201225372 六、發明說明： 【發明所屬之技術領域】 本發明係關於活性物質·電解質複合體及其製造方法 、及全固體型鋰-硫蓄電池，特別是關於具有使用醚系有 機溶劑之凝膠化電解質，且維持了電極活性物質粒子與電 解質之接觸性的活性物質·電解質複合體及其製造方法、 以及使用此活性物質-電解質複合體，在維持了電極活性 物質粒子與電解質的接觸性之下提高安全性，並且抑制放 電生成物之多硫化鋰及低硫化鋰向電解質中溶出的全固體 型鋰-硫蓄電池。 【先前技術】 鋰離子蓄電池比起其他種類的電池，具有高能量密度 、高出力等特徵，而多用於行動電話或筆記型電腦等的電 池。又，近年來，以油電混合車或電動車的普及爲目標進 行的硏究盛行，伴隨該油電混合車或電動車的硏究，而謀 求鋰離子蓄電池更加地高容量化。在如此之狀況下，將認 爲是高容量、低成本、環保的單體硫用於正極活性物質的 鋰-硫蓄電池正受到矚目。單體硫的理論容量爲 1 67 5m Ah/g ’已知比一般在鋰離子蓄電池使用的正極活性 物質容量（例如、LiC〇02:約14 0mAh/g)具有更大的容 量。 但是’將單體硫用於使用通常之有機系電解液的鋰離 子蓄電池之正極活性物質時，會有（1)因單體硫（S)爲 -5- 201225372 絕緣體，故爲了用作電極必需要大量的導電輔助材、（2 )因在蓄電池的放電反應所產生之中間生成物的多硫化鋰 (Li2Sx : x = 2〜8 )可溶於電解液，正極活性物質的利用效 率變得不佳，又，溶解後的多硫化鋰會與負極的Li金屬 反應，引起自我放電，因而充放電循環特性變得不佳、（ 3)因過放電而生成的低硫化鋰（Li2S )其爲絕緣、不溶 性，故會堆積於正極上，其爲不可逆容量（irreversible capacity )的主要成因，因而循環特性變得不佳等問題。 進一步，因使用有機電解液，會有產生電解液的洩漏/起 火的可能性，安全性上亦有問題。 再者，使用一般鋰離子電池所用之碳酸酯系有機溶劑 時，因多硫化鋰不會溶解，故認爲雖然能夠放電，但會變 得無法充電（例如，參照專利文獻1 )。 又’爲了提高電極混合料的機械強度，且提高電解液 的含浸性’已知有以電極混合料之全體重量爲基準而含有 5重量％以下範圍之膨潤石（smectite)等黏土礦物的電極 混合料，作爲含電極活性物質的電極混合料（例如，參照 專利文獻2)。此情況下，黏土礦物係含於電極混合料中 ’係用作獎料以提局機械強度、電解液之含浸性、並且提 高電解液的濕潤性。 進一步地，已知有由將電解質溶解於有機化合物而得 之電解液、藉由與該電解液混合以形成凝膠的高分子材料 、與展現有膨潤性之層狀黏土化合物粒子的混合物而成之 固體狀電解質（例如，參照專利文獻3 )。該技術中，爲 -6- 201225372 了形成凝膠，係使用聚偏二氟乙烯（PVdF )等高分子材 料。 又進一步，在使用了有機系電解液的鋰離子蓄電池中 ，因電池漏液或電池的重複使用，由負極析出樹枝狀鋰（ 枝晶），故產生短路而引發起火現象等，其安全面受到指 摘。考慮到鋰離子蓄電池會使用在各種用途，故必須更加 重視漏液的抑制或安全性等。因此，如電池自體之構造的 探討、不可燃電解液之開發、無機固體電解質之開發等的 提高漏液之抑制或安全性等之鋰離子蓄電池的開發是爲當 務之急。 [先前技術文獻] [專利文獻] [專利文獻1 ]日本特開2006-32143號公報 [專利文獻2 ]日本特開2008-71757號公報 [專利文獻3 ]日本特開平1 0 - 2 6 9 8 4 4號公報 【發明內容】 [發明所欲解決的課題] 本發明的課題在解決上述之習知技術的問題點，且在 提供使用可防止電解液洩漏的凝膠化電解質、且可維持電 極活性物質之粒子與電解質的接觸性之活性物質-電解質 複合體及其製造方法、以及使用該複合體且安全性高、可 提高循環特性之全固體型鋰-硫蓄電池。 201225372 [用以解決課題之手段] 有鑑於上述課題’本發明者等進行了關於在使用了醚 系有機溶劑的電解液中添加如膨潤石之膨潤性層狀黏土礦 物，以使電解液凝膠化（固體化）的探討，成功地使用凝 膠化電解質維持了活性物質-電解質複合體的界面活性、 並且抑制了放電生成物之多硫化鋰（Li2Sx : χ = 2~8 )向電 解質中溶出、並藉由將放電生成物持續保持於正極，以抑 制與負極之Li金屬的反應（亦即、抑制自我放電），而 實現了提高充放電循環特性，而完成本發明。 本發明之活性物質·電解質複合體，係爲以指定比例 混合活性物質、導電輔助材、及黏結材而得之電極材料， 其特徵爲：於在集電體上設有正極活性物質爲單體硫或含 鋰硫化物之電極材料之電極上，設有包含醚系有機溶劑、 且由鋰離子傳導性電解液與膨潤性層狀黏土礦物的混合物 而成的凝膠化電解質，並對該電極施加使該凝膠化電解質 液化之強度的振動而成。 上述之活性物質-電解質複合體，其中膨潤性層狀黏 土礦物爲膨潤石系層狀黏土礦物、或雲母系層狀黏土礦物 〇 上述之活性物質-電解質複合體，其中含鋰硫化物爲 硫化鋰（Li2S )。 本發明之活性物質-電解質複合體的製造方法，其特 徵係：以指定比例混合活性物質、導電輔助材、及黏結材 而得之電極材料，且於在集電體上設有正極活性物質爲單 -8- 201225372 體硫或含鋰硫化物之電極材料而成之電極上，塗布包含醚 系有機溶劑、且由鋰離子傳導性電解液與膨潤性層狀黏土 礦物的混合物而成的凝膠化電解質，接著對經塗布有凝膠 化電解質的電極施加使該凝膠化電解質液化之強度的振動 ，使凝膠化電解質液化而浸透入電極內，以製造活性物 質-電解質複合體。 上述活性物質-電解質複合體之製造方法，其中膨潤 性層狀黏土礦物爲膨潤石系層狀黏土礦物、或雲母系層狀 黏土礦物。 上述活性物質-電解質複合體之製造方法，其中含鋰 硫化物爲硫化鋰（Li2S )。 本發明之全固體型鋰-硫蓄電池，其特徵爲使用上述 活性物質-電解質複合體。 上述全固體型鋰-硫蓄電池，其中活性物質-電解質複 合體爲正極活性物質-電解質複合體。 上述全固體型鋰-硫蓄電池，其中活性物質-電解質複 合體爲負極活性物質-電解質複合體。 上述全固體型鋰-硫蓄電池，其中活性物質-電解質複 合體爲正極活性物質-電解質複合體及負極活性物質-電解 質複合體。 [發明之效果] 依照本發明，藉由使用將使用了醚系有機溶劑的電解 液凝膠化而成的凝膠化電解質，可發揮能夠提供抑制電解 -9- 201225372 液的洩漏、且可在維持電極活性物質粒子與電解質 性之下，提高安全性、並且抑制放電生成物之多硫 低硫化鋰向電解質中溶出的全固體型鋰-硫蓄電池 【實施方式】 以下，說明本發明的實施形態。 依照本發明之活性物質-電解質複合體的實施 該活性物質-電解質複合體係爲以指定比例混合活 、導電輔助材、及黏結材而得之電極材料，於在集 設有正極活性物質爲單體硫或含鋰硫化物（例如、 :Li2S )之電極材料之電極上，設置包括醚系有機 且由鋰離子傳導性電解液、與由膨潤石系層狀黏土 雲母系層狀黏土礦物中所選出之指定量的膨潤性層 礦物之混合物而成的凝膠化電解質，並對該電極施 凝膠化電解質液化之強度的物理振動而成者。只要 凝膠化電解質液化之程度的振動，則其振動方法並 限制。例如，若以手持而施加振動、或以超音波等 動，則凝膠化電解質會液化，並向電極內浸透，而 覆全體活性物質的周圍。另外，該活性物質-電解 體，可使用於正極亦可使用於負極。 上述活性物質係包含由單體硫（S )、硫化鋰 )等含鋰硫化物中選出之已知正極活性物質；或者 、碳黑等碳系物質 '矽系物質、錫系物質、矽-碳 的接觸 化鋰及 的效果 形態， 性物質 電體上 硫化鋰 溶劑、 礦物及 狀黏土 加使該 係可使 無特殊 施加振 能夠包 質複合 (Li2S ，由碳 系物質 -10- 201225372 趣鈦氧化物（例如、Li4Ti5〇i2等）、Li金屬、Li-Al合 金等中選出之已知負極活性物質。 作爲導電輔助材者，只要在目標之鋰-硫蓄電池不產 生化學變化、且係具有導電性的物質，即可使用，並無特 殊限制。例如’能夠使用石墨、各種碳黑、導電性纖維、 或銅粉末、鐵粉末等金屬粉末等。 作爲黏結材者’只要在目標之鋰-硫蓄電池不產生化 學變化、且具有作爲黏結材之作用的物質，即可使用，並 無特殊限制。例如，能夠使用聚偏二氟乙嫌（PVdF )、 聚乙烯、聚丙烯、聚四氟乙烯（PTFE)等。 作爲集電體者，只要在目標之鋰-硫蓄電池不產生化 學變化、且具有導電性的物質，即可使用，並無特殊限制 。例如’能夠使用由不鏽鋼、鋁、鎳、鈦等所選出之正極 集電體；或者，由銅、不鏽鋼、鋁、鎳、鈦等所選出之負 極集電體。 本發明中使用的凝膠化電解質，係如上述，爲包含醚 系有機溶劑、且由鋰離子傳導性電解液、與由膨潤石系層 狀黏土礦物或雲母系層狀黏土礦物中所選出之指定量的膨 潤性層狀黏土礦物之混合物而成者。此時，凝膠化電解質 較佳係於有機溶劑中添加膨潤性層狀黏土礦物，且使該黏 土礦物充分膨潤之後，將其如以下所述般添加於電解液中 、或與電解質混合而製造，但並非受如此方法所限制’只 要能夠製造本發明之凝膠化電解質，其添加順序並無限制 -11 - 201225372 作爲上述醚系有機溶劑者，能夠使用鋰離子蓄電池所 用之已知溶劑，並無特殊限制。例如，能夠使用1，3-二氧 環戊烷（DOL)、四氫呋喃、2·甲基四氫呋喃、1，4 -二噁 烷、I,2-二甲氧基乙烷、二乙醚、1，2-二乙氧基乙烷 '三 伸乙甘醇二甲醚等。又，亦可混合2種以上之該等醚系有 機溶劑來使用。 作爲添加於電解液之有機溶劑的鋰鹽，可使用一般被 使用者。例如，能夠使用由 LiC丨04、LiPF6、LiAsF6、 LiN(CF3S02)2、LiBF4、LiCF3S03、LiSbF6 等所選出之電 解質經溶解於有機溶劑者。 作爲上述膨潤石系層狀黏土礦物者，只要係展現搖溶 性者，即可使用，並無特殊限制。例如，能夠使用皂土、 合成鋰皂石、水輝石 '三水鋁石、綠泥石、高嶺石、禾樂 石、葉蠟石、滑石、蒙脫石、輕石、伊萊石、貝德石、砂 鐵石、鉻膨潤石、及合成膨潤石（Co-op Chemical (股） 製、商品名：Lucentite STN)等，較佳爲水輝石、皂土、 蒙脫石、合成膨潤石（Co-op Chemical (股）製、商品名 :Lucentite STN)等。 作爲上述雲母系層狀黏土礦物者，只要係展現搖溶性 者’即可使用，並無特殊限制。例如，能夠使用雲母、脆 雲母、白雲母、鈉雲母、金雲母、及黑雲母等，較佳爲雲 母等。 本發明所使用的膨潤性層狀黏土礦物，係藉由添加於 溶劑而展現搖溶性之性質。所謂搖溶性，意指持續受到剪 -12- 201225372 切應力（振動）時，其黏度逐漸降低，而成爲液狀；又， 當使其靜止時其黏度逐漸上昇，最終成爲固體狀的現象。 本發明之目的係利用此搖溶性之性質，一開始先使凝膠化 電解質液化，使凝膠化電解質散佈於電極全體，將活性物 質之周圍充分包覆，與僅使用電解液時同樣地降低活性物 質-電解質之界面的接觸電阻之後，藉由使其固體化，而 提高安全性與提升電池性能。亦即、本發明係爲一邊對在 集電體（例如、A1箔、Cu箔等）上設有包含電極活性物 質的電極材料而成的電極施加超音波等物理振動，一邊使 於電極表面塗布之凝膠化電解質向電極內部浸透，藉以將 活性物質的表面全部以電解質均句地包覆，實現活性物 質-電解質界面之接觸電阻的減少、同時抑制放電生成物 之多硫化鋰（Li2Sx: x = 2~8)向電解質中溶出：且藉由將 放電生成物持續保持於正極，抑制與負極之Li金屬的反 應，藉以實現充放電循環特性的提高。 上述之鋰離子傳導性電解液與膨潤性層狀黏土礦物的 混合比例，只要以能夠使電解液展現搖溶性的量作適當摻 合即可。隨著膨潤性層狀黏土礦物增多，會逐漸固體化， 變得不展現搖溶性，又，隨著膨潤性層狀黏土礦物變少， 就越接近液體，因此會產生與使用電解液時相同的問題。 例如’由搖溶性的觀點，膨潤性層狀黏土礦物的添加量較 佳爲以此混合物的全重量爲基準，在2wt%~l〇wt%左右的 範圍內。低於2 wt%時會有不展現搖溶性的傾向，超過 l〇wt%時，比起i〇wt%，會有進行凝膠化的傾向，而不展 -13- 201225372 現搖溶性。 依照本發明之活性物質-電解質複合體之製造方法的 實施形態，該製造方法係在將上述活性物質、上述導電輔 助材、及上述黏結材以指定比例（例如、重量比45:45 :10)混合而得之電極材料塗布於上述集電體上而成的電 極上，塗布上述凝膠化電解質，接著對於經塗布凝膠化電 解質的電極，施加使該凝膠化電解質液化之強度的上述振 動（較佳爲超音波振動），使液化後的凝膠化電解質向電 極內均勻地浸透，並使活性物質的周圍以電解質包覆來製 造。 上述活性物質、上述導電輔助材、及上述黏結材，係 例如以如下的方式來摻合。導電輔助材係以正極全體重量 爲基準，混合1〜50wt%、較佳爲混合30〜50wt%。低於 lwt%時無法發揮充分的導電性、超過50wt%時會產生正 極活性物質的量減少、容量變小的問題。黏結材係以正極 全體重量爲基準，混合l~50wt%、較佳爲混合5~30wt%。 低於lwt%時，黏結能力會變低、超過50wt%時會產生正 極活性物質的量減少、容量變小的問題。 依照本發明之鋰-硫蓄電池的實施形態，該蓄電池係 爲使用上述凝膠化電解質者，使該凝膠化電解質浸透入集 電體上的正極材料內’而用作正極複合體；及/或使該凝 膠化電解質浸透入集電體上的負極材料內，而用作負極複 合體。使用本發明之凝膠化電解質，因振動而液化的電解 質會自動地浸透入於集電體之A1箔（正極）或c u箱（負 -14 - 201225372 極）塗布的正極（負極）材料內，電解質係包覆全部活性 物質的周圍，藉此活性物質-電解質之界面的接觸電阻會 降低，又，藉由抑制放電生成物之多硫化鋰（Li2Sx: x = 2〜8 )向電解質中溶出、且將放電生成物持續保持於正 極而抑制與負極之Li金屬反應，來提高充放電循環特性 〇 本發明之鋰-硫蓄電池中，爲了防止正極與負極的短 路，可用亦可不使用通常所使用的隔離膜。在使用的情況 時，只要係通常已知之隔離膜即可。例如，能夠使用多孔 質聚丙烯薄膜（Celgard公司製；商品名：Celgard#2400 )等。 依照本發明，·如圖1(a)所示，能夠將活性物質11 、黏結材1 2、導電輔助材1 3以指定比例混合後之電極材 料塗布於集電體14上，得到電極，並在該電極上，塗布 含有有機溶劑，且由鋰離子傳導性電解液與膨潤性層狀黏 土礦物構成之凝膠化電解質15，並藉由施加振動（例如 、超音波振動等），來製造活性物質-電解質複合體（電 極複合體）。能夠將經如此製造之活性物質-電解液複合 體用作電極，且用已知的方法組裝鋰-硫蓄電池。藉油對 凝膠化電解質施加振動，如圖1 ( a )所示，凝膠化電解 質15會液化，並且包覆全部活性物質11的周圍。 另一方面，如圖1(b)所示，不對凝膠化電解質15 施加振動時，塗布於電極上之凝膠化電解質15僅停滯於 電極表面，而不浸透至內部，僅包覆表面層之活性物質 -15- 201225372 11的周圍。因此，無法達成所期望的目的。圖1(b)中 之參照數字11、12、13、及14係與圖1 (a)相同。 以下，列舉出實施例及比較例來具體說明本發明。201225372 6. Technical Field of the Invention The present invention relates to an active material/electrolyte composite, a method for producing the same, and an all-solid lithium-sulfur battery, and more particularly to gelation using an ether-based organic solvent. An active material/electrolyte composite in which an electrolyte and a contact property between an electrode active material particle and an electrolyte are maintained, a method for producing the same, and a use of the active material-electrolyte composite to maintain contact between an electrode active material particle and an electrolyte An all-solid lithium-sulfur storage battery which improves safety and suppresses dissolution of lithium sulfide and low lithium sulfide of the discharge product into the electrolyte. [Prior Art] Lithium-ion batteries are characterized by high energy density and high output compared to other types of batteries, and are often used in batteries such as mobile phones or notebook computers. In addition, in recent years, research is progressing on the spread of hybrid electric vehicles and electric vehicles. With the investigation of hybrid electric vehicles and electric vehicles, the capacity of lithium ion batteries has increased. Under such circumstances, a lithium-sulfur battery which is considered to be a high-capacity, low-cost, and environmentally-friendly monomer sulfur for a positive electrode active material is attracting attention. The theoretical capacity of the monomeric sulfur is 1 67 5 m Ah/g'. It is known to have a larger capacity than the positive electrode active material capacity (e.g., LiC〇02: about 140 mAh/g) which is generally used in lithium ion secondary batteries. However, when the monomer sulfur is used as a positive electrode active material of a lithium ion secondary battery using a usual organic electrolyte, (1) since the monomer sulfur (S) is a -5 to 201225372 insulator, it is necessary to be used as an electrode. A large amount of conductive auxiliary material is required, and (2) lithium polysulfide (Li2Sx: x = 2 to 8) which is an intermediate product generated by a discharge reaction of the battery is soluble in the electrolyte, and the utilization efficiency of the positive electrode active material does not become Preferably, the dissolved lithium polysulfide reacts with the Li metal of the negative electrode to cause self-discharge, so that the charge and discharge cycle characteristics become poor, and (3) the low lithium sulfide (Li2S) generated by overdischarge is insulated. Insoluble, it accumulates on the positive electrode, which is a major cause of irreversible capacity, and thus the cycle characteristics are not good. Further, the use of the organic electrolytic solution may cause leakage or ignition of the electrolytic solution, and there is also a problem in safety. In addition, when a carbonate-based organic solvent used in a general lithium ion battery is used, since lithium polysulfide does not dissolve, it is considered that although it can be discharged, it is impossible to charge (for example, see Patent Document 1). Further, in order to increase the mechanical strength of the electrode mixture and to improve the impregnation property of the electrolyte solution, it is known that electrode mixture of clay minerals such as smectite in a range of 5% by weight or less based on the total weight of the electrode mixture is known. The material is an electrode mixture containing an electrode active material (for example, refer to Patent Document 2). In this case, the clay mineral is contained in the electrode mixture as a prize to improve mechanical strength, impregnation of the electrolyte, and improve the wettability of the electrolyte. Further, an electrolyte obtained by dissolving an electrolyte in an organic compound, a polymer material mixed with the electrolyte to form a gel, and a mixture of particles of a layered clay compound exhibiting swelling property are known. The solid electrolyte (for example, refer to Patent Document 3). In this technique, a gel is formed for -6-201225372, and a polymer material such as polyvinylidene fluoride (PVdF) is used. Further, in a lithium ion secondary battery using an organic electrolytic solution, dendritic lithium (dendritic) is precipitated from the negative electrode due to leakage of the battery or repeated use of the battery, so that a short circuit occurs and a fire phenomenon occurs, and the safety surface is affected. Accusation. Considering that lithium ion batteries are used in various applications, it is necessary to pay more attention to the suppression or safety of leakage. Therefore, the development of lithium ion batteries, such as the discussion of the structure of the battery itself, the development of non-flammable electrolytes, and the development of inorganic solid electrolytes, such as suppression of leakage or safety, are urgently required. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2008-32757 [Patent Document 2] JP-A-2008-71757 (Patent Document 3) Japanese Patent Laid-Open No. 1 0 - 2 6 9 8 [4] Japanese Patent Application No. 4, No. 4, SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The problem of the present invention is to solve the problems of the above-described conventional techniques, and to provide a gelled electrolyte capable of preventing electrolyte leakage and to maintain an electrode An active material-electrolyte composite having contact property between particles of an active material and an electrolyte, a method for producing the same, and an all-solid lithium-sulfur battery having high safety and high cycle characteristics by using the composite. 201225372 [Means for Solving the Problem] In view of the above-mentioned problem, the inventors of the present invention have added a swellable layered clay mineral such as bentonite to an electrolytic solution using an ether-based organic solvent to make the electrolyte gel Discussion of solidification (solidification), successful use of a gelled electrolyte to maintain the interfacial activity of the active material-electrolyte complex, and to inhibit dissolution of lithium polysulfide (Li2Sx: χ = 2~8) into the electrolyte Further, by maintaining the discharge product on the positive electrode and suppressing the reaction with the Li metal of the negative electrode (that is, suppressing self-discharge), the charge/discharge cycle characteristics are improved, and the present invention has been completed. The active material/electrolyte composite of the present invention is an electrode material obtained by mixing an active material, a conductive auxiliary material, and a binder in a predetermined ratio, and is characterized in that a positive electrode active material is provided as a monomer on a current collector. a gelled electrolyte comprising an ether-based organic solvent and a mixture of a lithium ion conductive electrolyte and a swellable layered clay mineral, and the electrode is provided on the electrode of the electrode material of sulfur or a lithium-containing sulfide The vibration of the strength at which the gelled electrolyte is liquefied is applied. The above active material-electrolyte composite, wherein the swellable layered clay mineral is a bentonite layered clay mineral or a mica layered clay mineral, the active material-electrolyte complex described above, wherein the lithium sulfide is lithium sulfide (Li2S). The method for producing an active material-electrolyte composite according to the present invention is characterized in that an electrode material obtained by mixing an active material, a conductive auxiliary material, and a binder at a predetermined ratio is provided, and a positive electrode active material is provided on the current collector. Single-8-201225372 Electrode composed of a mixture of a lithium-ion conductive electrolyte and a swellable layered clay mineral on an electrode made of a body material of sulfur or a lithium-containing sulfide. The electrolyte is applied, and then the electrode coated with the gelled electrolyte is subjected to vibration for liquefying the gelled electrolyte, and the gelled electrolyte is liquefied and impregnated into the electrode to produce an active material-electrolyte composite. The above method for producing an active material-electrolyte composite, wherein the swellable layered clay mineral is a bentonite layered clay mineral or a mica layered clay mineral. A method for producing the above-described active material-electrolyte composite, wherein the lithium-containing sulfide is lithium sulfide (Li2S). The all solid lithium-sulfur battery of the present invention is characterized in that the above active material-electrolyte composite is used. The above all solid lithium-sulfur battery, wherein the active material-electrolyte composite is a positive electrode active material-electrolyte composite. The all-solid type lithium-sulfur battery described above, wherein the active material-electrolyte composite is a negative electrode active material-electrolyte composite. The all-solid type lithium-sulfur battery described above, wherein the active material-electrolyte composite is a positive electrode active material-electrolyte composite and a negative electrode active material-electrolyte composite. [Effect of the Invention] According to the present invention, by using a gelled electrolyte obtained by gelling an electrolytic solution using an ether-based organic solvent, it is possible to provide a solution for suppressing leakage of the electrolytic solution-9-201225372, and An all-solid lithium-sulfur battery that maintains the safety of the electrode active material particles and the electrolyte property and suppresses the discharge of the polysulfide and low lithium sulfide of the discharge product into the electrolyte. [Embodiment] Hereinafter, an embodiment of the present invention will be described. . The active material-electrolyte composite according to the present invention is an electrode material obtained by mixing a living material, a conductive auxiliary material, and a binder in a specified ratio, and the positive electrode active material is a monomer. An electrode comprising an electrode material of sulfur or a lithium-containing sulfide (for example, : Li2S), comprising an ether-based organic material selected from a lithium ion conductive electrolyte and a layered clay mineral composed of a bentonite layered clay mica system A gelled electrolyte obtained by mixing a predetermined amount of a swellable layer mineral, and the electrode is subjected to physical vibration of the strength of liquefaction of the gelled electrolyte. As long as the gelled electrolyte is liquefied to a degree of vibration, the vibration method is limited. For example, when vibration is applied by hand or by ultrasonic waves, the gelled electrolyte is liquefied and permeated into the electrode to cover the entire periphery of the active material. Further, the active material-electrolyte can be used for the positive electrode or can be used for the negative electrode. The active material includes a known positive electrode active material selected from lithium-containing sulfides such as monomer sulfur (S) or lithium sulfide; or a carbon-based material such as carbon black, a lanthanide substance, a tin-based substance, and a ruthenium-carbon. The contact lithium has an effect form, and the lithium sulfide solvent, minerals and clays of the material substance can be added to the system to allow the coating to be compounded without special application of vibration (Li2S, which is oxidized by the carbonaceous material -10- 201225372 A known negative electrode active material selected from the group consisting of, for example, Li4Ti5〇i2, Li metal, Li-Al alloy, etc. As a conductive auxiliary material, as long as the target lithium-sulfur battery does not undergo chemical change and is electrically conductive The substance can be used without any particular limitation. For example, 'the use of graphite, various carbon blacks, conductive fibers, or metal powders such as copper powder and iron powder can be used. As a binder, as long as the target is lithium-sulfur The battery does not cause chemical changes and has a function as a binder, and can be used without particular limitation. For example, it is possible to use polyvinylidene fluoride (PVdF), polyethylene, polypropylene. Polytetrafluoroethylene (PTFE), etc. As a current collector, it is not particularly limited as long as it does not cause chemical changes and has conductivity in the target lithium-sulfur battery, and is not particularly limited. a selected positive electrode current collector of stainless steel, aluminum, nickel, titanium, or the like; or a negative electrode current collector selected from copper, stainless steel, aluminum, nickel, titanium, etc. The gelled electrolyte used in the present invention is as described above. It is a mixture of an ether-based organic solvent and a lithium ion conductive electrolyte, and a specified amount of a swellable layered clay mineral selected from a bentonite layered clay mineral or a mica layered clay mineral. In this case, the gelled electrolyte is preferably added to the organic solvent to add a swellable layered clay mineral, and after the clay mineral is sufficiently swollen, it is added to the electrolyte or mixed with the electrolyte as described below. And manufactured, but not limited by such a method', as long as the gelled electrolyte of the present invention can be produced, the order of addition is not limited -11 - 201225372 as the above-mentioned ether-based organic solvent A known solvent which can be used for a lithium ion secondary battery is not particularly limited. For example, 1,3-dioxocyclopentane (DOL), tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, I can be used. , 2-dimethoxyethane, diethyl ether, 1,2-diethoxyethane, tri-ethylene glycol dimethyl ether, etc. Further, two or more kinds of these ether-based organic solvents may be mixed. The lithium salt to be added as an organic solvent to the electrolytic solution can be generally used by a user. For example, an electrolyte selected from LiC丨04, LiPF6, LiAsF6, LiN(CF3S02)2, LiBF4, LiCF3S03, LiSbF6, or the like can be used. When it is dissolved in an organic solvent, the bentonite layered clay mineral can be used as long as it exhibits solubility, and is not particularly limited. For example, bentonite, laponite, hectorite' gibbsite, chlorite, kaolinite, helite, pyrophyllite, talc, montmorillonite, pumice, ilyite, bead can be used. Stone, sandstone, chrome bentonite, and synthetic bentonite (Co-op Chemical, trade name: Lucentite STN), etc., preferably hectorite, bentonite, montmorillonite, synthetic bentonite (Co- Op Chemical (stock), trade name: Lucentite STN). The above mica-based layered clay mineral can be used as long as it exhibits a thixotropic property, and is not particularly limited. For example, mica, crisp mica, muscovite, sodium mica, phlogopite, and biotite can be used, and mica or the like is preferable. The swellable layered clay mineral used in the present invention exhibits the property of thixotropic property by being added to a solvent. The so-called thixotropy means that when the shear stress (vibration) is continuously sheared, the viscosity gradually decreases and becomes liquid; in addition, when it is at rest, its viscosity gradually rises and eventually becomes a solid phenomenon. The object of the present invention is to liquefy the gelled electrolyte at the beginning, to liquefy the gelled electrolyte, to spread the gelled electrolyte to the entire electrode, to sufficiently coat the periphery of the active material, and to reduce it in the same manner as when only the electrolyte is used. After the contact resistance at the interface of the active material-electrolyte, by solidifying it, safety is improved and battery performance is improved. In other words, the present invention applies a physical vibration such as ultrasonic waves to an electrode provided with an electrode material containing an electrode active material on a current collector (for example, an A1 foil or a Cu foil), and coats the surface of the electrode. The gelled electrolyte is impregnated into the interior of the electrode, whereby the surface of the active material is entirely coated with the electrolyte to achieve a reduction in contact resistance at the active material-electrolyte interface, and at the same time suppressing lithium sulfide (Li2Sx: x of the discharge product). = 2 to 8) Dissolving into the electrolyte: By continuously maintaining the discharge product on the positive electrode, the reaction with the Li metal of the negative electrode is suppressed, thereby improving the charge-discharge cycle characteristics. The mixing ratio of the lithium ion conductive electrolyte and the swellable layered clay mineral described above may be appropriately blended in such an amount as to exhibit the solubility of the electrolyte. As the swellable layered clay minerals increase, they gradually solidify and become less soluble, and as the swellable layered clay minerals become smaller, the closer to the liquid, the same as when the electrolyte is used. problem. For example, from the viewpoint of the solubility, the amount of the swellable layered clay mineral is preferably in the range of from about 2% by weight to about 1% by weight based on the total weight of the mixture. When it is less than 2 wt%, there is a tendency to exhibit no thixotropic property. When it exceeds l〇wt%, gelation tends to occur compared with i〇wt%, and the tendency to melt is not exhibited. According to an embodiment of the method for producing an active material-electrolyte composite of the present invention, the production method is characterized in that the active material, the conductive auxiliary material, and the binder are at a predetermined ratio (for example, a weight ratio of 45:45:10) The electrode material obtained by mixing the electrode material is applied onto the electrode formed on the current collector, and the gelled electrolyte is applied, and then the vibration of the gelled electrolyte is applied to the electrode coated with the gelled electrolyte. (Ultrasonic vibration is preferred), and the gelled electrolyte after liquefaction is uniformly impregnated into the electrode, and the periphery of the active material is coated with an electrolyte. The active material, the conductive auxiliary material, and the above-mentioned binder are blended, for example, in the following manner. The conductive auxiliary material is mixed in an amount of 1 to 50% by weight, preferably 30 to 50% by weight based on the total weight of the positive electrode. When the amount is less than 1% by weight, sufficient conductivity cannot be exhibited, and when it exceeds 50% by weight, the amount of the positive electrode active material decreases and the capacity becomes small. The binder is mixed by 1 to 50% by weight, preferably 5 to 30% by weight based on the total weight of the positive electrode. When the amount is less than 1% by weight, the bonding ability is lowered, and when it exceeds 50% by weight, the amount of the positive electrode active material decreases and the capacity becomes small. According to an embodiment of the lithium-sulfur battery of the present invention, the battery is used as a positive electrode composite by using the gelled electrolyte to impregnate the gelled electrolyte into a positive electrode material on the current collector; and/ Alternatively, the gelled electrolyte is impregnated into the negative electrode material on the current collector to serve as a negative electrode composite. By using the gelled electrolyte of the present invention, the electrolyte liquefied by vibration is automatically impregnated into the A1 foil (positive electrode) or the cu box (negative-14 - 201225372 pole) coated positive electrode (negative electrode) material of the current collector, The electrolyte coats the periphery of all the active materials, whereby the contact resistance at the interface of the active material-electrolyte is lowered, and the lithium sulfide (Li2Sx: x = 2 to 8) which suppresses the discharge product is eluted into the electrolyte. Further, the discharge product is continuously held on the positive electrode to suppress the reaction with the Li metal of the negative electrode to improve the charge/discharge cycle characteristics. In the lithium-sulfur storage battery of the present invention, in order to prevent the short circuit between the positive electrode and the negative electrode, it is possible to use or not to use the commonly used one. Isolation membrane. In the case of use, it is only required to be a separator which is generally known. For example, a porous polypropylene film (manufactured by Celgard Co., Ltd.; trade name: Celgard #2400) can be used. According to the present invention, as shown in Fig. 1(a), the electrode material obtained by mixing the active material 11 and the binder 1 and the conductive auxiliary material 13 in a predetermined ratio can be applied to the current collector 14 to obtain an electrode. On the electrode, a gelled electrolyte 15 containing an organic solvent and composed of a lithium ion conductive electrolyte and a swellable layered clay mineral is applied, and an activity is generated by applying vibration (for example, ultrasonic vibration). Material-electrolyte complex (electrode complex). The thus-produced active material-electrolyte composite can be used as an electrode, and a lithium-sulfur storage battery can be assembled by a known method. The oil is applied to the gelled electrolyte by oil, and as shown in Fig. 1 (a), the gelled electrolyte 15 is liquefied and covers the entire periphery of the active material 11. On the other hand, as shown in Fig. 1(b), when vibration is not applied to the gelled electrolyte 15, the gelled electrolyte 15 applied to the electrode is only stagnated on the surface of the electrode without being soaked to the inside, and only the surface layer is coated. The active substance -15- 201225372 11 around. Therefore, the desired purpose cannot be achieved. Reference numerals 11, 12, 13, and 14 in Fig. 1(b) are the same as those in Fig. 1(a). Hereinafter, the present invention will be specifically described by way of examples and comparative examples.
[實施例IJ 於醚系有機溶劑之1、2_二甲氧基乙烷（DME) 2g中 ’添加膨潤性層狀黏土礦物之親油性合成膨潤石（Co-op Chemical (股）製、商品名：Lucentite STN) lOOmg，使 其充分膨潤。電解液係使用3mol/L的LiN(CF3S02)2 ( DME : DOL = 9 : lvol% )。對上述經充分膨潤之含有膨潤 石的二甲氧基乙烷溶液添加電解液567mg，以製造凝膠化 電解質。 [實施例2] 對實施例1中製造的凝膠化電解質施加超音波振動。 在施加振動的期間，凝膠化電解質會液化，停止振動，並 藉由之後的放置，確認了其會凝膠化（固體化）。 [實施例3] 使用硫（S ) ( Kishida化學（股）製）作爲正極活性 物質、使用乙炔黑（AB )作爲導電輔助材、使用PVdF作 爲黏結材，且將該等以重量比4 5 : 4 5 : 1 0混合而得的正 極材料塗布在集電體之A1箔上’而得到正極。將於實施 例1中製造之凝膠化電解質塗布於正極表面上，並藉由施 -16- 201225372 加超音波振動，使凝膠化電解質液化’如圖1 ( a )所示 般浸透於正極內，以製造活性物質-電解質複合體。結果 ，如圖1 (a)所示，全部之活性物質的表面均以電解質 包覆。將經如此製造之正極複合體用作正極、將使用Li 金屬用作負極，而組裝203 2型鋰-硫蓄電池’並進行充放 電試驗。此情況時，充放電的電流値設爲192.74gA/cm2 (相當於0.1C rate (充放電速率））、截止電壓設爲 1.5-2.8V、重複進行充放電43循環。另外，因爲係將單 體硫用作正極，故由放電反應開始測定。 (比較例1 ) 除了不施加超音波振動以外，係遵照實施例3記載的 方法來組裝鋰·硫蓄電池，進行充放電試驗。此情況時， 充放電的電流値設爲190μΑ/(；ιη2 (相當於0.1 C rate)。 各自對於實施例3及比較例1製造之鋰-硫蓄電池探 討第1循環之放電曲線後，比較例1的放電容量比實施例 3的放電容量爲低。因此，使用本發明之凝膠化電解質， 並施加振動所製造的鋰-硫蓄電池，電解質充分地浸透入 正極內，比起不施加振動而製造的鋰-硫蓄電池，可得到 高能量密度。 (比較例2 ) 電解液係使用 3mol/L 的 LiN(CF3S02)2 ( DME : DOL = 9 ： lvol% )。除了隔離膜係使用多孔質聚丙烯薄膜 -17- 201225372 (Celgard公司製；商品名：Celgard#2400)以外，係遵 照實施例3記載的方法來組裝鋰·硫蓄電池，進行充放電 試驗。此情況時，充放電的電流値設爲1 8 9.75 pA/cm2 ( 相當於〇.1C rate)，重複進行充放電4 5循環。另外，因 爲係將單體硫用作正極，故由放電反應開始測定。 將實施例3及比較例2中製造的鋰-硫蓄電池各自的 第1循環之放電曲線示於圖2。圖2中，縱軸爲E/V( Li/Li+)、橫軸爲放電容量（mAh/g (活性物質））。由 圖2明顯可知，兩者之初期放電容量均爲1 〇〇〇mAh/g，可 知得到高放電容量。 又，將以實施例3及比較例2中製造的鋰-硫蓄電池 各自的重複循環特性而得的放電容量示於圖3。圖3中， 縱軸爲放電容量（mAh/g (活性物質））、橫軸爲循環次 數。由圖3明顯可知，2 0循環以後，實施例3的放電容 量變得比比較例2的放電容量更大，可知循環特性有所提 高。 (比較例3 ) 使用硫（S) (Kishida化學（股）製）作爲正極活性 物質、使用乙炔黑（AB)作爲導電輔助材、使用PVdF作 爲黏結材，且將該等以重量比45 ·· 45 : 1 0混合而得的正 極材料塗布在集電體之A1箔上，而得到正極。使用經如 此製造之正極，並使用lmol/L的LiCL04(EC (碳酸伸乙 酯）：DEC (碳酸二乙醋）=1: lvol%)之電解液、使用 -18- 201225372 多孔質聚丙烯薄膜（Celgard#2400 )作爲隔離膜、使用Li 金屬作爲負極，而組裝2 0 3 2型鋰-硫蓄電池，並進行充放 電試驗。此情況時，充放電的電流値設爲3 55.08 μΑ/(：ηι2 (相當於0.1 C rate )、截止電壓設爲1.4-3.0V，重複進 行充放電3循環。另外，因爲係將單體硫用作正極，故由 放電反應開始測定。 將於比較例3製造之鋰-硫蓄電池的充放電曲線的第 1循環（1st)、第2循環（2nd)及第3循環（3rd)，示 於圖4。圖4中，縱軸爲E/V ( Li/Li+ )、橫軸爲放電容 量（mAh/g (活性物質））。由圖4明顯可知，使用碳酸 酯系有機溶劑時雖能夠放電，但無法充電。 (比較例4) 除 了使用 lmol/L 的 LiPF6(EC: DEC = 1: lv〇l%)的 電解液作爲電解質以外，係用與比較例3相同的方法進行 鋰-硫蓄電池的製造與充放電測定。結果，得到了與比較 例3相同的結果。 因此，由以上的實施例及比較例可知，使用以醚系有 機溶劑而得的凝膠化電解質，且施加振動來製造的鋰-硫 蓄電池，電解質充分地浸透入正極內，且抑制了放電生成 物之多硫化鋰（Li2Sx: x = 2〜8)向電解質中溶出，因此能 夠將放電生成物持續保持於正極而抑制與負極之Li金屬 的反應，可得到高的充放電特性。 -19- 201225372 [實施例4] 分別使用 ，3-二氧 、四氫呋喃、2 -甲基四氫呋 喃 、！’4·二螺院、二乙酸、二乙氧基乙院、及 伸乙 甘醇二甲iH乍爲醚系有機溶劑，以取代實施例！中使用的 二甲氧基乙院’來製造凝膠化電解質，並遵照實施例 3記載的方法製造鋰-硫冑電池帛，可知能夠得到與圖2 及3所示結果相同的充放電曲線及放電容量。 [實施例5] 除了使用LizS以取代實施例3中使用的正極活性物 質之硫以外，遵照實施例3記載的方法製造鋰-硫蓄電池 後，可知能夠得到與圖2及3所示結果相同的充放電曲線 及放電容量。 [實施例6] 本實施例中’改變實施例1中使用之合成膨潤石的添 加量，遵照實施例1記載的方法，用以下（1)〜（7)的 摻合比例來製造電解質，並對於所得到之電解質，遵照實 施例2來施加超音波振動，且觀察其狀態。以下之合成膨 潤石添加量係爲相對於所得之電解質重量的比例。 (1) 合成膨潤石：50rng + DEC: 2g +電解液：567mg (合 成膨潤石添加量：1.91 wt% ) (2) 合成膨潤石：100mg + DEC: 2g +電解液：567mg (合 成膨潤石添加量：3.75wt% ) -20- 201225372 (3 )合成膨潤石：15〇mg + DEC : 2g +電解液：5 67mg (合 成膨潤石添加量：5.52wt%) (4)合成膨潤石：200mg + DEC: 2g +電解液：567mg (合 成膨潤石添加量：7.23wt% ) (5 )合成膨潤石：3 00mg + DEC : 2g +電解液：5 67mg (合 成膨潤石添加量：l〇.5wt% ) (6 )合成膨潤石：450mg + DEC : 2g +電解液·· 567mg (合 成膨潤石添加量：14.9wt% ) (7 )合成膨潤石：650mg + DEC : 2g +電解液：567mg (合 成膨潤石添加量：20.2wt%) 上述製造物〜（7)當中，（1)爲液體狀態，觀 察不到搖溶性，（2 )具有搖溶性，（3 )具有搖溶性，（ 4)雖較上述（3)更進一步凝膠化，但仍有搖溶性，（5 )係較上述（4)更進一步凝膠化，幾乎接近固體，觀察 不到搖溶性’（6 )係幾乎爲固體，觀察不到搖溶性，（7 )係幾乎爲固體，觀察不到搖溶性。 由上述（1)〜（7)的結果加以考量，由搖溶性的觀 點’膨潤性層狀黏土礦物的添加量較佳爲2wt%〜1〇wt%左 右的範圍。 [實施例7] 除了使用水輝石、皂土、蒙脫石以取代實施例丨中使 用合成膨潤石以外，遵照實施例3記載的方法來製造鋰_ 硫蓄電池後，W知能夠得到與圖2及3所示結果相同的充 -21 - 201225372 放電曲線及放電容量。 [產業上之可利用性] 依照本發明，不需要複雜的製造過程，即可提供維持 高的充放電循環特性且安全性提高的鋰-硫蓄電池，因此 能夠利用於使用鋰-硫蓄電池的各種產業。 【圖式簡單說明】 圖1爲用以說明使用本發明之活性物質-電解質複合 體之電極的狀態之槪略示意圖，（a )爲遵照本發明施加 振動來製造的情況> (b )爲用以比較而不施加振動來製 造的情況。 圖2爲顯示實施例3及比較例2中製造的鋰-硫蓄電 池各自的充放電曲線之曲線圖。 圖3爲顯示實施例3及比較例2中製造的鋰-硫蓄電 池於各自的重複循環特性中得到的放電容量曲線之曲線圖 〇 圖4爲顯示比較例3中製造的鋰-硫蓄電池之充放電 曲線之曲線圖。 【主要元件符號說明】 1 1 :活性物質 1 2 :黏結材 1 3 :導電輔助材 -22- 201225372 14 :集電體 1 5 :凝膠化電解質[Example IJ] A lipophilic synthetic bentonite (Co-op Chemical, product, manufactured by adding a swellable layered clay mineral to 2 g of 1,2-dimethoxyethane (DME) in an etheric organic solvent) Name: Lucentite STN) lOOmg, making it fully swellable. For the electrolytic solution, 3 mol/L of LiN(CF3S02)2 (DME: DOL = 9: lvol%) was used. To the above-mentioned sufficiently swollen bentonite-containing dimethoxyethane solution, 567 mg of an electrolytic solution was added to produce a gelated electrolyte. [Example 2] Ultrasonic vibration was applied to the gelled electrolyte produced in Example 1. During the application of the vibration, the gelled electrolyte was liquefied, the vibration was stopped, and it was confirmed by the subsequent placement that it gelled (solidified). [Example 3] Sulfur (S) (manufactured by Kishida Chemical Co., Ltd.) was used as a positive electrode active material, acetylene black (AB) was used as a conductive auxiliary material, and PVdF was used as a binder, and the weight ratio was 4 5 : 4 5 : 10 0 The obtained positive electrode material was coated on the A1 foil of the current collector to obtain a positive electrode. The gelled electrolyte prepared in Example 1 was coated on the surface of the positive electrode, and the gelled electrolyte was liquefied by applying ultrasonic vibration by applying -16-201225372 'soaked to the positive electrode as shown in Fig. 1 (a) Internally, an active material-electrolyte complex is produced. As a result, as shown in Fig. 1 (a), the surfaces of all the active materials were coated with an electrolyte. The thus-produced positive electrode composite was used as a positive electrode, and Li metal was used as a negative electrode, and a 2032 type lithium-sulfur battery was assembled and subjected to a charge and discharge test. In this case, the charge/discharge current 値 was set to 192.74 gA/cm 2 (corresponding to 0.1 C rate (charge and discharge rate)), the cutoff voltage was set to 1.5 to 2.8 V, and charge and discharge were repeated for 43 cycles. Further, since the monomer sulfur is used as the positive electrode, the measurement is started from the discharge reaction. (Comparative Example 1) A lithium-sulfur storage battery was assembled in accordance with the method described in Example 3 except that ultrasonic vibration was not applied, and a charge and discharge test was performed. In this case, the charge/discharge current 値 was set to 190 μM/(;1 ηη2 (corresponding to 0.1 C rate). The lithium-sulfur battery manufactured in Example 3 and Comparative Example 1 was examined for the discharge curve of the first cycle, and the comparative example was used. The discharge capacity of 1 is lower than the discharge capacity of Example 3. Therefore, by using the gelled electrolyte of the present invention and applying a vibration to produce a lithium-sulfur battery, the electrolyte is sufficiently saturated into the positive electrode as compared with no vibration. The manufactured lithium-sulfur battery was able to obtain a high energy density. (Comparative Example 2) 3 mol/L of LiN(CF3S02)2 (DME: DOL = 9: lvol%) was used as the electrolyte. In addition to the propylene film-17-201225372 (manufactured by Celgard Co., Ltd.; trade name: Celgard #2400), a lithium-sulfur battery was assembled in accordance with the method described in Example 3, and a charge and discharge test was performed. In this case, current charging and discharging were performed. When it was 1 8 9.75 pA/cm2 (corresponding to 〇.1C rate), charging and discharging were repeated for 45 cycles. Further, since monomeric sulfur was used as the positive electrode, measurement was started from the discharge reaction. Example 3 and Comparative Example Lithium-sulfur produced in 2 The discharge curve of the first cycle of each battery is shown in Fig. 2. In Fig. 2, the vertical axis is E/V (Li/Li+), and the horizontal axis is the discharge capacity (mAh/g (active material)). The initial discharge capacity of both was 1 〇〇〇 mAh/g, and it was found that a high discharge capacity was obtained. Further, discharges obtained by repeating cycle characteristics of the lithium-sulfur batteries manufactured in Example 3 and Comparative Example 2 were obtained. The capacity is shown in Fig. 3. In Fig. 3, the vertical axis represents the discharge capacity (mAh/g (active material)) and the horizontal axis represents the number of cycles. As is apparent from Fig. 3, after 20 cycles, the discharge capacity of the third embodiment becomes Compared with the discharge capacity of Comparative Example 2, it was found that the cycle characteristics were improved. (Comparative Example 3) Sulfur (S) (manufactured by Kishida Chemical Co., Ltd.) was used as a positive electrode active material, and acetylene black (AB) was used as a conductive auxiliary material. PVdF was used as the binder, and the positive electrode material obtained by mixing the weight ratio of 45··45:10 was applied onto the A1 foil of the current collector to obtain a positive electrode. The positive electrode thus produced was used and used. Lmol/L of LiCL04 (EC (ethyl carbonate): DEC (diethyl carbonate) = 1: lvol %) Electrolyte, a -18-201225372 porous polypropylene film (Celgard #2400) was used as a separator, and Li metal was used as a negative electrode, and a 2 0 3 2 type lithium-sulfur battery was assembled and subjected to a charge and discharge test. In the case, the charge/discharge current 値 is set to 3 55.08 μΑ/(:ηι2 (corresponding to 0.1 C rate ), the cutoff voltage is set to 1.4-3.0 V, and charging and discharging are repeated for 3 cycles. Further, since the monomer sulfur is used as the positive electrode, the measurement is started from the discharge reaction. The first cycle (1st), the second cycle (2nd), and the third cycle (3rd) of the charge-discharge curve of the lithium-sulfur battery manufactured in Comparative Example 3 are shown in Fig. 4. In Fig. 4, the vertical axis is E/V (Li/Li+), and the horizontal axis is the discharge capacity (mAh/g (active material)). As is apparent from Fig. 4, when a carbonate-based organic solvent is used, it can be discharged, but it cannot be charged. (Comparative Example 4) The production and charging and discharging of a lithium-sulfur battery were carried out in the same manner as in Comparative Example 3 except that an electrolyte solution of 1 mol/L of LiPF6 (EC: DEC = 1: lv〇l%) was used as the electrolyte. Determination. As a result, the same results as in Comparative Example 3 were obtained. Therefore, it is understood from the above examples and comparative examples that a lithium-sulfur battery produced by applying a vibrating electrolyte obtained from an ether-based organic solvent and vibrating is sufficiently impregnated into the positive electrode and suppresses discharge generation. Since the lithium polysulfide (Li2Sx: x = 2 to 8) is eluted into the electrolyte, the discharge product can be continuously held on the positive electrode to suppress the reaction with the Li metal of the negative electrode, and high charge and discharge characteristics can be obtained. -19-201225372 [Example 4] Separately, 3-dioxy, tetrahydrofuran, 2-methyltetrahydrofuran, '4· Erluoyuan, diacetic acid, diethoxy b-yard, and ethylene glycol diethyl iH乍 are ether-based organic solvents, in place of the examples! A lithium-sulfur battery was produced by the method described in Example 3, and it was found that the same charge and discharge curves as those shown in FIGS. 2 and 3 can be obtained. Discharge capacity. [Example 5] A lithium-sulfur battery was produced in accordance with the method described in Example 3, except that the sulfur of the positive electrode active material used in Example 3 was replaced by LizS, and it was found that the same results as those shown in Figs. 2 and 3 were obtained. Charge and discharge curve and discharge capacity. [Example 6] In the present Example, 'the amount of the synthetic bentonite used in Example 1 was changed, and the electrolyte was produced by the blending ratio of the following (1) to (7) according to the method described in Example 1 and For the obtained electrolyte, ultrasonic vibration was applied in accordance with Example 2, and the state thereof was observed. The following synthetic bentonite addition amount is a ratio with respect to the obtained electrolyte weight. (1) Synthetic bentonite: 50rng + DEC: 2g + electrolyte: 567mg (synthetic bentonite addition: 1.91 wt%) (2) Synthetic bentonite: 100mg + DEC: 2g + electrolyte: 567mg (synthetic bentonite added Amount: 3.75wt%) -20- 201225372 (3) Synthetic bentonite: 15〇mg + DEC : 2g + electrolyte: 5 67mg (synthetic bentonite addition amount: 5.52wt%) (4) Synthetic bentonite: 200mg + DEC: 2g + electrolyte: 567mg (synthetic bentonite addition: 7.23wt%) (5) synthetic bentonite: 300mg + DEC: 2g + electrolyte: 5 67mg (synthetic bentonite addition: l〇.5wt% (6) synthetic bentonite: 450mg + DEC: 2g + electrolyte · · 567mg (synthetic bentonite addition: 14.9wt%) (7) synthetic bentonite: 650mg + DEC: 2g + electrolyte: 567mg (synthetic swelling Stone addition amount: 20.2% by weight) Among the above-mentioned products (7), (1) is in a liquid state, no solubility is observed, (2) has a thixotropic property, (3) has a thixotropic property, and (4) is more than the above. (3) Further gelation, but still soluble, (5) is gelatinized further than the above (4), almost close to solid, and no thaw solubility '(6) system is observed. As a solid, thixotropic observed, (7) based almost solid, thixotropic observed. From the results of the above (1) to (7), the amount of the swellable layered clay mineral added by the viewpoint of the thixotropic property is preferably in the range of 2 wt% to 1 〇 wt%. [Example 7] A lithium-sulfur battery was produced in accordance with the method described in Example 3, except that hectorite, bentonite, and montmorillonite were used instead of synthetic bentonite in the Example, and it was found that FIG. 2 was obtained. And the results shown in 3 are the same as the charge - 21 - 201225372 discharge curve and discharge capacity. [Industrial Applicability] According to the present invention, it is possible to provide a lithium-sulfur storage battery which maintains high charge/discharge cycle characteristics and has improved safety without requiring a complicated manufacturing process, and thus can be utilized for various lithium-sulfur storage batteries. industry. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view for explaining a state in which an electrode of an active material-electrolyte composite of the present invention is used, (a) a case where vibration is applied in accordance with the present invention> (b) A case where it is manufactured by comparison without applying vibration. Fig. 2 is a graph showing the charge and discharge curves of the respective lithium-sulfur storage batteries produced in Example 3 and Comparative Example 2. 3 is a graph showing a discharge capacity curve obtained in the respective repetitive cycle characteristics of the lithium-sulfur storage batteries manufactured in Example 3 and Comparative Example 2, and FIG. 4 is a view showing the charge of the lithium-sulfur storage battery manufactured in Comparative Example 3. A graph of the discharge curve. [Explanation of main component symbols] 1 1 : Active material 1 2 : Adhesive material 1 3 : Conductive auxiliary material -22- 201225372 14 : Current collector 1 5 : Gelled electrolyte