岡孝至
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日商琳得科股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Electrochemistry (AREA)
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Abstract

A solid electrolyte comprising metal oxide particles and an electrolytic solution that contains a lithium salt and a carbonate solvent, the viscosity of the electrolytic solution at 23 DEG C as measured according to JIS Z 8803:2011 being 7 mPa.s or higher.

Description

固體電解質、固體電解質之製造方法，及電池Solid electrolyte, manufacturing method of solid electrolyte, and battery

本發明關於固體電解質、固體電解質之製造方法，及電池。The present invention relates to a solid electrolyte, a method for manufacturing the solid electrolyte, and a battery.

固體電解質係與電解液相異，並無漏液的憂慮，而能形成輕量且可撓性之電解質膜。因此，期待固體電解質應用在使用鋰離子等之二次電池等。例如，文獻1(日本特開2017-059432號公報)提出一種類固體電解質(quasi-solid state electrolyte)，其包含金屬氧化物與離子傳導材料，且特定之離子傳導材料係被載持於金屬氧化物粒子。 文獻1記載之類固體電解質係使用甘醇二甲醚(glyme)類或N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨雙(三氟甲烷磺醯基)醯亞胺之任意一者，與包含雙(氟磺醯基)醯亞胺鋰之鋰鹽之混合物作為離子傳導材料。該離子傳導材料為離子液體系之電解液。然而，使用離子液體系統之電解液之固體電解質在鋰離子遷移數(transport number)等之特性上並不充足。又，在更加嚴苛用環境下，使用離子液體系統之電解液之固體電解質在對鋰金屬之安定性等之特性上並不充足。因此，固體電解質在作為固體電解質之特性被要求更加改善更安定之循環充放電性能等。又，至今已知在電解液之黏度過低之情況，會難以取得固體電解質。 The solid electrolyte system is different from the electrolyte solution, and there is no worry of leakage, and a lightweight and flexible electrolyte membrane can be formed. Therefore, solid electrolytes are expected to be applied to secondary batteries using lithium ions or the like. For example, Document 1 (Japanese Unexamined Patent Publication No. 2017-059432) proposes a quasi-solid state electrolyte, which includes a metal oxide and an ion-conducting material, and a specific ion-conducting material is supported on the metal oxide matter particles. The solid electrolyte system described in Document 1 uses glyme or N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonate) A mixture of any one of acyl)imides and a lithium salt containing lithium bis(fluorosulfonyl)imide as an ion-conducting material. The ion-conducting material is the electrolyte of the ionic liquid system. However, the solid electrolyte using the electrolytic solution of the ionic liquid system is not sufficient in characteristics such as lithium ion transport number. Also, in a more severe environment, the solid electrolyte using the electrolyte solution of the ionic liquid system is not sufficient in characteristics such as stability to lithium metal. Therefore, the characteristics of the solid electrolyte as a solid electrolyte are required to improve the stable cycle charge and discharge performance and the like. Also, it has been known so far that it is difficult to obtain a solid electrolyte when the viscosity of the electrolyte is too low.

本發明之目的在於提供固體電解質之膜化為容易，鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高之固體電解質、該固體電解質之製造方法，以及具備該固體電解質之電池。 [1]　一種固體電解質，其含有：包含鋰鹽及碳酸酯系溶劑之電解液，與金屬氧化物粒子，根據JIS Z 8803：2011所測量之在23℃之前述電解液之黏度為7mPa・s以上。 [2]　如[1]之固體電解質，其中前述鋰鹽為選自由雙(氟磺醯基)醯亞胺鋰、及硼氟化鋰所成群之至少一種。 [3]　如[1]或[2]記載之固體電解質，其中前述碳酸酯系溶劑為選自由碳酸二甲酯、及碳酸伸丙酯所成群之至少一種。 [4]　如[1]至[3]中任一項記載之固體電解質，其中前述電解液所包含之前述鋰鹽對前述碳酸酯系溶劑之莫耳比(鋰鹽/碳酸酯系溶劑)為1/4以上1/1以下。 [5]　如[1]至[4]中任一項記載之固體電解質，其中前述金屬氧化物粒子為二氧化矽粒子。 [6]　如[1]至[5]中任一項記載之固體電解質，其中前述金屬氧化物粒子藉由BET法所測量之比表面積為160m 2/g以上700m 2/g以下。 [7]　如[1]至[6]中任一項記載之固體電解質，其中更含有接著劑。 [8]　如[7]記載之固體電解質，其中前述接著劑包含丙烯酸系聚合物。 [9]　如[8]記載之固體電解質，其中前述丙烯酸系聚合物包含源自丙烯酸系聚合性化合物之構成單位，前述丙烯酸系聚合性化合物包含反應速率常數k p為700L・mol -1・s -1以上之單官能(甲基)丙烯酸酯化合物。 [10]　如[9]記載之固體電解質，其中前述丙烯酸系聚合性化合物更包含前述單官能(甲基)丙烯酸酯化合物以外之多官能(甲基)丙烯酸酯化合物。 [11]　如[10]記載之固體電解質，其中前述多官能(甲基)丙烯酸酯化合物為選自由1,9-雙(丙烯醯氧基)壬烷、三羥甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、及二季戊四醇六丙烯酸酯所成群之至少一種。 [12]　如[10]或[11]記載之固體電解質，其中前述源自丙烯酸系聚合性化合物之構成單位包含選自由前述源自單官能(甲基)丙烯酸酯化合物之構成單位、及前述源自多官能(甲基)丙烯酸酯化合物之構成單位所成群之至少一種，將前述源自單官能(甲基)丙烯酸酯化合物之構成單位與前述源自多官能(甲基)丙烯酸酯化合物之構成單位之合計設為100莫耳%時，前述源自單官能(甲基)丙烯酸酯化合物之構成單位之含量為90莫耳%以上100莫耳%以下，前述源自多官能(甲基)丙烯酸酯化合物之構成單位之含量為0莫耳%以上10莫耳%以下。 [13]　一種電池，其具備如[1]至[12]中任一項記載之固體電解質。 [14]　一種固體電解質之製造方法，其係製造如[8]至[12]中任一項記載之固體電解質之方法，且具備：混合前述電解液、前述金屬氧化物粒子、前述丙烯酸系聚合性化合物、及光聚合起始劑而調製混合物的步驟；使前述混合物成形而取得成形物的步驟；及，藉由對前述成形物照射紫外線而取得包含前述丙烯酸系聚合性化合物經硬化之前述丙烯酸系聚合物之固體電解質的步驟。 根據本發明之一態樣，提供固體電解質之膜化為容易，鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高之固體電解質、該固體電解質之製造方法，以及具備該固體電解質之電池。 The purpose of the present invention is to provide a solid electrolyte that is easy to form into a film, has a high transfer number of lithium ions, ion conductivity, and high stability to lithium metal, a method for manufacturing the solid electrolyte, and a device with the solid electrolyte. Battery. [1] A solid electrolyte comprising: an electrolyte solution containing a lithium salt and a carbonate-based solvent, and metal oxide particles, the viscosity of the electrolyte solution at 23°C measured in accordance with JIS Z 8803:2011 is 7mPa·s above. [2] The solid electrolyte according to [1], wherein the lithium salt is at least one selected from the group consisting of lithium bis(fluorosulfonyl)imide and lithium borofluoride. [3] The solid electrolyte according to [1] or [2], wherein the carbonate-based solvent is at least one selected from the group consisting of dimethyl carbonate and propylene carbonate. [4] The solid electrolyte according to any one of [1] to [3], wherein the molar ratio of the lithium salt contained in the electrolytic solution to the carbonate-based solvent (lithium salt/carbonate-based solvent) is More than 1/4 and less than 1/1. [5] The solid electrolyte according to any one of [1] to [4], wherein the metal oxide particles are silica particles. [6] The solid electrolyte according to any one of [1] to [5], wherein the specific surface area of the metal oxide particles measured by the BET method is not less than 160 m 2 /g and not more than 700 m 2 /g. [7] The solid electrolyte according to any one of [1] to [6], further comprising a binder. [8] The solid electrolyte according to [7], wherein the adhesive includes an acrylic polymer. [9] The solid electrolyte as described in [8], wherein the acrylic polymer includes a structural unit derived from an acrylic polymeric compound, and the acrylic polymeric compound includes a reaction rate constant k p of 700 L·mol -1 ·s -1 or more monofunctional (meth)acrylate compounds. [10] The solid electrolyte according to [9], wherein the acrylic polymerizable compound further includes a polyfunctional (meth)acrylate compound other than the monofunctional (meth)acrylate compound. [11] The solid electrolyte as described in [10], wherein the polyfunctional (meth)acrylate compound is selected from the group consisting of 1,9-bis(acryloxy)nonane, trimethylolpropane triacrylate, pentaerythritol At least one of the group consisting of tetraacrylate and dipentaerythritol hexaacrylate. [12] The solid electrolyte according to [10] or [11], wherein the structural unit derived from the acrylic polymeric compound is selected from the structural unit derived from the monofunctional (meth)acrylate compound, and the source At least one of the constituent units derived from polyfunctional (meth)acrylate compounds, wherein the constituent units derived from monofunctional (meth)acrylate compounds and the aforementioned constituent units derived from polyfunctional (meth)acrylate compounds When the total of the constituent units is 100 mol%, the content of the constituent units derived from the monofunctional (meth)acrylate compound is 90 mol% to 100 mol%, and the aforementioned polyfunctional (meth)acrylate The content of the structural unit of the acrylate compound is not less than 0 mol % and not more than 10 mol %. [13] A battery comprising the solid electrolyte according to any one of [1] to [12]. [14] A method for producing a solid electrolyte, which is a method for producing the solid electrolyte described in any one of [8] to [12], comprising: mixing the electrolyte solution, the metal oxide particles, the acrylic polymer a step of preparing a mixture with a reactive compound and a photopolymerization initiator; a step of molding the mixture to obtain a molded product; and obtaining the hardened acrylic acid containing the acrylic polymerizable compound by irradiating the molded product with ultraviolet rays. It is a step of polymer solid electrolyte. According to one aspect of the present invention, there are provided solid electrolytes which are easy to form into a solid electrolyte film, have high transfer number of lithium ions, high ion conductivity, and high stability to lithium metal, a method for producing the solid electrolyte, and a solid electrolyte having the same Solid electrolyte batteries.

以下，關於本發明舉出實施形態為例來進進行說明。本發明並不受限於實施形態之內容。 [固體電解質] 說明關於本實施形態之固體電解質。 本實施形態之固體電解質含有：包含鋰鹽及碳酸酯系溶劑之電解液，與金屬氧化物粒子。且，本實施形態之固體電解質在根據JIS Z 8803：2011所測量之在23℃之前述電解液之黏度為7mPa・s以上。根據本實施形態之固體電解質，可取得固體電解質之膜化為容易，鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高之固體電解質。其理由係推測如以下所述。 本實施形態之固體電解質中，藉由含有電解液與金屬氧化物粒子，而電解液之觸變性(以下，有稱為搖變性的情況)提升。又，電解液在23℃之黏度為7mPa・s以上時，使搖變性提升之效果會更加提高。因此，變得能達成包含金屬氧化物粒子與電解液之混合物之膜化。藉由變得能達成該膜化，而變得能抑制電解液之離子傳導性受損，且能抑制電解液之漏出。根據以上，推測本實施形態之固體電解質可取得固體電解質之膜化為容易，鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高(該等特性之中，尤其係對鋰金屬之安定性為高)之固體電解質。 ＜電解液＞ 本實施形態之電解液係藉由包含鋰鹽與碳酸酯系溶劑而得者。 (鋰鹽) 本實施形態之鋰鹽，例如具體地可舉舉出，六氟磷酸鋰(LiPF 6)、雙(三氟甲烷磺醯基)醯亞胺鋰(LiTFSI)、雙(氟磺醯基)醯亞胺鋰(lithium bis(fluorosulfonyl)imide) (LiFSI)、2-三氟甲基-4,5-二氰基咪唑酸鋰(LiTDI)、4,5-二氰基-1,2,3-三唑酸鋰(LiDCTA)、雙(五氟乙基磺醯基)醯亞胺鋰(LiBETI)、硼氟化鋰(lithium borofluoride)(LiBF 4)、雙(草酸根)硼酸鋰(LiBOB)、硝酸鋰(LiNO 3)、氯化鋰(LiCl)、溴化鋰(LiBr)、及氟化鋰(LiF)等。 該等之中，在變得容易取得鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高之固體電解質的觀點上，鋰鹽係以選自雙(氟磺醯基)醯亞胺鋰、及硼氟化鋰之至少1種為佳。鋰鹽係可單獨使用雙(氟磺醯基)醯亞胺鋰(LiFSI)、及硼氟化鋰(LiBF 4)之任一種，亦可併用該等2種。在固體電解質中鋰鹽係能存在作為鋰金屬之陽離子及該陽離子之相對離子。藉由使用該等之鋰鹽，尤其係對鋰金屬之安定性會更加提升。 (碳酸酯系溶劑) 本實施形態之碳酸酯系溶劑，具體地可舉出例如，碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸乙基甲酯(EMC)、碳酸二丙酯(DPC)、碳酸甲基丙酯(MPC)、碳酸乙基丙酯(EPC)、碳酸伸乙酯(EC)、碳酸伸丙酯(PC)、及碳酸伸丁酯(BC)等。該等之中，在變得容易取得鋰離子之遷移數、離子傳導率及對鋰金屬之安定性為高之固體電解質的觀點上，碳酸酯系溶劑係以選自碳酸二甲酯、及碳酸伸丙酯之至少一種為佳。碳酸酯系溶劑係可單獨使用一種碳酸二甲酯(DMC)、及碳酸伸丙酯(PC)之任一者，亦可併用該等2種。在此，本實施形態中之碳酸酯系溶劑係表示分子構造中具有碳酸酯骨架之化合物。 (鋰鹽與碳酸酯系溶劑之莫耳比) 本實施形態之電解液中，鋰鹽對碳酸酯系溶劑之莫耳比(鋰鹽/碳酸酯系溶劑)係以1/4以上1/1以下為佳。該莫耳比在1/4以上時，對鋰金屬之安定性容易提升。另一方面，該莫耳比在1/1以下時，鋰鹽變得容易溶解於碳酸酯系溶劑。在變得容易取得鋰離子之遷移數、離子傳導率及對鋰金屬之安定性為高之固體電解質的觀點上，該莫耳比可為1/3以上1/1以下，亦可為1/2以上1/1以下。 其理由並不明確，但本實施形態之電解液為組合選自雙(氟磺醯基)醯亞胺鋰、及硼氟化鋰之至少一種之鋰鹽，與，選自碳酸二甲酯、及碳酸伸丙酯之至少一種之碳酸酯系溶劑而成之電解液的情況，在與組合該等鋰鹽以外之鋰鹽，與，該等碳酸酯系溶劑以外之碳酸酯系溶劑而成之電解液的情況相比，對鋰金屬之安定性會更加優異。又，在組合選自雙(氟磺醯基)醯亞胺鋰、及硼氟化鋰之至少一種之鋰鹽，與，與選自碳酸二甲酯、及碳酸伸丙酯之至少一種之碳酸酯系溶劑而成之電解液的情況，鋰鹽與碳酸酯系溶劑之含量以莫耳比計，在1/4以上1/1以下之範圍內包含的情況，對鋰金屬之安定性會更加優異。 固體電解質中之電解液之含量在變得容易取得鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高之固體電解質的觀點上，相對於固體電解質全體，以75質量%以上為佳，以77質量%以上為較佳，以78質量%以上為更佳，以79質量%以上為較更佳。又，在相同觀點上，相對於固體電解質全體，固體電解質中之電解液之含量係以90質量%以下為佳，以89質量%以下為較佳，以88質量%以下為更佳。 (黏度) 本實施形態之固體電解質中，電解液之黏度為7mPa・s以上。在更容易作成固體電解質之膜化之觀點上，電解液之黏度係以9mPa・s以上為佳，以11mPa・s以上為較佳，以20mPa・s以上為更佳，以30mPa・s以上為較更佳，以40mPa・s以上再更佳。 電解液之黏度之上限並無特別限定。例如，在考慮到取得鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高之固體電解質時，電解液之黏度之上限例如，可為500mPa・s以下，也可為300mPa・s以下。 電解液之黏度係根據JIS Z 8803：2011在23℃下進行測量。電解液之黏度之測量例如，以利用振動式黏度計之測量方法為佳。電解液之黏度在測量固體電解質中之電解液黏度的情況，抽出固體電解質中之電解液，使用例如振動式黏度計來測量經抽出之電解液之黏度即可。 ＜金屬氧化物粒子＞ 本實施形態之固體電解質含有金屬氧化物粒子。本實施形態之固體電解質中藉由包含電解液與金屬氧化物粒子，而成為電解液被載持於金屬氧化物粒子之狀態。在此，本實施形態中，被載持之狀態係指表示金屬氧化物粒子之表面之至少一部分被電解液被覆的狀態。 金屬氧化物粒子在容易作成固體電解質之膜化之觀點上，藉由BET法所測量之比表面積係以160m 2/g以上700m 2/g以下為佳。金屬氧化物粒子之比表面積(BET法)在160m 2/g以上時，搖變性容易提升，變得容易形成包含金屬氧化物粒子與電解液之混合物(亦即，固體電解質)之膜。又，比表面積(BET法)為700m 2/g以下時，與電解液之混合性變得良好，而變得容易形成固體電解質之膜。在更容易作成固體電解質之膜化之觀點上，金屬氧化物粒子之比表面積(BET法)係以165m 2/g以上為較佳，以170m 2/g以上為更佳。又，在相同觀點上，以600m 2/g以下為較佳，以520m 2/g以下為更佳。在此，BET法係指使固體粒子吸附氣體分子(通常氮氣)，從已吸附之氣體分子之量來測量固體粒子之比表面積的方法。比表面積之測量係可使用各種BET測量裝置來進行測量。 金屬氧化物粒子係可單獨使用一種顯示上述比表面積之金屬氧化物粒子，亦可併用2種以上之比表面積相異之金屬氧化物粒子。金屬氧化物粒子之種類並無特別限定，可舉出例如，二氧化矽粒子、氧化鋁粒子、氧化鋯粒子、氧化鈰粒子、矽酸鎂粒子、矽酸鈣粒子、氧化鋅粒子、氧化銻粒子、氧化銦粒子、氧化錫粒子、氧化鈦粒子、氧化鐵粒子、氧化鎂粒子、氫氧化鋁粒子、氫氧化鎂粒子、鈦酸鉀粒子、及鈦酸鋇粒子等。金屬氧化物粒子係可單獨使用1個該等之金屬氧化物粒子，亦可併用2種以上。該等之中，金屬氧化物粒子在搖變性提升的觀點上，以選自二氧化矽粒子、氧化鋁粒子、氧化鋯粒子、氧化鎂粒子、及鈦酸鋇粒子之至少一種為佳。金屬氧化物粒子在輕量且粒子徑為之觀點上，以二氧化矽粒子為較佳。 使用二氧化矽粒子作為金屬氧化物粒子的情況，二氧化矽粒子可為濕式二氧化矽粒子，也可為乾式二氧化矽粒子。濕式二氧化矽粒子係可舉出例如，藉由矽酸鈉與礦酸之中和反應而得之沉降法、及溶膠凝膠法之濕式二氧化矽粒子。又，乾式二氧化矽粒子可舉出使矽烷化合物燃燒而得之燃燒法二氧化矽粒子(氣相二氧化矽粒子)、及使金屬矽粉爆發性燃燒而得之爆燃法二氧化矽粒子。二氧化矽粒子為乾式二氧化矽粒子時，由於可抑制來自二氧化矽粒子所造成之水分混入，而容易抑制電解質劣化。因此，在抑制電解質劣化之觀點上，二氧化矽粒子係以乾式二氧化矽粒子為佳，以氣相二氧化矽粒子為較佳。 固體電解質中之金屬氧化物粒子之含量在容易作成固體電解質之膜化之觀點上，相對於固體電解質全體，以4質量%以上為佳，以5質量%以上為較佳，以6質量%以上為更佳。又，在相同觀點上，相對於固體電解質全體，固體電解質中之金屬氧化物粒子之含量係以16質量%以下為佳，以15質量%以下為較佳，以14質量%以下為更佳。 ＜接著劑＞ 本實施形態之固體電解質可包含或亦可不包含接著劑。本實施形態之固體電解質在變得容易形成固體電解質之膜之觀點上，亦可包含接著劑。本實施形態之固體電解質在包含接著劑之情況，接著劑之種類並無特別限定。本實施形態之固體電解質在包含接著劑之情況，在固體電解質之膜化變得更加容易，並且對鋰金屬之安定性變得更加容易提升之觀點上，接著劑係以含有包含丙烯酸系聚合物之接著劑為佳。本實施形態之固體電解質中，在包含接著劑之情況，接著劑例如可為包含丙烯酸系聚合物且包含丙烯酸系聚合物以外之聚合物態樣，也可為不包含丙烯酸系聚合物以外之聚合物，而單獨包含丙烯酸系聚合物的態樣。接著劑係以單獨包含丙烯酸系聚合物為較佳。 (丙烯酸系聚合物) 本實施形態之固體電解質中，丙烯酸系聚合物包含源自丙烯酸系聚合性化合物之構成單位。亦即，丙烯酸系聚合物係使丙烯酸系聚合性化合物作為單體進行聚合後之樹脂，於主鏈中包含源自丙烯酸系聚合性化合物之構成單位的樹脂。在此，「源自」係意指在單體進行聚合時，接受了必要之構造變化。 [丙烯酸系聚合性化合物] 丙烯酸系聚合性化合物包含(甲基)丙烯酸酯化合物。丙烯酸系聚合性化合物係可僅包含單官能(甲基)丙烯酸酯化合物，亦可包含單官能(甲基)丙烯酸酯化合物與多官能(甲基)丙烯酸酯化合物雙方。 本說明書中，「(甲基)丙烯醯基」係在表示「丙烯醯基」及「甲基丙烯醯基」雙方的情況所使用之記述，關於其他類似用語亦為相同。 本說明書中，多官能(甲基)丙烯酸酯化合物意指2官能以上之(甲基)丙烯酸酯化合物。 ・單官能(甲基)丙烯酸酯化合物 本實施形態之固體電解質在容易作成固體電解質之膜化之觀點上，以包含反應速率常數k p為700L・mol -1・s -1以上之單官能(甲基)丙烯酸酯化合物作為丙烯酸系聚合性化合物為佳。在相同觀點上，丙烯酸系聚合性化合物所包含之單官能(甲基)丙烯酸酯化合物之反應速率常數k p係以710L・mol -1・s -1以上為較佳，以720L・mol -1・s -1以上為更佳。丙烯酸系聚合性化合物所包含之單官能(甲基)丙烯酸酯化合物之反應速率常數k p之上限並無特別限定，例如，可為40000L・mol -1・s -1以下，也可為35000L・mol -1・s -1以下。本說明書中，有將反應速率常數k p為700L・mol -1・s -1以上之單官能(甲基)丙烯酸酯化合物稱為(A)成分的情況。在使用反應速率常數k p為700L・mol -1・s -1以上之單官能(甲基)丙烯酸酯化合物時，認為單官能(甲基)丙烯酸酯化合物之反應性會提升，且藉由分子量增大，而固體電解質變得容易膜化。 反應速率常數k p為700L・mol -1・s -1以上之單官能(甲基)丙烯酸酯化合物並無特別限定，例如，可為(甲基)丙烯酸，也可為(甲基)丙烯酸烷酯。反應速率常數k p為700L・mol -1・s -1以上之單官能(甲基)丙烯酸酯化合物係以具有碳數1以上3以下之烷基之(甲基)丙烯酸烷酯為佳。具體地可舉出例如，(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、及(甲基)丙烯酸異丙酯等。該等之中，反應速率常數k p為700L・mol -1・s -1以上之單官能(甲基)丙烯酸酯化合物係以(甲基)丙烯酸甲酯為較佳。又，藉由使用反應速率常數k p為700L・mol -1・s -1以上之單官能(甲基)丙烯酸酯化合物，而變得更容易取得鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高之固體電解質。 ・多官能(甲基)丙烯酸酯化合物 本實施形態之固體電解質在容易作成固體電解質之膜化之觀點上，以更包含單官能(甲基)丙烯酸酯化合物以外之多官能(甲基)丙烯酸酯化合物作為丙烯酸系聚合性化合物為佳。在更包含單官能(甲基)丙烯酸酯化合物以外之多官能(甲基)丙烯酸酯化合物作為丙烯酸系聚合性化合物時，變得更容易取得鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高之固體電解質。本說明書中，有將多官能(甲基)丙烯酸酯化合物稱為(B)成分的情況。 多官能(甲基)丙烯酸酯化合物只要係反應速率常數k p為700L・mol -1・s -1以上之單官能(甲基)丙烯酸酯化合物以外之2官能以上之(甲基)丙烯酸酯化合物，即無特別限定。多官能(甲基)丙烯酸酯化合物在作成容易取得鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高之固體電解質的觀點上，以及容易作成固體電解質之膜化之觀點上，以不具有丙烯醯基以外之反應性基之多官能(甲基)丙烯酸酯化合物為佳。 多官能(甲基)丙烯酸酯化合物，例如，具體地可舉出，1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二丙烯酸酯(1,9-雙(丙烯醯氧基)壬烷)、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、新戊二醇己二酸酯二(甲基)丙烯酸酯、羥基叔戊酸新戊二醇二(甲基)丙烯酸酯、二環戊二基(甲基)丙烯酸酯、二羥甲基二環戊烷二(甲基)丙烯酸酯、三環癸烷二甲醇(甲基)丙烯酸酯、及金剛烷二(甲基)丙烯酸酯等之2官能(甲基)丙烯酸酯化合物；三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、及季戊四醇三(甲基)丙烯酸酯等之3官能(甲基)丙烯酸酯化合物；二丙三醇四(甲基)丙烯酸酯、及季戊四醇四(甲基)丙烯酸酯等之4官能(甲基)丙烯酸酯化合物；二季戊四醇五(甲基)丙烯酸酯等之5官能(甲基)丙烯酸酯化合物；二季戊四醇六(甲基)丙烯酸酯等之6官能(甲基)丙烯酸酯化合物等。 該等之中，在作成容易取得鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高之固體電解質的觀點上，以及容易作成固體電解質之膜化之觀點上，多官能(甲基)丙烯酸酯化合物係以選自1,9-雙(丙烯醯氧基)壬烷、三羥甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、及二季戊四醇六丙烯酸酯所成群之至少一種為佳。 本實施形態之固體電解質中，丙烯酸系聚合物所包含之源自丙烯酸系聚合性化合物之構成單位係以包含選自由源自單官能(甲基)丙烯酸酯化合物之構成單位、及源自多官能(甲基)丙烯酸酯化合物之構成單位所成群之至少一種為佳。源自丙烯酸系聚合性化合物之構成單位係以包含源自單官能(甲基)丙烯酸酯化合物之構成單位為較佳。源自丙烯酸系聚合性化合物之構成單位係以包含源自單官能(甲基)丙烯酸酯化合物之構成單位，與源自多官能(甲基)丙烯酸酯化合物之構成單位為更佳。在容易作成固體電解質之膜化之觀點上，源自單官能(甲基)丙烯酸酯化合物之構成單位、及源自多官能(甲基)丙烯酸酯化合物之構成單位之含量係以在以下所示之範圍為佳。又，源自單官能(甲基)丙烯酸酯化合物之構成單位、及源自多官能(甲基)丙烯酸酯化合物之構成單位之含量位於以下所示之範圍時，變得更容易取得鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高之固體電解質。 將源自單官能(甲基)丙烯酸酯化合物之構成單位與源自多官能(甲基)丙烯酸酯化合物之構成單位之合計設為100莫耳%時，源自單官能(甲基)丙烯酸酯化合物之構成單位之含量係以90莫耳%以上為佳，以91莫耳%以上為較佳，以93莫耳%以上為更佳。 將源自單官能(甲基)丙烯酸酯化合物之構成單位與源自多官能(甲基)丙烯酸酯化合物之構成單位之合計設為100莫耳%時，源自單官能(甲基)丙烯酸酯化合物之構成單位之含量係以100莫耳%以下為佳，以99莫耳%以下為較佳，以97莫耳%以下為更佳。 將源自單官能(甲基)丙烯酸酯化合物之構成單位與源自多官能(甲基)丙烯酸酯化合物之構成單位之合計設為100莫耳%時，源自多官能(甲基)丙烯酸酯化合物之構成單位之含量係以0莫耳%以上為佳，以1莫耳%以上為較佳，以3莫耳%以上為更佳。 將源自單官能(甲基)丙烯酸酯化合物之構成單位與源自多官能(甲基)丙烯酸酯化合物之構成單位之合計設為100莫耳%時，源自多官能(甲基)丙烯酸酯化合物之構成單位之含量係以10莫耳%以下為佳，以9莫耳%以下為較佳，以7莫耳%以下為更佳。 固體電解質中之丙烯酸系聚合物之含量在容易作成固體電解質之膜化之觀點上，相對於固體電解質全體，以3質量%以上為佳，以4質量%以上為較佳，以5質量%以上為更佳。又，在相同觀點上，相對於固體電解質全體，固體電解質中之丙烯酸系聚合物之含量係以10質量%以下為佳，以9質量%以下為較佳，以8質量%以下為更佳。 [光聚合起始劑] 本實施形態之固體電解質為了取得丙烯酸系聚合物，以使用光聚合起始劑為佳。本實施形態之固體電解質中，丙烯酸系聚合物係例如，藉由使包含丙烯酸系聚合性化合物與光聚合起始劑之接著劑用組成物進行聚合而得。 光聚合起始劑並無特別限定，可舉出如在使丙烯酸系聚合性化合物硬化為目的所使用之公知之化合物。光聚合起始劑係以會感應紫外線之光聚合起始劑為佳。光聚合起始劑矽可單獨使用1種，亦可併用2種以上。 光聚合起始劑例如，具體地可舉出，4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α’-二甲基苯乙酮、2-甲基-2-羥基苯丙酮、及1-羥基環己基苯基酮等之α-縮酮系化合物；甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、及2-甲基-1-[4-(甲硫基)-苯基]-2-嗎啉基丙烷-1等之苯乙酮系化合物；安息香乙基醚、安息香異丙基醚、及茴香偶姻甲基醚(anisoin methy ether)等之安息香醚系化合物；苄基二甲基縮酮等之縮酮系化合物；2-萘磺醯氯等之芳香族磺醯氯系化合物；1-苯酮-1,1-丙二酮2-(o-乙氧基羰基)肟等之光活性肟系化合物；二苯甲酮、苄醯基安息香酸、及3,3’-二甲基-4-甲氧基二苯甲酮等之二苯甲酮系化合物；噻噸酮(thioxanthone)、2-氯噻噸酮、2-甲基噻噸酮、2,4-二甲基噻噸酮、異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二乙基噻噸酮、及2,4-二異丙基噻噸酮等之噻噸酮系化合物；樟腦醌；鹵化酮；醯基膦氧化物；醯基膦酸酯；寡[2-羥基-2-甲基-1-(4-(1-甲基乙烯基)苯基)丙酮]等。 固體電解質中之接著劑之含量在容易作成固體電解質之膜化之觀點上，相對於固體電解質全體，以3質量%以上為佳，以4質量%以上為較佳，以5質量%以上為更佳。又，在相同觀點上，相對於固體電解質全體，固體電解質中之接著劑之含量係以10質量%以下為佳，以9質量%以下為較佳，以8質量%以下為更佳。 本實施形態之固體電解質在一態樣中係以含有：前述之本實施形態之包含鋰鹽及碳酸酯系溶劑之電解液、金屬氧化物粒子，及包含丙烯酸系聚合物之接著劑為佳。本實施形態之固體電解質只要不損及本發明之目的，亦可包含該等以外之成分。 ＜金屬氧化物與電解液與接著劑之質量比＞ 本實施形態之固體電解質在容易作成固體電解質之膜化之觀點上，在將電解液、金屬氧化物粒子與接著劑之合計含量設為100質量%時，以下述所示之含量為佳。又，電解液、金屬氧化物粒子、及接著劑之合計含量中，電解液、金屬氧化物粒子、及接著劑之含量在下述所示之範圍時，變得更加容易取得鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高之固體電解質。 以電解液之含量在77質量%以上90質量%以下，金屬氧化物粒子之含量在4質量%以上16質量%以下，接著劑之含量在3質量%以上10質量%以下為佳。 以電解液之含量在78質量%以上89質量%以下，金屬氧化物粒子之含量在5質量%以上15質量%以下，接著劑之含量在4質量%以上9質量%以下為較佳。 以電解液之含量在79質量%以上88質量%以下，金屬氧化物粒子之含量在6質量%以上14質量%以下，接著劑之含量在5質量%以上8質量%以下為更佳。 [固體電解質之製造方法] 其次，說明關於本實施形態之固體電解質在含有包含丙烯酸系聚合物之接著劑的情況下，本實施形態之固體電解質之較佳製造方法。本實施形態之固體電解質之製造方法為作為固體電解質之製造方法一例，而並非係受限於下述所說明之製造方法者。 本實施形態之固體電解質之製造方法具備下述步驟。 混合電解液、金屬氧化物粒子、丙烯酸系聚合性化合物、及光聚合起始劑而調製混合物的步驟(步驟1) 使混合物成形而取得成形物的步驟(步驟2) 對成形物照射紫外線而取得包含丙烯酸系聚合性化合物經硬化之丙烯酸系聚合物之固體電解質的步驟(步驟3) 其中，電解液包含鋰鹽及碳酸酯系溶劑，且根據JIS Z 8803：2011所測量之在23℃之黏度為7mPa・s以上。 根據本實施形態之固體電解質之較佳製造方法，可取得固體電解質之膜化為容易，鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高之固體電解質。又，根據本實施形態之較佳之固體電解質之製造方法，藉由使用丙烯酸系聚合性化合物及光聚合起始劑作為取得丙烯酸系聚合物用之接著劑用組成物，而取得固體電解質用之成形性提升。成形性會提升之理由係認為如以下所述。本實施形態之固體電解質之製造方法在混合取得固體電解質用之原材料時，即使不施加強剪切力，仍變得可容易取得固體電解質。因此，本實施形態之固體電解質之製造方法中成形性會提升。 (步驟1) 步驟1為混合取得固體電解質用之原材料而取得混合物的步驟。步驟1中，首先，作為取得固體電解質用之原材料，分別準備在前述之包含鋰鹽、及碳酸酯系溶劑之電解液、前述之金屬氧化物粒子，及前述之丙烯酸系聚合物中所說明之丙烯酸系聚合性化合物及光聚合起始劑。準備在23℃之黏度為7mPa・s以上之電解液作為電解液。丙烯酸系聚合性化合物及光聚合起始劑係也可準備作為包含兩者之接著劑用組成物。其次，對於該等經準備之原材料，秤量作為目的之量。其後，藉由混合已秤量之各原材料，而調製出混合物。混合物之調整係亦可藉由使用公知之攪拌裝置等攪拌各原材料來進行調製。本實施形態之固體電解質之製造方法中，混合物之調製可不賦予強剪切力。步驟1所調製之混合物為固體電解質形成用之混合物。 步驟1中，在混合金屬氧化物粒子、電解液，及作為接著劑用組成物之丙烯酸系聚合性化合物及光聚合起始劑時，例如，以使用以下之比率進行混合為佳。將金屬氧化物粒子、電解液及接著劑用組成物之合計含量設為100質量%時，金屬氧化物粒子、電解液及接著劑用組成物之混合比率，例如以質量基準計，以金屬氧化物粒子在4質量%以上16質量%以下，電解液在77質量%以上90質量%以下，接著劑用組成物在3質量%以上10質量%以下為佳。 接著劑用組成物中，丙烯酸系聚合性化合物與光聚合起始劑之含量在將丙烯酸系聚合性化合物與光聚合起始劑之合計含量設為100莫耳%時，例如，以丙烯酸系聚合性化合物之含量在90莫耳%以上99.9莫耳%以下，光聚合起始劑在0.1莫耳%以上10莫耳%以下為佳。 (步驟2) 步驟2為由步驟1所調製之混合物取得成形物的步驟。步驟2係藉由使步驟1所調製之混合物進行成形而取得成形物。混合物之成形並無特別限定，例如，可藉由將混合物塗佈於支撐體之表面形成塗膜來進行成形。又，混合物之成形係例如，可藉由使用會顯示剝離性之模具施以壓縮成形來進行成形。顯示剝離性之模具例如，可為在薄膜之表面施加有離型處理支離型薄膜。 (步驟3) 步驟3為由步驟2所得之成形物取得固體電解質的步驟。步驟3係藉由對步驟2中經成形之成形物照射紫外線，而丙烯酸系聚合性化合物進行硬化而形成丙烯酸系聚合物。其後，取得包含前述之電解液、前述之金屬氧化物粒子，及經硬化之丙烯酸系聚合物的固體電解質。對成形體照射紫外線之裝置並無特別限定，只要會使丙烯酸系聚合性化合物硬化的裝置即可。例如，照射紫外線之裝置可為具備紫外線LED燈的裝置，可為具備高壓水銀燈的裝置，也可為具備金屬鹵素燈的裝置。 對成形體照射紫外線(UV)之條件並無特別限定，只要係會使丙烯酸系聚合性化合物硬化之條件即可。照射紫外線時之最大照度及累積光量係可舉出例如以下之條件。最大照度例如，可為5mW/cm 2以上，可為10mW/cm 2以上，也可為50mW/cm 2以上。又，最大照度可為1000mW/cm 2以下，可為700mW/cm 2以下，也可為500mW/cm 2以下。累積光量例如，可為50mJ/cm 2以上，可為100mJ/cm 2以上，也可為500mJ/cm 2以上。又，累積光量可為5000mJ/cm 2以下，可為3000mJ/cm 2以下，也可為2000mJ/cm 2以下。 藉由經過以上之步驟1、步驟2、及步驟3而取得本實施形態之一例之固體電解質。亦即，藉由上述步驟，而取得一種固體電解質，其含有：包含鋰鹽以及碳酸酯系溶劑之電解液、金屬氧化物粒子，及包含丙烯酸系聚合物之接著劑，且根據JIS Z 8803：2011所測量之在23℃之前述電解液之黏度為7mPa・s以上。 [電池] 其次，說明關於本實施形態之電池。 本實施形態之電池具備本實施形態之固體電解質。本實施形態中，以具備作為本實施形態之固體電解質作為電池之電解質層之構成材料為佳。電池係藉由陽極、陰極，與配置於陽極及陰極之間之電解質層來構成。藉由作成此種構成，而可取得各特性優異之電池。又，作為電池，以二次電池為佳，以鋰離子二次電池為較佳。本實施形態之鋰離子二次電池所具備之各種構件並無特別限定，可使用例如一般使用於電池中之材料。 尚且，本發明並不受限於前述實施形態，在能達成本發明之目的之範圍內之變形、改良等皆係包括在本發明中。 [實施例] 以下舉出實施例更加詳細說明本發明，本發明並非係受限於該等實施例者。尚且，以下之實施例及比較例中之測量或評價係藉由以下所示之方法來進行。 [電解液之黏度測量] 電解液之黏度係根據JIS Z 8803：2011，使用振動式黏度計(股份有限公司賽康尼克公司製，VM-10A-L)，在23℃下進行測量。振動式黏度計之校正係使用根據JIS Z 8809：2011之黏度計校正用標準液，在23℃下進行校正。黏度計校正用標準液係使用日本油脂股份有限公司製之JS2.5、JS50、及JS200的3種類。 [固體電解質之離子傳導率測量] 將固體電解質膜切出直徑6mm之圓形，以2枚之不鏽鋼板夾住作為電極，並測量不鏽鋼板間之阻抗。測量係使用對電極間施加交流(施加電壓為10mV)而測量電阻成分之交流阻抗法，從取得之科爾作圖(Cole-Cole plot)之實數阻抗截距來算出離子傳導率。尚且，測量係使用恆電位/恆電流儀(Potentiostat/galvanostat)(VMP-300 biologic公司製)。 離子傳導率(σ A)係藉由下述數式(F1)來求出。 σ A=L A/(R A×S A)・・・(F1) 數式(F1)中，σ A表示離子傳導率(單位：S・cm -1)，R A表示電阻(單位：Ω)，S A表示固體電解質膜之測量時之剖面積(單位：cm 2)，L A表示電極間距離(單位：cm)。 測量溫度為25℃。又，從複數阻抗之測量結果來算出離子傳導率(σ A)。 [電解液之離子傳導率測量] 使用直徑19mm之圓形之網布(α-UX SCREEN 150-035/380TW，股份有限公司NBC Meshtec公司製)作為間隔器。其後，使以指定處方來摻合使用於實施例或比較例之鋰鹽及碳酸酯系溶劑而成之電解液含浸於間隔器，並以2枚直徑16mm之不鏽鋼板夾住作為電極，且測量不鏽鋼板間之阻抗。測量係使用對於施加電極間交流(施加電壓為10mV)而測量電阻成分之交流阻抗法，從取得之科爾作圖之實數阻抗截距來算出離子傳導率。尚且，測量係使用恆電位/恆電流儀(VMP-300 biologic公司製)。 離子傳導率(σ B)係藉由下述數式(F2)來求出。 σ B=L B/(R B×S B)・・・(F2) 數式(F2)中，σ B表示離子傳導率(單位：S・cm -1)，R B表示電阻(單位：Ω)，S B表示電極之剖面積(單位：cm 2)，L B表示電極間距離(單位：cm)。 測量溫度為25℃。又，從複數阻抗之測量結果來算出離子傳導率(σ B)。 [對鋰金屬之安定性評價(溶解析出試驗)] 將固體電解質膜切出直徑19mm之圓形，並以2枚鋰金屬夾住作為電極，而製作出鋰對稱單元。鋰金屬電極係作成直徑16mm。在溫度25℃下將電流密度設為3mA/cm 2，使氧化電流流通至3mAh/cm 2為止後，接著使還原電流流通至3mAh/cm 2為止。重複該一連串作業200循環，測量經過200循環後之電壓變化。藉由該電壓測量來調查鋰金屬之溶解析出行為。在無短路等且電壓為固定下會重複溶解・析出時，即可確認到對鋰金屬為安定。將在從初期循環之電壓至±20mV以內之電位下運轉之循環次數作為安定運轉循環數，並比較各例之對鋰金屬之安定性。 [鋰離子遷移數測量] 將取得之固體電解質膜切出直徑6mm之圓形，以2枚鋰板夾住作為電極而製作出單元。其中，將單元連接至恆電位/恆電流儀(VMP-300 biologic公司製)，在25℃下經過2時間以上後開始測量。測量係首先進行複數阻抗測量來算出電阻值(R 0)後，施加30mV之電壓，進行直流極化測量。測量初期電流值(I 0)與電流值成為固定時之穩定電流值(I S)。確認有穩定電流後，再次進行複數阻抗測量而算出電阻值(R S)。鋰離子遷移數(t +)係藉由下述數式(F3)來求出(伊凡(Evans)之式)。 t +=Is(ΔV-I 0×R 0)/I 0(ΔV-I S×R S)・・・(F3) 數式(F3)中，ΔV表示施加電壓，R 0、R S、I 0及I S係與上述相同。 [實施例1] 準備雙(氟磺醯基)醯亞胺鋰(LiFSI)作為鋰鹽。準備碳酸二甲酯(DMC)作為碳酸酯系溶劑。準備氣相二氧化矽粒子(AEROSIL(註冊商標)380，日本Aerosil股份有限公司，由BET法所得之比表面積350m 2/g-410m 2/g)作為金屬氧化物粒子。為了取得構成接著劑之丙烯酸系聚合物，準備甲基丙烯酸酯((A)成分)與1,9-雙(丙烯醯氧基)壬烷((B)成分)作為丙烯酸系聚合性化合物，並準備1-羥基環己基苯基酮作為光聚合起始劑。在此，甲基丙烯酸酯((A)成分)係該當於單官能(甲基)丙烯酸酯化合物，且反應速率常數k p為720L・mol -1・s -1。 尚且，比表面積350m 2/g-410m 2/g係表示比表面積從350m 2/g至410m 2/g之範圍。以下，關於其他類似之記述亦為相同。 表1中，甲基丙烯酸酯係以「MA」表示，1,9-雙(丙烯醯氧基)壬烷係以「1,9-NDDA」表示。關於以下之實施例，相同之(A)成分及相同之(B)成分在表1中則為同樣地記述。 將雙(氟磺醯基)醯亞胺鋰(LiFSI)與碳酸二甲酯(DMC)以莫耳比會成為1/2(=LiFSI/DMC)之方式進行秤量，良好攪拌而調製出電解液。將甲基丙烯酸酯與1,9-雙(丙烯醯氧基)壬烷以莫耳比會成為95/5(=甲基丙烯酸酯/1,9-雙(丙烯醯氧基)壬烷)之方式進行秤量後，進行混合而調製出混合物之丙烯酸系聚合性化合物。並且，將作為混合物之丙烯酸系聚合性化合物與作為光聚合起始劑之1-羥基環己基苯基酮以莫耳比會成為97/3(=丙烯酸系聚合性化合物/光聚合起始劑)之方式進行混合，而調製出接著劑用組成物。其次，將氣相二氧化矽粒子、電解液及接著劑用組成物之合計設為100質量%時，以成為15質量%/82質量%/3質量%(=氣相二氧化矽粒子/電解液/接著劑用組成物)之方式進行秤量，良好混合而取得固體電解質膜形成用之混合物。 其後，在離型薄膜(琳得科股份有限公司製，製品名「PET38AL-5」)上，將固體電解質膜形成用之混合物壓縮成形為100μm之厚度而取得成形物。藉由對該成形物進行紫外線(UV)之照射[最大照度：180mW/cm 2，累積光量：1000mJ/cm 2，使用Eyegraphics公司製照度光量計(控制部EYE UV METER UVPF-A2，受光部EYE UV METER PD-365A2)測量]，並使接著劑用組成物硬化，而取得含有包含丙烯酸系聚合物之接著劑之固體電解質膜。實施例1之固體電解質膜中，將氣相二氧化矽粒子、電解液及包含丙烯酸系聚合物之接著劑之合計含量設為100質量%時，氣相二氧化矽粒子、電解液、及包含丙烯酸系聚合物之接著劑之個別含量係如同表1所示。 [實施例2] 除了使雙(氟磺醯基)醯亞胺鋰(LiFSI)與碳酸二甲酯(DMC)以莫耳比計成為1/3(=LiFSI/DMC)之方式進行秤量，良好攪拌而調製出電解液以外，其他係與實施例1同樣地操作而製作出固體電解質膜。 [實施例3] 準備硼氟化鋰(LiBF 4)作為鋰鹽。 除了使硼氟化鋰(LiBF 4)與碳酸二甲酯(DMC)以莫耳比計成為1/2(=LiBF 4/DMC)之方式進行秤量，良好攪拌而調製出電解液以外，其他係與實施例1同樣地操作而製作出固體電解質膜。 [實施例4] 準備硼氟化鋰(LiBF 4)作為鋰鹽。 除了使硼氟化鋰(LiBF 4)與碳酸二甲酯(DMC)以莫耳比計成為1/3(=LiBF 4/DMC)之方式進行秤量，良好攪拌而調製出電解液以外，其他係與實施例1同樣地操作而製作出固體電解質膜。 [實施例5] 準備碳酸伸丙酯(PC)作為碳酸酯系溶劑。 除了使雙(氟磺醯基)醯亞胺鋰(LiFSI)與碳酸伸丙酯(PC)以莫耳比計成為1/2(=LiFSI/PC)之方式進行秤量，良好攪拌而調製出電解液以外，其他係與實施例1同樣地操作而製作出固體電解質膜。 [比較例1] 除了使雙(氟磺醯基)醯亞胺鋰(LiFSI)與碳酸二甲酯(DMC)以莫耳比計成為1/12(=LiFSI/DMC)之方式進行秤量，良好攪拌而調製出電解液以外，其他係與實施例1同樣地操作來製作固體電解質膜，但並無法取得膜。 [比較例2] 除了使雙(氟磺醯基)醯亞胺鋰(LiFSI)與碳酸二甲酯(DMC)以莫耳比計成為1/6(=LiFSI/DMC)之方式進行秤量，良好攪拌而調製出電解液以外，其他係與實施例1同樣地操作來製作固體電解質膜，但無法取得膜。 [比較例3] 準備硼氟化鋰(LiBF 4)作為鋰鹽。 除了使硼氟化鋰(LiBF 4)與碳酸二甲酯(DMC)以莫耳比計成為1/12(=LiBF 4/DMC)之方式進行秤量，良好攪拌而調製出電解液以外，其他係與實施例1同樣地操作來製作固體電解質膜，但無法取得膜。 [比較例4] 準備硼氟化鋰(LiBF 4)作為鋰鹽。 除了使硼氟化鋰(LiBF 4)與碳酸二甲酯(DMC)以莫耳比計成為1/6(=LiBF 4/DMC)之方式進行秤量，良好攪拌而調製出電解液以外，其他係與實施例1同樣地操作來製作固體電解質膜，但無法取得膜。 [比較例5] 準備雙(氟磺醯基)醯亞胺鋰(LiFSI)作為鋰鹽。準備非為碳酸酯系溶劑之四乙二醇二甲基醚(G4)作為溶劑。準備氣相二氧化矽粒子(AEROSIL(註冊商標)380，日本Aerosil股份有限公司，由BET法所得之比表面積350m 2/g-410m 2/g)作為金屬氧化物粒子。準備聚四氟乙烯(PTFE)作為接著劑。 使雙(氟磺醯基)醯亞胺鋰(LiFSI)與四乙二醇二甲基醚(G4)以莫耳比計成為1/1(=LiFSI/G4)之方式進行秤量，良好攪拌而調製出電解液。其次，使電解液與氣相二氧化矽粒子以質量比計成為80/20(=電解液/氣相二氧化矽粒子)之方式進行秤量並良好地混合。並且，相對於電解液與氣相二氧化矽粒子之合計100質量份，添加聚四氟乙烯(PTFE)5質量份，並使用瑪瑙研缽進行良好混合。其後，將該混合物在氟樹脂製模具上進行壓縮成形而取得固體電解質膜。比較例5之固體電解質膜中，將氣相二氧化矽粒子、電解液及接著劑之合計含量設為100質量%時，氣相二氧化矽粒子、電解液、接著劑之個別之含量係如同表1所示。 [比較例6] 準備雙(三氟甲烷磺醯基)醯亞胺鋰(LiTFSI)作為鋰鹽。 除了使雙(三氟甲烷磺醯基)醯亞胺鋰(LiTFSI)與碳酸二甲酯(DMC)以莫耳比計成為1/6(=LiTFSI/DMC)之方式進行秤量，良好攪拌而調製出電解液以外，其他係與實施例1同樣地操作來製作固體電解質膜，但無法取得膜。 [比較例7] 準備碳酸二乙酯(DEC)作為碳酸酯系溶劑。 除了使雙(氟磺醯基)醯亞胺鋰(LiFSI)與碳酸二乙酯(DEC)以莫耳比計成為1/6(=LiFSI/DEC)之方式進行秤量，良好攪拌而調製出電解液以外，其他係與實施例1同樣地操作來製作固體電解質膜，但無法取得膜。 [電解液之黏度與固體電解質之評價] 對於實施例1~5及比較例1~7所使用之電解液，根據前述之黏度測量方法來測量黏度。又，對於實施例1~5及比較例5取得之固體電解質膜進行前述之溶解析出試驗、離子傳導率測量、及鋰離子遷移數測量。對於各實施例、及比較例5進行前述之電解液之離子傳導率測量。 將各例之固體電解質膜之組成展示於表1，將溶解析出試驗、離子傳導率測量、及鋰離子遷移數測量之測量結果展示於表2。表1中，Li鹽表示鋰鹽，溶劑表示碳酸酯系溶劑。 電解液之黏度未滿7mPa・s之各比較例皆無法取得固體電解質之膜。 關於溶解析出試驗之結果，得知各實施例皆可取得200循環以上，且安定運轉200循環以上。相對於此，比較例則未滿200循環。比較例中，隨循環經過之同時而電壓持續上升，而並未安定地運轉。 關於鋰離子遷移數之結果，得知各實施例之鋰離子遷移數皆超過0.5。一般而言，離子液體系統之電解液會有鋰離子遷移數低的傾向。例如，離子液體系統之電解液之鋰離子遷移數為0.5以下。且，比較例5之鋰離子遷移數為0.35。相對於此，得知各實施例之固體電解質具有優勢性。 根據以上，得知各實施例取得之固體電解質膜容易膜化。又，得知在與比較例5取得之固體電解質膜相比，鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性之各特性為高。因此，確認到本發明之固體電解質係固體電解質之膜化為容易，鋰離子之遷移數、離子傳導率、及對鋰金屬之安定性為高。 Hereinafter, embodiments of the present invention will be described as examples. The present invention is not limited to the content of the embodiments. [Solid Electrolyte] The solid electrolyte of this embodiment will be described. The solid electrolyte of this embodiment includes: an electrolytic solution containing a lithium salt and a carbonate-based solvent, and metal oxide particles. In addition, the solid electrolyte of this embodiment has a viscosity of 7 mPa·s or more at 23° C. measured in accordance with JIS Z 8803:2011. According to the solid electrolyte of this embodiment, it is easy to form a solid electrolyte film, and it is possible to obtain a solid electrolyte having a high transfer number of lithium ions, ion conductivity, and stability to lithium metal. The reason is presumed to be as follows. In the solid electrolyte of this embodiment, the thixotropy (hereinafter, sometimes referred to as thixotropy) of the electrolyte is improved by containing the electrolyte and the metal oxide particles. Also, when the viscosity of the electrolyte solution at 23°C is 7 mPa·s or more, the effect of improving the thixotropy will be further enhanced. Therefore, it becomes possible to form a film containing a mixture of metal oxide particles and an electrolytic solution. By achieving this film formation, it becomes possible to suppress the ion conductivity of the electrolytic solution from being impaired, and to suppress leakage of the electrolytic solution. Based on the above, it is speculated that the solid electrolyte of the present embodiment can be easily formed into a solid electrolyte film, and the migration number of lithium ions, ion conductivity, and stability to lithium metal are high (among these characteristics, especially for lithium Metal stability is high) solid electrolyte. <Electrolyte solution> The electrolyte solution of this embodiment is obtained by containing a lithium salt and a carbonate-based solvent. (Lithium salt) Lithium salts in this embodiment include, for example, lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), bis(fluorosulfonyl)imide Lithium bis(fluorosulfonyl)imide (LiFSI), 2-trifluoromethyl-4,5-dicyanoimidazolate lithium (LiTDI), 4,5-dicyano-1,2,3- Lithium triazole acid (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium borofluoride (LiBF 4 ), lithium bis(oxalato)borate (LiBOB), Lithium nitrate (LiNO 3 ), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), etc. Among them, from the viewpoint of making it easier to obtain a solid electrolyte with high lithium ion mobility, ion conductivity, and stability to lithium metal, the lithium salt is selected from bis(fluorosulfonyl)acyl At least one of lithium imide and lithium borofluoride is preferable. As the lithium salt, either lithium bis(fluorosulfonyl)imide lithium (LiFSI) or lithium borofluoride (LiBF 4 ) can be used alone, or these two can be used in combination. Lithium salts can exist as cations of lithium metal and counter ions of the cations in the solid electrolyte. By using these lithium salts, the stability to lithium metal can be further improved. (Carbonate-based solvents) The carbonate-based solvents of this embodiment specifically include, for example, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dipropylene carbonate ester (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), ethylene carbonate (EC), propylene carbonate (PC), and butyl carbonate (BC), etc. Among these, the carbonate-based solvent is selected from dimethyl carbonate, carbonic acid, and At least one kind of propylene ester is preferred. As the carbonate-based solvent, one of dimethyl carbonate (DMC) and propylene carbonate (PC) may be used alone, or these two may be used in combination. Here, the carbonate-based solvent in this embodiment means a compound having a carbonate skeleton in its molecular structure. (Molar ratio of lithium salt to carbonate-based solvent) In the electrolytic solution of the present embodiment, the molar ratio of lithium salt to carbonate-based solvent (lithium salt/carbonate-based solvent) is 1/4 to 1/1 The following is preferred. When the molar ratio is more than 1/4, the stability to lithium metal is easily improved. On the other hand, when the molar ratio is 1/1 or less, the lithium salt is easily dissolved in the carbonate-based solvent. From the viewpoint of making it easier to obtain a solid electrolyte with high lithium ion transfer number, ion conductivity, and high stability to lithium metal, the molar ratio may be 1/3 or more and 1/1 or less, or may be 1/3 More than 2 and less than 1/1. The reason is not clear, but the electrolytic solution of this embodiment is a combination of at least one lithium salt selected from lithium bis(fluorosulfonyl)imide and lithium borofluoride, and a lithium salt selected from dimethyl carbonate, In the case of an electrolytic solution made of at least one carbonate-based solvent of propylene carbonate, a lithium salt other than these lithium salts and a carbonate-based solvent other than these carbonate-based solvents are combined Compared with the electrolyte solution, the stability to lithium metal is more excellent. Also, in combination with at least one lithium salt selected from lithium bis(fluorosulfonyl)imide and lithium borofluoride, and at least one carbonic acid selected from dimethyl carbonate and propylene carbonate In the case of an electrolyte solution made of an ester solvent, the stability of the lithium metal will be more stable if the content of the lithium salt and the carbonate solvent is in the range of 1/4 to 1/1 in terms of molar ratio. excellent. The content of the electrolytic solution in the solid electrolyte is 75% by mass or more relative to the entire solid electrolyte from the viewpoint of making it easier to obtain a solid electrolyte with a high lithium ion transfer number, ion conductivity, and stability to lithium metal. Preferably, it is more than 77 mass %, more preferably 78 mass % or more, and more preferably 79 mass % or more. Also, from the same viewpoint, the content of the electrolytic solution in the solid electrolyte is preferably 90% by mass or less, more preferably 89% by mass or less, and more preferably 88% by mass or less, relative to the entire solid electrolyte. (Viscosity) In the solid electrolyte of this embodiment, the viscosity of the electrolytic solution is 7 mPa·s or more. From the point of view of making it easier to form a solid electrolyte film, the viscosity of the electrolyte is preferably 9mPa·s or higher, more preferably 11mPa·s or higher, more preferably 20mPa·s or higher, and 30mPa·s or higher More preferably, more than 40mPa・s is even better. The upper limit of the viscosity of the electrolytic solution is not particularly limited. For example, when taking into account the transfer number of lithium ions, ion conductivity, and solid electrolyte with high stability to lithium metal, the upper limit of the viscosity of the electrolyte may be, for example, 500 mPa·s or less, or 300 mPa·s below s. The viscosity of the electrolyte is measured at 23°C according to JIS Z 8803:2011. As for the measurement of the viscosity of the electrolyte, for example, a measurement method using a vibrating viscometer is preferable. Electrolyte Viscosity In the case of measuring the viscosity of the electrolyte in the solid electrolyte, it is sufficient to extract the electrolyte in the solid electrolyte and use, for example, a vibrating viscometer to measure the viscosity of the extracted electrolyte. <Metal Oxide Particles> The solid electrolyte of the present embodiment contains metal oxide particles. In the solid electrolyte of the present embodiment, the electrolytic solution is supported on the metal oxide particles by containing the electrolytic solution and the metal oxide particles. Here, in the present embodiment, the supported state means a state in which at least a part of the surface of the metal oxide particle is covered with an electrolytic solution. From the standpoint of ease of forming a solid electrolyte film into a metal oxide particle, the specific surface area measured by the BET method is preferably not less than 160 m 2 /g and not more than 700 m 2 /g. When the specific surface area (BET method) of the metal oxide particles is 160 m 2 /g or more, the thixotropy tends to improve, and it becomes easy to form a film containing a mixture of the metal oxide particles and the electrolytic solution (that is, a solid electrolyte). Also, when the specific surface area (BET method) is 700 m 2 /g or less, the miscibility with the electrolytic solution becomes good, and it becomes easy to form a solid electrolyte film. From the viewpoint of making it easier to form a solid electrolyte film, the specific surface area (BET method) of the metal oxide particles is preferably at least 165 m 2 /g, more preferably at least 170 m 2 /g. Also, from the same viewpoint, it is preferably not more than 600 m 2 /g, more preferably not more than 520 m 2 /g. Here, the BET method refers to a method of measuring the specific surface area of solid particles from the amount of adsorbed gas molecules by making solid particles adsorb gas molecules (usually nitrogen). The specific surface area can be measured using various BET measuring devices. As the metal oxide particle, one kind of metal oxide particle having the above-mentioned specific surface area may be used alone, or two or more kinds of metal oxide particles having different specific surface areas may be used in combination. The type of metal oxide particles is not particularly limited, and examples thereof include silica particles, alumina particles, zirconia particles, cerium oxide particles, magnesium silicate particles, calcium silicate particles, zinc oxide particles, and antimony oxide particles , indium oxide particles, tin oxide particles, titanium oxide particles, iron oxide particles, magnesium oxide particles, aluminum hydroxide particles, magnesium hydroxide particles, potassium titanate particles, and barium titanate particles. Metal oxide particles may be used alone or in combination of two or more. Among them, the metal oxide particles are preferably at least one selected from the group consisting of silica particles, alumina particles, zirconia particles, magnesia particles, and barium titanate particles from the viewpoint of improving thixotropy. The metal oxide particles are preferably silica particles in terms of light weight and small particle diameter. When silica particles are used as the metal oxide particles, the silica particles may be wet silica particles or dry silica particles. The wet-type silica particles include, for example, the wet-type silica particles of the sedimentation method obtained by neutralizing sodium silicate and mineral acid, and the wet-type silica particles of the sol-gel method. In addition, examples of dry silica particles include combustion method silica particles (fumed silica particles) obtained by burning a silane compound, and deflagration method silica particles obtained by explosively burning metal silicon powder. When the silica particles are dry-type silica particles, the incorporation of moisture from the silica particles can be suppressed, thereby easily suppressing deterioration of the electrolyte. Therefore, from the viewpoint of inhibiting the deterioration of the electrolyte, dry silica particles are preferred, and fumed silica particles are preferred. The content of the metal oxide particles in the solid electrolyte is preferably at least 4% by mass, more preferably at least 5% by mass, and at least 6% by mass relative to the entire solid electrolyte from the viewpoint of making it easier to form a film of the solid electrolyte. for better. Also, from the same viewpoint, the content of metal oxide particles in the solid electrolyte is preferably not more than 16 mass %, more preferably not more than 15 mass %, more preferably not more than 14 mass %, relative to the entire solid electrolyte. <Adhesive> The solid electrolyte of this embodiment may or may not contain an adhesive. The solid electrolyte of this embodiment may also contain a binder from the viewpoint of making it easier to form a solid electrolyte film. When the solid electrolyte of the present embodiment includes an adhesive, the type of the adhesive is not particularly limited. When the solid electrolyte of this embodiment contains an adhesive, it is easier to form a film of the solid electrolyte, and the stability of the lithium metal becomes easier to improve. The adhesive contains an acrylic polymer. The adhesive is better. In the solid electrolyte of this embodiment, when an adhesive is included, the adhesive may be in the form of polymers other than acrylic polymers, for example, or may not include polymers other than acrylic polymers. matter, but contains the form of acrylic polymer alone. It is preferable that the adhesive system alone contains an acrylic polymer. (Acrylic Polymer) In the solid electrolyte of the present embodiment, the acrylic polymer includes a structural unit derived from an acrylic polymerizable compound. That is, the acrylic polymer is a resin obtained by polymerizing an acrylic polymerizable compound as a monomer, and includes a resin having a constituent unit derived from the acrylic polymerizable compound in the main chain. Here, "derived from" means that a monomer undergoes a necessary structural change when it is polymerized. [Acrylic polymeric compound] The acrylic polymeric compound includes a (meth)acrylate compound. The acrylic polymeric compound may contain only a monofunctional (meth)acrylate compound, or may contain both a monofunctional (meth)acrylate compound and a polyfunctional (meth)acrylate compound. In this specification, "(meth)acryl" is a description used when referring to both "acryl" and "methacryl", and the same applies to other similar terms. In this specification, a polyfunctional (meth)acrylate compound means the (meth)acrylate compound more than bifunctional.・Monofunctional (meth)acrylate compound The solid electrolyte of this embodiment includes monofunctional ( A meth)acrylate compound is preferable as an acrylic polymeric compound. From the same point of view, the reaction rate constant k p of the monofunctional (meth)acrylate compound contained in the acrylic polymer compound is preferably 710L·mol -1 ·s -1 or higher, and 720L·mol -1・S -1 or more is more preferable. The upper limit of the reaction rate constant k p of the monofunctional (meth)acrylate compound contained in the acrylic polymerizable compound is not particularly limited, for example, it may be 40000L・mol -1・s -1 or less, or 35000L・mol -1・s -1 or less. In this specification, the monofunctional (meth)acrylate compound whose reaction rate constant kp is 700 L・mol -1・s -1 or more may be called (A) component. When using a monofunctional (meth)acrylate compound whose reaction rate constant k p is 700L·mol -1 ·s -1 or more, it is considered that the reactivity of the monofunctional (meth)acrylate compound will increase, and the molecular weight increases, and the solid electrolyte becomes easy to form a film. The monofunctional (meth)acrylate compound whose reaction rate constant k p is 700 L·mol -1 ·s -1 or more is not particularly limited, for example, it may be (meth)acrylic acid or (meth)acrylic acid alkyl ester. The monofunctional (meth)acrylate compound having a reaction rate constant k p of 700 L·mol -1 ·s -1 or more is preferably an alkyl (meth)acrylate having an alkyl group with 1 to 3 carbons. Specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, etc. are mentioned. Among them, the monofunctional (meth)acrylate compound whose reaction rate constant k p is 700 L·mol -1 ·s -1 or more is preferably methyl (meth)acrylate. In addition, by using a monofunctional (meth)acrylate compound whose reaction rate constant k p is 700 L·mol -1 ·s -1 or more, it becomes easier to obtain the transfer number of lithium ions, ion conductivity, and Lithium metal is a solid electrolyte with high stability.・Multifunctional (meth)acrylate compound The solid electrolyte of this embodiment further includes polyfunctional (meth)acrylates other than monofunctional (meth)acrylate compounds from the viewpoint of making it easier to form a solid electrolyte into a film The compound is preferably an acrylic polymer compound. When a polyfunctional (meth)acrylate compound other than a monofunctional (meth)acrylate compound is further included as an acrylic polymerizable compound, it becomes easier to obtain the transfer number of lithium ions, ion conductivity, and lithium metal The stability is high solid electrolyte. In this specification, a polyfunctional (meth)acrylate compound may be called (B) component. Multifunctional (meth)acrylate compounds, as long as the reaction rate constant kp is 700L・mol -1・s -1 or more than monofunctional (meth)acrylate compounds, bifunctional or higher (meth)acrylate compounds , that is, there is no special limitation. The multifunctional (meth)acrylate compound is easy to obtain the transfer number of lithium ions, ion conductivity, and solid electrolyte with high stability to lithium metal, and it is easy to make a film of solid electrolyte , preferably a polyfunctional (meth)acrylate compound that does not have a reactive group other than an acryl group. Polyfunctional (meth)acrylate compounds, for example, specifically, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1, 9-nonanediol diacrylate (1,9-bis(acryloxy)nonane), neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl Glycol adipate di(meth)acrylate, hydroxy-tert-valeric acid neopentyl glycol di(meth)acrylate, dicyclopentadiyl(meth)acrylate, dimethyloldicyclopentane Bifunctional (meth)acrylate compounds such as di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, and adamantane di(meth)acrylate; trimethylolpropane tri( Trifunctional (meth)acrylate compounds such as meth)acrylate, dipentaerythritol tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; diglycerol tetra(meth)acrylate, and Tetrafunctional (meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate; pentafunctional (meth)acrylate compounds such as dipentaerythritol penta(meth)acrylate; dipentaerythritol hexa(meth)acrylate 6 functional (meth)acrylate compounds etc. Among them, polyfunctional ( The meth)acrylate compound is at least one selected from the group consisting of 1,9-bis(acryloxy)nonane, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate better. In the solid electrolyte of this embodiment, the structural unit derived from the acrylic polymerizable compound contained in the acrylic polymer is selected from the structural unit derived from a monofunctional (meth)acrylate compound, and the structural unit derived from a polyfunctional At least one kind of group of constituent units of the (meth)acrylate compound is preferable. It is preferable that the structural unit derived from an acrylic polymeric compound contains the structural unit derived from a monofunctional (meth)acrylate compound. The structural unit derived from an acrylic polymeric compound preferably contains the structural unit derived from a monofunctional (meth)acrylate compound, and the structural unit derived from a polyfunctional (meth)acrylate compound. From the standpoint of making it easier to form a solid electrolyte film, the contents of the constituent units derived from monofunctional (meth)acrylate compounds and the constituent units derived from polyfunctional (meth)acrylate compounds are as follows The range is better. In addition, when the content of the structural unit derived from the monofunctional (meth)acrylate compound and the structural unit derived from the polyfunctional (meth)acrylate compound falls within the range shown below, it becomes easier to obtain lithium ions. A solid electrolyte with high transfer number, ion conductivity, and stability to lithium metal. When the total of the constituent units derived from monofunctional (meth)acrylate compounds and the constituent units derived from polyfunctional (meth)acrylate compounds is 100 mol%, the amount derived from monofunctional (meth)acrylate The content of the constituent units of the compound is preferably at least 90 mol%, more preferably at least 91 mol%, more preferably at least 93 mol%. When the total of the constituent units derived from monofunctional (meth)acrylate compounds and the constituent units derived from polyfunctional (meth)acrylate compounds is 100 mol%, the amount derived from monofunctional (meth)acrylate The content of the constituent units of the compound is preferably not more than 100 mol%, more preferably not more than 99 mol%, more preferably not more than 97 mol%. When the total of the constituent units derived from monofunctional (meth)acrylate compounds and the constituent units derived from polyfunctional (meth)acrylate compounds is 100 mole %, the polyfunctional (meth)acrylate derived The content of the constituent units of the compound is preferably at least 0 mol%, more preferably at least 1 mol%, more preferably at least 3 mol%. When the total of the constituent units derived from monofunctional (meth)acrylate compounds and the constituent units derived from polyfunctional (meth)acrylate compounds is 100 mole %, the polyfunctional (meth)acrylate derived The content of the constituent units of the compound is preferably not more than 10 mol%, more preferably not more than 9 mol%, more preferably not more than 7 mol%. The content of the acrylic polymer in the solid electrolyte is preferably at least 3% by mass, more preferably at least 4% by mass, and at least 5% by mass relative to the entire solid electrolyte from the viewpoint of ease of forming a film of the solid electrolyte for better. Also, from the same viewpoint, the content of the acrylic polymer in the solid electrolyte is preferably 10% by mass or less, more preferably 9% by mass or less, more preferably 8% by mass or less, relative to the entire solid electrolyte. [Photopolymerization initiator] In order to obtain an acrylic polymer, the solid electrolyte of this embodiment preferably uses a photopolymerization initiator. In the solid electrolyte of the present embodiment, the acrylic polymer is obtained, for example, by polymerizing an adhesive composition including an acrylic polymerizable compound and a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and known compounds used for the purpose of curing an acrylic polymerizable compound can be mentioned. The photopolymerization initiator is preferably a photopolymerization initiator responsive to ultraviolet rays. The photopolymerization initiator silicon may be used alone or in combination of two or more. Examples of photopolymerization initiators include, specifically, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α-hydroxy-α,α′-dimethylbenzene α-ketal compounds such as ethyl ketone, 2-methyl-2-hydroxypropiophenone, and 1-hydroxycyclohexyl phenylketone; methoxyacetophenone, 2,2-dimethoxy-2- Benzene such as phenylacetophenone, 2,2-diethoxyacetophenone, and 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinopropane-1 Ethanone-based compounds; benzoin ether-based compounds such as benzoin ethyl ether, benzoin isopropyl ether, and anisoin methy ether; ketal-based compounds such as benzyl dimethyl ketal;2 -Aromatic sulfonyl chloride-based compounds such as naphthalenesulfonyl chloride; photoactive oxime-based compounds such as 1-benzophenone-1,1-propanedione 2-(o-ethoxycarbonyl)oxime; benzophenone , benzyl benzoic acid, and benzophenone compounds such as 3,3'-dimethyl-4-methoxybenzophenone; thioxanthone (thioxanthone), 2-chlorothioxanthone, 2 -Methylthioxanthone, 2,4-Dimethylthioxanthone, Isopropylthioxanthone, 2,4-Dichlorothioxanthone, 2,4-Diethylthioxanthone, and 2,4 - Thioxanthone series compounds such as diisopropylthioxanthone; camphorquinone; halogenated ketones; acyl phosphine oxides; acyl phosphonates; (1-methylvinyl)phenyl)acetone] and the like. The content of the adhesive in the solid electrolyte is preferably at least 3% by mass, more preferably at least 4% by mass, and more preferably at least 5% by mass relative to the entire solid electrolyte from the viewpoint of making it easier to form a film of the solid electrolyte. good. Also, from the same viewpoint, the content of the binder in the solid electrolyte is preferably 10% by mass or less, more preferably 9% by mass or less, more preferably 8% by mass or less, relative to the entire solid electrolyte. In one aspect, the solid electrolyte of this embodiment preferably contains: the electrolyte solution containing lithium salt and carbonate-based solvent, metal oxide particles, and an adhesive containing acrylic polymer in the above-mentioned embodiment. The solid electrolyte of this embodiment may contain components other than these as long as the object of the present invention is not impaired. <Mass Ratio of Metal Oxide, Electrolyte Solution, and Adhesive> The solid electrolyte of this embodiment is made into a solid electrolyte film, and the total content of the electrolyte solution, metal oxide particles, and adhesive is set to 100. % by mass, the content shown below is preferable. In addition, in the total content of the electrolyte solution, metal oxide particles, and adhesive, when the contents of the electrolyte solution, metal oxide particles, and adhesive are in the following ranges, it becomes easier to obtain the transfer number of lithium ions, A solid electrolyte with high ion conductivity and stability to lithium metal. Preferably, the content of the electrolyte is not less than 77% by mass and not more than 90% by mass, the content of metal oxide particles is not less than 4% by mass and not more than 16% by mass, and the content of the adhesive is preferably not less than 3% by mass and not more than 10% by mass. Preferably, the content of the electrolyte is not less than 78% by mass and not more than 89% by mass, the content of metal oxide particles is not less than 5% by mass and not more than 15% by mass, and the content of the adhesive is not less than 4% by mass and not more than 9% by mass. The content of the electrolyte is more than 79% by mass and not more than 88% by mass, the content of metal oxide particles is not less than 6% by mass and not more than 14% by mass, and the content of the adhesive is more than 5% by mass and not more than 8% by mass. [Method for Producing Solid Electrolyte] Next, a preferable method for producing the solid electrolyte of the present embodiment will be described in the case where the solid electrolyte of the present embodiment contains an adhesive containing an acrylic polymer. The manufacturing method of the solid electrolyte of this embodiment is an example of the manufacturing method of the solid electrolyte, and is not limited to the manufacturing method demonstrated below. The manufacturing method of the solid electrolyte of this embodiment has the following steps. Step of preparing a mixture by mixing electrolyte solution, metal oxide particles, acrylic polymerizable compound, and photopolymerization initiator (Step 1) Step of molding the mixture to obtain a molded product (Step 2) Obtaining a molded product by irradiating ultraviolet rays Step of Solid Electrolyte Containing Acrylic Polymer Hardened by Acrylic Polymer Compound (Step 3) Wherein the electrolytic solution contains lithium salt and carbonate-based solvent, and the viscosity at 23°C is measured according to JIS Z 8803:2011 It is above 7mPa・s. According to the preferable manufacturing method of the solid electrolyte of this embodiment, it is easy to form a solid electrolyte film, and a solid electrolyte with a high lithium ion migration number, ion conductivity, and stability to lithium metal can be obtained. In addition, according to a preferred method of producing a solid electrolyte of this embodiment, a molded solid electrolyte is obtained by using an acrylic polymerizable compound and a photopolymerization initiator as an adhesive composition for obtaining an acrylic polymer. sexual enhancement. The reason why formability improves is thought to be as follows. In the method for producing a solid electrolyte of this embodiment, when mixing raw materials for obtaining a solid electrolyte, the solid electrolyte can be easily obtained without applying a strong shearing force. Therefore, formability is improved in the manufacturing method of the solid electrolyte of this embodiment. (Step 1) Step 1 is a step of mixing raw materials for obtaining a solid electrolyte to obtain a mixture. In step 1, first, as the raw materials for obtaining the solid electrolyte, the electrolyte solution containing the lithium salt and the carbonate-based solvent, the aforementioned metal oxide particles, and the aforementioned acrylic polymer are respectively prepared. Acrylic polymerizable compound and photopolymerization initiator. An electrolyte solution having a viscosity of 7 mPa·s or higher at 23°C was prepared as the electrolyte solution. An acrylic polymerizable compound and a photopolymerization initiator can also be prepared as a composition for an adhesive agent containing both. Secondly, for these prepared raw materials, weighing is used as the target amount. Thereafter, a mixture was prepared by mixing the weighed raw materials. The adjustment of the mixture can also be prepared by stirring each raw material using a known stirring device or the like. In the method for producing the solid electrolyte of this embodiment, the mixture may be prepared without imparting strong shearing force. The mixture prepared in step 1 is a mixture for forming a solid electrolyte. In the step 1, when mixing the metal oxide particles, the electrolytic solution, and the acrylic polymerizable compound and the photopolymerization initiator as the adhesive composition, it is preferable to mix in the following ratio, for example. When the total content of metal oxide particles, electrolytic solution, and adhesive composition is 100% by mass, the mixing ratio of metal oxide particles, electrolytic solution, and adhesive composition is, for example, based on the mass of the metal oxide Preferably, the particle size is 4 mass % to 16 mass %, the electrolyte solution is 77 mass % to 90 mass %, and the adhesive composition is preferably 3 mass % to 10 mass %. In the adhesive composition, the content of the acrylic polymerizable compound and the photopolymerization initiator is 100 mol% of the total content of the acrylic polymerizable compound and the photopolymerization initiator. The content of the active compound is more than 90 mol% and less than 99.9 mol%, and the photopolymerization initiator is preferably at least 0.1 mol% and less than 10 mol%. (Step 2) Step 2 is a step of obtaining a molded product from the mixture prepared in Step 1. In step 2, a molded product is obtained by molding the mixture prepared in step 1. The molding of the mixture is not particularly limited. For example, molding can be performed by applying the mixture on the surface of a support to form a coating film. In addition, the molding of the mixture can be performed, for example, by compression molding using a mold that exhibits peelability. The mold exhibiting peelability may be, for example, a release-type film on which a release treatment is applied on the surface of the film. (Step 3) Step 3 is a step of obtaining a solid electrolyte from the molded product obtained in Step 2. In step 3, an acrylic polymer is formed by irradiating the molded product formed in step 2 with ultraviolet rays to harden the acrylic polymer compound. Thereafter, a solid electrolyte comprising the aforementioned electrolyte solution, the aforementioned metal oxide particles, and a hardened acrylic polymer was obtained. The device for irradiating the molded body with ultraviolet rays is not particularly limited, as long as it hardens the acrylic polymer compound. For example, the device for irradiating ultraviolet rays may be a device provided with an ultraviolet LED lamp, a device provided with a high-pressure mercury lamp, or a device provided with a metal halide lamp. The conditions for irradiating the molded body with ultraviolet rays (UV) are not particularly limited as long as the acrylic polymerizable compound can be cured. The maximum illuminance and cumulative light intensity when irradiating ultraviolet rays include, for example, the following conditions. The maximum illuminance may be, for example, 5 mW/cm 2 or more, 10 mW/cm 2 or more, or 50 mW/cm 2 or more. In addition, the maximum illuminance may be 1000 mW/cm 2 or less, 700 mW/cm 2 or less, or 500 mW/cm 2 or less. The accumulated light amount may be, for example, 50 mJ/cm 2 or more, 100 mJ/cm 2 or more, or 500 mJ/cm 2 or more. In addition, the accumulated light amount may be 5000 mJ/cm 2 or less, 3000 mJ/cm 2 or less, or 2000 mJ/cm 2 or less. The solid electrolyte of an example of this embodiment is obtained by going through the above step 1, step 2, and step 3. That is, through the above steps, a solid electrolyte is obtained, which contains: an electrolyte solution containing lithium salt and a carbonate-based solvent, metal oxide particles, and an adhesive containing an acrylic polymer, and according to JIS Z 8803: The viscosity of the aforementioned electrolyte at 23°C measured in 2011 was above 7mPa·s. [Battery] Next, the battery of this embodiment will be described. The battery of this embodiment includes the solid electrolyte of this embodiment. In this embodiment, it is preferable to have the solid electrolyte of this embodiment as a constituent material of the electrolyte layer of the battery. A battery is composed of an anode, a cathode, and an electrolyte layer disposed between the anode and the cathode. With such a configuration, a battery excellent in various characteristics can be obtained. Moreover, as a battery, a secondary battery is preferable, and a lithium ion secondary battery is preferable. Various members included in the lithium ion secondary battery of this embodiment are not particularly limited, and materials generally used in batteries, for example, can be used. Furthermore, the present invention is not limited to the foregoing embodiments, and modifications, improvements, and the like within the scope of achieving the object of the present invention are included in the present invention. [Examples] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, the measurement or evaluation in the following examples and comparative examples was performed by the method shown below. [Measurement of Viscosity of Electrolyte] The viscosity of the electrolyte was measured at 23° C. using a vibrating viscometer (manufactured by Seconic Co., Ltd., VM-10A-L) in accordance with JIS Z 8803:2011. Calibration of the vibrating viscometer is carried out at 23°C using the standard solution for viscometer calibration according to JIS Z 8809:2011. Three types of standard solutions, JS2.5, JS50, and JS200 manufactured by NOF Co., Ltd., were used for viscometer calibration. [Measurement of Ionic Conductivity of Solid Electrolyte] The solid electrolyte membrane was cut out into a circle with a diameter of 6mm, sandwiched between two stainless steel plates as electrodes, and the impedance between the stainless steel plates was measured. The measurement system uses the AC impedance method of measuring the resistance component by applying an AC (applied voltage: 10mV) between the electrodes, and calculates the ionic conductivity from the obtained real impedance intercept of the Cole-Cole plot. In addition, the measurement system used a potentiostat/galvanostat (manufactured by VMP-300 biologic). The ion conductivity (σ A ) was obtained by the following formula (F1). σ A =L A /(R A ×S A )・・・(F1) In the formula (F1), σ A represents the ion conductivity (unit: S・cm -1 ), and R A represents the resistance (unit: Ω ), S A represents the cross-sectional area of the solid electrolyte membrane (unit: cm 2 ), and LA represents the distance between electrodes (unit: cm). The measurement temperature was 25°C. Also, the ion conductivity (σ A ) was calculated from the measurement result of the complex impedance. [Measurement of Ion Conductivity of Electrolyte Solution] A circular mesh cloth (α-UX SCREEN 150-035/380TW, manufactured by NBC Meshtec Co., Ltd.) with a diameter of 19 mm was used as a spacer. Thereafter, the spacer was impregnated with an electrolyte solution obtained by blending lithium salts and carbonate-based solvents used in Examples or Comparative Examples with a specified prescription, and sandwiched between two stainless steel plates with a diameter of 16mm as electrodes, and Measure the resistance between stainless steel plates. The measurement system uses the AC impedance method of measuring the resistance component by applying an alternating current between the electrodes (the applied voltage is 10 mV), and calculates the ion conductivity from the obtained real-number impedance intercept of the Cole plot. In addition, a potentiostat/galvanostat (manufactured by VMP-300 biologic) was used for the measurement system. The ion conductivity (σ B ) was obtained by the following formula (F2). σ B =L B /(R B ×S B )・・・(F2) In the formula (F2), σ B represents the ion conductivity (unit: S cm -1 ), and R B represents the resistance (unit: Ω ), S B represents the cross-sectional area of electrodes (unit: cm 2 ), and L B represents the distance between electrodes (unit: cm). The measurement temperature was 25°C. Also, the ion conductivity (σ B ) was calculated from the measurement result of the complex impedance. [Evaluation of Stability of Lithium Metal (Dissolution and Desorption Test)] The solid electrolyte membrane was cut out into a circle with a diameter of 19 mm, and sandwiched between two lithium metals as electrodes to produce a lithium symmetric unit. The lithium metal electrode system is made with a diameter of 16mm. The current density was set at 3 mA/cm 2 at a temperature of 25° C., the oxidation current was passed to 3 mAh/cm 2 , and then the reduction current was passed to 3 mAh/cm 2 . This series of operations was repeated for 200 cycles, and the voltage change after 200 cycles was measured. The dissolution and desorption behavior of lithium metal was investigated by this voltage measurement. It was confirmed that it is stable to lithium metal when dissolution and precipitation are repeated at a constant voltage without a short circuit or the like. The number of cycles of operation at a potential within ±20mV from the initial cycle voltage was taken as the number of stable operation cycles, and the stability of each example to lithium metal was compared. [Measurement of lithium ion transfer number] The obtained solid electrolyte membrane was cut out into a circle with a diameter of 6mm, sandwiched between two lithium plates as electrodes to produce a unit. However, the cell was connected to a potentiostat/galvanostat (manufactured by VMP-300 biologic), and measurement was started after 2 hours or more had passed at 25°C. The measurement system first performs complex impedance measurement to calculate the resistance value (R 0 ), and then applies a voltage of 30mV to perform DC polarization measurement. Measure the initial current value (I 0 ) and the stable current value (I S ) when the current value becomes constant. After confirming that there is a stable current, the complex impedance measurement is performed again to calculate the resistance value (R S ). The lithium ion transfer number (t + ) was obtained by the following formula (F3) (Evans' formula). t + =Is(ΔV-I 0 ×R 0 )/I 0 (ΔV-I S ×R S )・・・(F3) In formula (F3), ΔV represents the applied voltage, R 0 , R S , I 0 and IS are the same as above. [Example 1] Lithium bis(fluorosulfonyl)imide (LiFSI) was prepared as a lithium salt. Dimethyl carbonate (DMC) was prepared as a carbonate-based solvent. Fumed silica particles (AEROSIL (registered trademark) 380, Aerosil Japan Co., Ltd., specific surface area 350 m 2 /g to 410 m 2 /g obtained by the BET method) were prepared as metal oxide particles. In order to obtain the acrylic polymer constituting the adhesive, methacrylate (component (A)) and 1,9-bis(acryloxy)nonane (component (B)) were prepared as acrylic polymer compounds, and Prepare 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator. Here, methacrylate (component (A)) corresponds to a monofunctional (meth)acrylate compound, and the reaction rate constant k p is 720 L·mol -1 ·s -1 . In addition, the specific surface area of 350m 2 /g-410m 2 /g means that the specific surface area ranges from 350m 2 /g to 410m 2 /g. Hereinafter, the same applies to other similar descriptions. In Table 1, methacrylate is represented by "MA", and 1,9-bis(acryloxy)nonane is represented by "1,9-NDDA". Regarding the following examples, the same (A) component and the same (B) component are described in the same manner in Table 1. Weigh lithium bis(fluorosulfonyl)imide (LiFSI) and dimethyl carbonate (DMC) in such a way that the molar ratio becomes 1/2 (=LiFSI/DMC), and stir well to prepare an electrolyte solution . The molar ratio of methacrylate and 1,9-bis(acryloxy)nonane will be 95/5 (=methacrylate/1,9-bis(acryloxy)nonane) The acrylic polymeric compound of the mixture is prepared by mixing after weighing. And, the molar ratio of the acrylic polymerizable compound as a mixture and 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator becomes 97/3 (=acrylic polymerizable compound/photopolymerization initiator) Mix in a manner to prepare a composition for an adhesive. Next, when the total of fumed silica particles, electrolytic solution, and adhesive composition is 100% by mass, 15% by mass/82% by mass/3% by mass (=fumed silica particles/electrolyte Liquid/adhesive composition) were weighed and well mixed to obtain a mixture for forming a solid electrolyte membrane. Thereafter, the solid electrolyte membrane-forming mixture was compression-molded on a release film (manufactured by Lintec Corporation, product name "PET38AL-5") to a thickness of 100 μm to obtain a molded product. By irradiating the molded article with ultraviolet (UV) [maximum illuminance: 180mW/cm 2 , cumulative light intensity: 1000mJ/cm 2 , use an illuminance light meter (control part EYE UV METER UVPF-A2, light receiving part EYE UV METER PD-365A2) measurement], and harden the adhesive composition to obtain a solid electrolyte membrane containing an adhesive containing an acrylic polymer. In the solid electrolyte membrane of Example 1, when the total content of the fumed silica particles, the electrolytic solution, and the adhesive containing the acrylic polymer is 100% by mass, the fumed silica particles, the electrolytic solution, and the adhesive containing the acrylic polymer The individual content of the adhesive of the acrylic polymer is as shown in Table 1. [Example 2] Except that lithium bis(fluorosulfonyl)imide (LiFSI) and dimethyl carbonate (DMC) were weighed so that the molar ratio was 1/3 (=LiFSI/DMC), good A solid electrolyte membrane was produced in the same manner as in Example 1, except that an electrolytic solution was prepared by stirring. [Example 3] Lithium borofluoride (LiBF 4 ) was prepared as a lithium salt. In addition to weighing lithium borofluoride (LiBF 4 ) and dimethyl carbonate (DMC) in a molar ratio of 1/2 (=LiBF 4 /DMC), stirring well to prepare an electrolyte, other systems A solid electrolyte membrane was produced in the same manner as in Example 1. [Example 4] Lithium borofluoride (LiBF 4 ) was prepared as a lithium salt. In addition to weighing lithium borofluoride (LiBF 4 ) and dimethyl carbonate (DMC) in a molar ratio of 1/3 (=LiBF 4 /DMC), stirring well to prepare an electrolyte, other systems A solid electrolyte membrane was produced in the same manner as in Example 1. [Example 5] Propylene carbonate (PC) was prepared as a carbonate-based solvent. In addition to weighing lithium bis(fluorosulfonyl)imide (LiFSI) and propylene carbonate (PC) in a molar ratio of 1/2 (=LiFSI/PC), stir well to prepare an electrolytic A solid electrolyte membrane was produced in the same manner as in Example 1 except for the liquid. [Comparative Example 1] Except that lithium bis(fluorosulfonyl)imide (LiFSI) and dimethyl carbonate (DMC) were weighed so that the molar ratio was 1/12 (=LiFSI/DMC), good The solid electrolyte membrane was produced in the same manner as in Example 1 except that the electrolyte solution was prepared by stirring, but the membrane could not be obtained. [Comparative Example 2] Except that lithium bis(fluorosulfonyl)imide (LiFSI) and dimethyl carbonate (DMC) were weighed so that the molar ratio was 1/6 (=LiFSI/DMC), good The solid electrolyte membrane was produced in the same manner as in Example 1, except that the electrolytic solution was prepared by stirring, but the membrane could not be obtained. [Comparative Example 3] Lithium borofluoride (LiBF 4 ) was prepared as a lithium salt. In addition to weighing lithium borofluoride (LiBF 4 ) and dimethyl carbonate (DMC) in a molar ratio of 1/12 (=LiBF 4 /DMC) and stirring well to prepare an electrolyte, other systems A solid electrolyte membrane was produced in the same manner as in Example 1, but the membrane could not be obtained. [Comparative Example 4] Lithium borofluoride (LiBF 4 ) was prepared as a lithium salt. In addition to weighing lithium borofluoride (LiBF 4 ) and dimethyl carbonate (DMC) in a molar ratio of 1/6 (=LiBF 4 /DMC), stirring well to prepare an electrolyte, other systems A solid electrolyte membrane was produced in the same manner as in Example 1, but the membrane could not be obtained. [Comparative Example 5] Lithium bis(fluorosulfonyl)imide (LiFSI) was prepared as a lithium salt. Tetraethylene glycol dimethyl ether (G4), which is not a carbonate-based solvent, was prepared as a solvent. Fumed silica particles (AEROSIL (registered trademark) 380, Aerosil Japan Co., Ltd., specific surface area 350 m 2 /g to 410 m 2 /g obtained by the BET method) were prepared as metal oxide particles. Prepare polytetrafluoroethylene (PTFE) as an adhesive. Weigh lithium bis(fluorosulfonyl)imide (LiFSI) and tetraethylene glycol dimethyl ether (G4) in a molar ratio of 1/1 (=LiFSI/G4), stir well and Prepare the electrolyte. Next, the electrolytic solution and the fumed silica particles were weighed and mixed well so that the mass ratio became 80/20 (=electrolyte solution/fumed silica particles). Then, 5 parts by mass of polytetrafluoroethylene (PTFE) was added to 100 parts by mass of the total of the electrolytic solution and the fumed silica particles, and mixed well using an agate mortar. Thereafter, the mixture was compression-molded on a fluororesin mold to obtain a solid electrolyte membrane. In the solid electrolyte membrane of Comparative Example 5, when the total content of fumed silica particles, electrolyte solution and adhesive is set to 100% by mass, the individual contents of fumed silica particles, electrolyte solution and adhesive are as follows: Table 1 shows. [Comparative Example 6] Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was prepared as a lithium salt. In addition to weighing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and dimethyl carbonate (DMC) in a molar ratio of 1/6 (=LiTFSI/DMC), well stirred and prepared Except for the electrolytic solution, the solid electrolyte membrane was produced in the same manner as in Example 1, but the membrane could not be obtained. [Comparative Example 7] Diethyl carbonate (DEC) was prepared as a carbonate-based solvent. In addition to weighing lithium bis(fluorosulfonyl)imide (LiFSI) and diethyl carbonate (DEC) in a molar ratio of 1/6 (=LiFSI/DEC), stir well to prepare an electrolytic Except for the liquid, the solid electrolyte membrane was produced in the same manner as in Example 1, but the membrane could not be obtained. [Evaluation of Viscosity of Electrolyte Solution and Solid Electrolyte] For the electrolyte solutions used in Examples 1 to 5 and Comparative Examples 1 to 7, the viscosity was measured according to the aforementioned viscosity measurement method. In addition, for the solid electrolyte membranes obtained in Examples 1 to 5 and Comparative Example 5, the aforementioned dissolution test, ion conductivity measurement, and lithium ion transfer number measurement were performed. The ion conductivity measurement of the electrolyte solution mentioned above was performed about each Example, and the comparative example 5. The composition of the solid electrolyte membrane of each example is shown in Table 1, and the measurement results of the dissolution test, ion conductivity measurement, and lithium ion transfer number measurement are shown in Table 2. In Table 1, Li salt represents a lithium salt, and solvent represents a carbonate-based solvent. In each comparative example in which the viscosity of the electrolyte solution was less than 7 mPa·s, a solid electrolyte film could not be obtained. With regard to the results of the dissolution test, it is known that each embodiment can achieve more than 200 cycles, and the stable operation is more than 200 cycles. On the other hand, the comparative example did not complete 200 cycles. In the comparative example, the voltage continued to rise as the cycle progressed, but stable operation was not performed. With regard to the results of the lithium ion migration number, it was known that the lithium ion migration number of each example exceeded 0.5. Generally speaking, the electrolyte of the ionic liquid system tends to have a low migration number of lithium ions. For example, the lithium ion migration number of the electrolyte solution of the ionic liquid system is 0.5 or less. In addition, the lithium ion migration number of Comparative Example 5 was 0.35. On the other hand, it is known that the solid electrolytes of the examples have advantages. From the above, it can be seen that the solid electrolyte membrane obtained in each of the examples is easily formed into a membrane. In addition, compared with the solid electrolyte membrane obtained in Comparative Example 5, it was found that the transfer number of lithium ions, ion conductivity, and stability to lithium metal were higher in each characteristic. Therefore, it was confirmed that the solid electrolyte of the present invention is easy to form a solid electrolyte film, and has a high transfer number of lithium ions, ion conductivity, and stability to lithium metal.

Claims (14)

一種固體電解質，其含有：包含鋰鹽及碳酸酯系溶劑之電解液，與金屬氧化物粒子，根據JIS Z 8803：2011所測量之在23℃之前述電解液之黏度為7mPa・s以上。A solid electrolyte comprising: an electrolyte solution containing a lithium salt and a carbonate-based solvent, and metal oxide particles, wherein the viscosity of the electrolyte solution at 23°C measured in accordance with JIS Z 8803:2011 is 7 mPa·s or more. 如請求項1之固體電解質，其中前述鋰鹽為選自由雙(氟磺醯基)醯亞胺鋰、及硼氟化鋰所成群之至少一種。The solid electrolyte according to claim 1, wherein the lithium salt is at least one selected from the group consisting of lithium bis(fluorosulfonyl)imide and lithium borofluoride. 如請求項1或請求項2之固體電解質，其中前述碳酸酯系溶劑為選自由碳酸二甲酯、及碳酸伸丙酯所成群之至少一種。The solid electrolyte according to claim 1 or claim 2, wherein the carbonate-based solvent is at least one selected from the group consisting of dimethyl carbonate and propylene carbonate. 如請求項1或請求項2之固體電解質，其中前述電解液所包含之前述鋰鹽對前述碳酸酯系溶劑之莫耳比(鋰鹽/碳酸酯系溶劑)為1/4以上1/1以下。The solid electrolyte according to claim 1 or claim 2, wherein the molar ratio of the lithium salt contained in the electrolytic solution to the carbonate-based solvent (lithium salt/carbonate-based solvent) is not less than 1/4 and not more than 1/1 . 如請求項1或請求項2之固體電解質，其中前述金屬氧化物粒子為二氧化矽粒子。The solid electrolyte according to claim 1 or claim 2, wherein the metal oxide particles are silicon dioxide particles. 如請求項1或請求項2之固體電解質，其中前述金屬氧化物粒子藉由BET法所測量之比表面積為160m 2/g以上700m 2/g以下。 The solid electrolyte according to claim 1 or claim 2, wherein the specific surface area of the metal oxide particles measured by the BET method is not less than 160 m 2 /g and not more than 700 m 2 /g. 如請求項1或請求項2之固體電解質，其中更含有接著劑。The solid electrolyte according to Claim 1 or Claim 2, further comprising an adhesive. 如請求項7之固體電解質，其中前述接著劑包含丙烯酸系聚合物。The solid electrolyte according to claim 7, wherein the adhesive comprises an acrylic polymer. 如請求項8之固體電解質，其中前述丙烯酸系聚合物包含源自丙烯酸系聚合性化合物之構成單位， 前述丙烯酸系聚合性化合物包含反應速率常數k p為700L・mol -1・s -1以上之單官能(甲基)丙烯酸酯化合物。 The solid electrolyte according to claim 8, wherein the acrylic polymer comprises constituent units derived from an acrylic polymeric compound, and the acrylic polymeric compound comprises a reaction rate constant kp of 700 L·mol -1 ·s -1 or more Monofunctional (meth)acrylate compound. 如請求項9之固體電解質，其中前述丙烯酸系聚合性化合物更包含前述單官能(甲基)丙烯酸酯化合物以外之多官能(甲基)丙烯酸酯化合物。The solid electrolyte according to claim 9, wherein the acrylic polymeric compound further includes a polyfunctional (meth)acrylate compound other than the monofunctional (meth)acrylate compound. 如請求項10之固體電解質，其中前述多官能(甲基)丙烯酸酯化合物為選自由1,9-雙(丙烯醯氧基)壬烷、三羥甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、及二季戊四醇六丙烯酸酯所成群之至少一種。As the solid electrolyte of claim item 10, wherein the aforementioned polyfunctional (meth)acrylate compound is selected from 1,9-bis(acryloxy)nonane, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and at least one of dipentaerythritol hexaacrylate group. 如請求項10之固體電解質，其中前述源自丙烯酸系聚合性化合物之構成單位包含選自由前述源自單官能(甲基)丙烯酸酯化合物之構成單位、及前述源自多官能(甲基)丙烯酸酯化合物之構成單位所成群之至少一種， 將前述源自單官能(甲基)丙烯酸酯化合物之構成單位與前述源自多官能(甲基)丙烯酸酯化合物之構成單位之合計設為100莫耳%時， 前述源自單官能(甲基)丙烯酸酯化合物之構成單位之含量為90莫耳%以上100莫耳%以下， 前述源自多官能(甲基)丙烯酸酯化合物之構成單位之含量為0莫耳%以上10莫耳%以下。 The solid electrolyte according to claim 10, wherein the structural unit derived from the acrylic polymeric compound comprises a structural unit derived from the aforementioned monofunctional (meth)acrylate compound, and the aforementioned polyfunctional (meth)acrylic acid At least one of the groups of constituent units of ester compounds, When the total of the constituent units derived from the monofunctional (meth)acrylate compound and the constituent units derived from the polyfunctional (meth)acrylate compound is 100 mol %, The content of the constituent units derived from the monofunctional (meth)acrylate compound is not less than 90 mol % and not more than 100 mol %, The content of the structural unit derived from the polyfunctional (meth)acrylate compound is not less than 0 mol % and not more than 10 mol %. 一種電池，其具備如請求項1至請求項12中任一項之固體電解質。A battery comprising the solid electrolyte according to any one of claim 1 to claim 12. 一種固體電解質之製造方法，其係製造如請求項8至請求項12中任一項之固體電解質之方法，且具備： 混合前述電解液、前述金屬氧化物粒子、前述丙烯酸系聚合性化合物、及光聚合起始劑而調製混合物的步驟； 使前述混合物成形而取得成形物的步驟；及， 藉由對前述成形物照射紫外線而取得包含前述丙烯酸系聚合性化合物經硬化之前述丙烯酸系聚合物之固體電解質的步驟。 A method of manufacturing a solid electrolyte, which is a method of manufacturing a solid electrolyte according to any one of claim 8 to claim 12, and has: a step of mixing the electrolytic solution, the metal oxide particles, the acrylic polymerizable compound, and the photopolymerization initiator to prepare a mixture; a step of forming the aforementioned mixture to obtain a shaped object; and, A step of obtaining a solid electrolyte comprising the acrylic polymer hardened by the acrylic polymerizable compound by irradiating the molded article with ultraviolet rays.
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