201100329 六、發明說明： 【發明所屬之技術領域】 本發明係關於四氟化硼酸鹽之製造方法及其製造裝置 ，更詳細而言，係關於可適用於蓄電元件之電解液之四氟 化硼酸鹽之製造方法、含四氟化硼酸鹽之電解液、及具備 該電解液之蓄電元件。 〇 【先前技術】 作爲傳統的四氟化硼酸鹽之製造方法，例如作爲四氟 化硼酸鋰之製造方法，可舉例如使碳酸鋰作用於硼氟酸溶 液而得到四氟化硼酸鋰之方法。以此方法產生的鹽係以 LiBF4 · H20所表示之硼氟化鋰· 1 7K合物，藉由200〇C程 度的加熱以進行脫水係必要的。然而，因爲以200°C程度 加熱，會使四氟化硼酸鋰分解，所以導致該純度降低。而 且，亦殘留數千ppm的水分。因此，就反應的控制性、 © 及所得製品純度等上，該製造方法並非令人滿意者。 爲解決此問題，例如下述專利文獻1係揭示於含氟化 鋰之鋰二次電池電解液用非水性有機溶劑中，吹入三氟化 硼氣體，藉由使氟化鋰與三氟化硼反應，製造四氟化硼酸 鋰之方法。 然而，前述之製造方法時，因爲氟化鋰對於有機溶劑 之溶解度小，所以該有機溶劑成懸濁狀（糊狀）。因此， 於製造過程，將難以使含氟化鋰之有機溶劑循環，有難以 連續過程製造四氟化硼酸鹽之問題。 -5- 201100329 專利文獻 專利文獻1 :特開平1 1 - 1 5 783 0號公報 【發明內容】 發明之揭示 發明所欲解決之課題 本發明係有鑑於則述問題而實施者，該目的係提供藉 由連續過程’可筒產率且效率佳地製造四氟化硼酸鹽之製 造方法、含四氟化硼酸鹽之電解液、及具備該電解液之蓄 電元件。 課題之解決手段 本申請書發明者等爲解決前述傳統上的問題點，就四 氟化硼酸鹽之製造方法、含四氟化硼酸鹽之電解液、及具 備該電解液之蓄電元件進行檢討。該結果係發現藉由採用 下述組成可達成前述目的，而完成本發明。 亦即，有關本發明之四氟化硼酸鹽之製造方法係爲解 決前述課題，具有溶解三氟化硼氣體於有機溶劑之第1步 驟、及加入對前述三氟化硼爲等價或其以下之化學計量之 氣化物（MFn，Μ係金屬或NH4，1$η$3)於則述有機 溶劑，使產生四氟化硼酸鹽的溶液之第2步驟、及藉由使 前述四氟化硼酸鹽的溶液於前述第一步驟循環，取代前述 有機溶劑，使三氟化硼氣體溶解於四氟化硼酸鹽的溶液之 第3步驟爲特徵。 -6 - 201100329 氟化物大致上係對有機溶劑爲難溶性。因此，吸收三 氟化硼氣體之前，若先加入氟化物於有機溶劑時，將成爲 懸濁（糊狀）狀態。因此，吸收三氟化硼時，於裝置內部 因固體氟化物引起阻塞，對運轉造成障礙。然而，若係以 前述方法，首先於第1步驟，使有機溶劑吸收三氟化硼氣 體後，於第2步驟添加氟化物於有機溶劑。藉此，於有機 溶劑中合成如下述化學反應式所示之四氟化硼酸鹽。另外 〇 ，因爲氟化物的添加量係對三氟化硼爲等價或其以下，所 以全部的氟化物與三氟化硼反應。該結果係未殘留未反應 的氟化物，可得到非糊狀之四氟化硼酸鹽溶液。藉此可使 四氟化硼酸鹽的溶液循環於第1步驟，取有機溶劑，使三 氟化硼氣體溶解於四氟化硼酸鹽的溶液（第3步驟）。亦 即，爲前述方法時，將可使用以吸收塔爲首之各種裝置， 並且亦可連續運轉，可提升四氟化硼酸鹽之生產性。 Ο [化 1] nBF3+ MFn-> M(BF4)n (但是，式中Μ於n=l時，爲Li、Na、K、Rb、Cs、 NH4 或 Ag、n= 2 時，爲 Ca、Mg、Ba、Zn、Cu 或 Pb、n =3時，爲A1或Fe。） 前述有機溶劑係以非水性有機溶劑、或非水性離子 '液 體爲宜。藉此，不發生三氟化硼或四氟化硼酸鹽水解以及 201100329 副產生三氟化砸或四氟化硼酸鹽之水合物，可吸收三氟化 硼。另外，三氟化硼或四氟化硼酸鹽水解時，產生氧氟化 硼酸或氟酸及硼酸等之酸性物質、或對有機溶劑’產生氧 氟化硼酸鹽、硼酸鹽等之不溶解成分。使用含此等酸性物 質、不溶解成分之電解液於蓄電元件時，造成蓄電元件的 腐蝕或電氣特性惡化等之不良影響。因此，作爲有機溶劑 ，以使用水分濃度低者爲宜。就如此觀點，前述有機溶劑 之水分濃度係以lOOppmw以下爲宜’以lOppmw以下尤 佳，以lppmw以下更好。 前述第1步驟及第3步驟係可使用吸收塔進行。若爲 本發明之製造方法時，因爲於溶解三氟化硼氣體於有機溶 劑及四氟化硼酸鹽之溶液後加入氟化物，所以不成爲懸濁 (糊狀）狀態。因此，即使於第1步驟及第3步驟使用吸 收塔，仍防止該內部發生阻塞，可連續運轉。該結果係可 提升四氟化硼酸鹽之生產性。 關於本發明之電解液係爲解決前述課題，含藉由前述 記載之四氟化硼酸鹽之製造方法所得之四氟化硼酸鹽爲特 徵。 另外，關於本發明之蓄電元件係爲解決前述課題，具 備前述記載之電解液爲特徵。作爲本發明之蓄電元件，可 列舉鋰離子二次電池。 發明之功效 本發明係藉由如前述說明的手段，達到如下所述之功 -8- 201100329 效。 亦即，依據本發明，對於吸收塔預先溶解三氟化硼氣 體之有機溶劑，於反應槽添加對前述三氟化硼爲等價或其 以下之化學計量之氟化物，使二者進行反應，可得到未殘 留氟化物之四氟化硼酸鹽的溶液。再次供給所得之四氟化 硼酸鹽的溶液於吸收塔，使進行循環，對此四氟硼酸鹽， 溶解三氟化硼氣體後，於反應槽，使氟化物與三氟化硼反 〇 應。亦即，依據本發明，藉由使四氟化硼酸鹽的溶液循環 ，無未反應的氟化物或雜質，可以連續的製造過程製造高 純度的四氟化硼酸鹽。另外，無需用以除去氟化物之過濾 步驟，於經濟上優異。 用以實施發明之最佳型態 關於本發明之實施型態，參考圖1下進行說明如下。 圖1係槪略地表示關於本發明之實施型態之四氟化硼酸鹽 〇 之製造裝置之說明圖。但是，說明中省略不需要的部份， 並且爲谷易說明，有圖式擴大或縮小的部份。 如圖1表示，有關本實施型態的製造裝置係具備第1 吸收塔1及第2吸收塔5、及第1槽2、第2槽6、及第3 槽10、及泵3、7、11、及第1冷卻器4及第2冷卻器8 、及脫氣塔9、及空氣泵12、及凝結器13。 放入規定量的有機溶劑於前述第1槽2及第2槽6。 以栗3及7分別供給第1槽2及第2槽6之液體於第1吸 收塔1及第2吸收塔5，進行循環運轉。接著，於第2吸 -9- 201100329 收塔5之塔底部供給三氟化硼（BF3 )氣體。三氟化硼係 可使用100%者，亦可混合惰性氣體適當稀釋者。藉由混 合惰性氣體，可緩和第1吸收塔1及第2吸收塔5時之發 熱。另外，就氟化氫，並無特別限制，可列舉N2、Ar、 乾燥空氣、二氧化碳。稀釋時使用的惰性氣體中的水分係 於水解三氟化硼或四氟化硼酸鹽、及不副產生三氟化硼或 四氟化硼酸鹽之水合物下，以lOOppmw以下之低水分爲 宜，以1 0 p P m W以下尤佳，以1 p p m W以下更好。三氟化 硼氣體藉由與有機溶劑於第2吸收塔5內對流接觸，溶解 於有機溶劑中（第1步驟）。三氟化硼對有機溶劑之吸收 熱係藉由設置於循環線路之第1冷卻器4及第2冷卻器8 除去，維持於適當的運轉溫度。 接著，供給溶解三氟化硼氣體之有機溶劑於第2槽6 。於第2槽6中，供給與三氟化硼等價或其以下之化學計 量之氟化物。藉此，三氟化硼與氟化物發生反應，產生四 氟化硼酸鹽（第2步驟）。下述反應式係表示三氟化硼與 氟化鋰之反應。 [化2] BF3 + LiF^ LiBF4 第2槽6所產生的四氟化硼酸鹽的溶液係通過配管， 由泵7所送出，供給於第2吸收塔5之塔頂部。供給於塔 -10- 201100329 底部之三氟化硼於第2吸收塔內爲此四氟化硼酸鹽的溶液 所吸收（第3步驟）。接著，於第2槽6，藉由連續進行 與氟化物之反應，提高四氟化硼酸鹽至所需濃度。藉由如 此的循環運轉，達成所定濃度，取出自泵7之部份溶液爲 製品。取出製品的同時，開始自外部供給有機溶劑於第1 吸收塔1，並且將泵3的液體供給對象，自第1吸收塔1 轉換成第2吸收塔5，進行四氟化硼酸鹽溶液的連續生產 〇 。此時，亦可接著使部份吸收液循環於第1吸收塔1下， 同時供給吸收液於第2吸收塔5。 氟化物對第2槽6之供給量係爲避免對有機溶劑爲難 溶性之氟化物成糊狀存在，所以對溶解於有機溶劑之三氟 化硼，以等價或其以下之化學計量爲宜。藉此，可避免裝 置中因糊狀的氟化物阻塞。作爲使三氟化硼對氟化物的化 學計量上過剩之方法，雖可藉由連續供給化學計量上對氟 化物過剩的三氟化硼而可實現，但因爲過剩的三氟硼必須 〇 於某一項步驟排出系統外，導致原料的損失，所以不宜。 對於使預先吸收運轉上適當過剩量之三氟化硼的液體，藉 由化學計量上等價供給三氟化硼及氟化物之方法更好。 另外，第2步驟使用之溶解過剩三氟化硼之四氟化硼 酸鹽的溶液雖供給於第3步驟中之第2吸收塔之塔頂部， 但該一部份亦供給於脫氣塔9。另外，被送往脫氣塔9之 四氟化硼酸鹽的溶液係藉由空氣泵12所減壓，餾去三氟 化硼。藉此，調整三氟化硼與氟化物成化學計量上等價之 四氟化硼酸鹽的溶液，自第3槽10取出製品。雖可加入 -11 - 201100329 與過剩溶解的三氟化硼化學計量上等價之氟化物，調整四 氟化硼酸鹽的溶液，但就連續生產性的觀點’以減壓餾去 過剩的三氟化硼爲宜。另外，爲提升藉由減壓以除去三氟 化硼的效率，亦可於脫氣塔9具備加熱器加熱。 前述餾去三氟化硼係以空氣泵12供給於第2吸收塔 5之塔底部。另外，於第2吸收塔5，使有機溶劑及/或四 氟化硼酸鹽的溶液對流接觸，進行回收、再利用。原料使 用的三氟化硼中含有少量的氟化氫時，亦可將四氟化硼酸 鹽的溶液以空氣泵12進行減壓，餾去氟化氫後，以凝結 器13凝結氟化氫去除。凝結器13所凝結的液體（排出液 體，drain)，雖含有有機溶劑、氟化氫、三氟化硼，但 可直接施以廢液處理進行廢棄，亦可因應需要，將氟化氫 、三氟化硼或有機溶劑回收再利用。作爲回收方法，可使 用蒸餾、萃取等之通常方法。 如此地本發明藉由使四氟化硼酸鹽的溶液循環，可產 率佳地連續地製造高純度的四氟化硼酸鹽。 另外’本發明中就工業上生產效率的觀點，雖以使用 吸收塔爲宜，但並非排除使用表面吸收或起泡之方法。另 外，第1吸收塔1及第2吸收塔5亦可使用塡充塔、板式 塔 '濕壁塔等中任一種型態的塔型吸收裝置。另外，吸收 的形式係可對流、並流中任一種。 前述第1步驟及第3步驟中，有機溶劑或四氟化硼酸 鹽的溶液中之三氟化硼的濃度係以1 5重量％以下爲宜， 以1 0重量％以下尤佳，以5重量％以下更好。有機溶劑中 -12- 201100329 三氟化硼氣體的濃度高時，有機溶劑與三氟化硼發生反應 ，可能引起有機溶劑的著色或變性、或固化。另外，吸收 熱變大，將難以控制液溫。 於前述第1步驟及第3步驟，三氟化硼氣體及有機溶 劑或四氟化硼酸鹽的溶液之氣液接觸溫度係以-40-1 00 °C 爲宜，以0~60°C尤佳。氣液接觸溫度若未滿-40°C時，因 有機溶劑凝固，所以不能連續運轉。另一方面，氣液接觸 〇 溫度若超過i〇〇°c時，有機溶劑及四氟化硼酸鹽的溶液中 三氟化硼的蒸氣壓變得過高，吸收效率降低，發生有機溶 劑與三氟化硼的反應之不適合狀態。 前述有機溶劑係以非水性有機溶劑或非水性離子液體 中至少任一方爲宜。另外，作爲非水性有機溶劑，進而以 非水性非質子性有機溶劑尤佳。因爲係非質子性，無提供 氫離子的能力，所以依本發明之製造方法所得之四氟化硼 酸鹽的溶液，可直接適用於鋰離子二次電池等之蓄電元件 〇 之電解液。 作爲前述非水性有機溶劑，並無特別限定，可舉例如 碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸伸乙烯酯（ vinylene carbonate)、碳酸二甲酯、碳酸二乙酯、碳酸甲 基乙酯、醋酸甲酯、醋酸乙酯、7-丁內酯、乙腈、二甲 基甲醯胺、1，2-二甲氧基乙烷、甲醇、異丙醇等。此等有 機溶劑中，就連續生產的觀點，產生的四氟化硼酸鹽不易 析出，亦即，以四氟化硼酸鹽溶解性高之碳酸乙烯酯、碳 酸丙烯酯、碳酸二甲酯、碳酸二乙酯 '碳酸甲基乙酯、乙 -13- 201100329 腈、1,2-二甲氧基乙烷爲宜。另外，此等非水性有機溶劑 係可單獨一種，或混合二種以上使用。 另外，作爲非水性非質子性有機溶劑，可舉例如環狀 碳酸酯、鏈狀碳酸酯、羧酸酯、腈、醯胺或醚化合物等。 此等非水性非質子性有機溶劑係可單獨一種，或混合 二種以上使用。 另外，作爲前述非水性離子液體，並無特別限定，可 舉例如4級銨或4級錢等之氟化物錯鹽或氟化物鹽。其中 作爲4級銨陽離子，可舉例如四烷基銨陽離子、咪唑鑰陽 離子、吡唑鑰陽離子、耻啶鑰陽離子、三唑鎗陽離子、嗒 哄鐵陽離子、噻唑鎗陽離子、噁唑鑰陽離子、嘧啶鎗陽離 子、吡嗪鎗陽離子等。另外，作爲前述4級鱗陽離子，可 舉例如四烷基鱗陽離子等。此等非水性離子液體係可單獨 一種，或混合二種以上使用，亦可溶解於前述非水性有機 溶劑使用。 前述有機溶劑亦可混合一種或二種以上非水性有機溶 劑、非水性離子液體使用。 作爲前述第2步驟所添加之氟化物（MFn ’ Μ係金屬 或NH4，l$nS3)，並不局限於LiF，可列舉NaF、KF 、RbF、CsF、NH4F、AgF、CaF2、MgF2 ' BaF2 ' Z11F2、 CuF2、RbF2、AIF3、FeF3等。此等氟化物係可單獨一種， 或混合二種以上使用。 作爲氟化物及三氟化硼氣體之反應溫度’以-50 °C 〜2 00°c爲宜，以- l〇°C〜l〇〇°C尤佳，以〇〜50°C更好。若未 -14- 201100329 滿-5 0 °C時，有有機溶劑凝固或四氟化硼酸鹽析出的可能 性。另一方面，若超過200°C時，產生的四氟化硼酸鹽分 解。 關於所得之四氟化硼酸鹽溶液，藉由將此濃縮及/或 冷卻而析出四氟化硼酸鹽，亦可藉由與溶劑分離而取出四 氟化硼酸鹽。 關於所得之四氟化硼酸鹽溶液，可直接作爲蓄電元件 0 之電解液使用，亦可混合一種或二種以上非水性非質子性 有機溶劑、非水性離子液體使用。 另外，製造四氟化硼酸鹽時使用的含硼成份氣體，具 體上係三氟化硼氣體，以使吸收於吸收液，進行回收·再 利用爲宜。作爲前述吸收液，可舉例如含水、氟酸水溶液 、及Μ ( Μ鹽係含至少一種選自 Li、Na、K、Rb、Cs、 NH4、Ag、Mg、Ca、Ba、Fe及A1所成群之碳酸鹽、氫氧 化物、鹵化物）之溶液。更具體上，可列舉〇〜80重量％ 〇 的水或氟化氫水溶液、或溶解Μ鹽（M係含至少一種選 自 Li、Na、Κ、Rb、Cs、NH4、Ag、Mg、Ca、Ba、Fe 及 A1所成群之碳酸鹽、氫氧化物、鹵化物）之〇〜80重量％ 的水或氟化氫水溶液。藉由吸三氟化硼氣體於吸收液’可 以 M(BF4)n(式中，lSnS3)及 / 或 HaBFb(OH)c-mH20 (式中，OSaSl，0‘bS4，0ScS3，〇SmS8)回收。 藉此，即使使用過多量的BF3氣體’仍可抑制原料的損失 〇 另外，製造四氟化硼酸鹽時，自第2吸收塔5流出的 -15- 201100329 三氟化硼係如圖1表示，以串聯的第1吸收塔1回收三氟 化硼。第1吸收塔1所得之含有三氟化硼之有機溶劑係供 應於第2吸收塔5。第1吸收塔1未能完全吸收的三氟化 硼亦可以前述所示的吸收方法進行回收·再利用。藉此’ 即使使用過多量的三氟化硼氣體時，仍可使用全量，抑制 原料損失。 【實施方式】 實施例 以下係舉例詳細地說明此發明之適合的實施例。但是 ，此實施例及比較例所記載之材料或配合量等係除非特別 限定記載，目的並非局限本發明範圍於此等，僅止於說明 例而已。 (實施例1 ) 本實施例係使用圖1表示的裝置進行。分別加入3 L 之市售電池級之碳酸二乙酯（水分濃度爲9ppmw)於氟樹 脂製之第1槽2及第2槽6後，使用泵3及7，開始於各 吸收塔及槽之循環運轉。此時，泵3及泵7的流量皆爲 lL/min。另外，第1槽2及第2槽6係分別使用第1冷卻 器4及第2冷卻器8，成爲2 0 °C之恆溫。 接著，於第2吸收塔5之塔底部，以3.4 1 g/min開始 供給三氟化硼氣體。使有機溶劑吸收三氟化硼氣體2分鐘 後，以1.3 Og/min開始供給氟化鋰於第2槽6。自氟化鋰 -16- 201100329 開始供給60分鐘後，以51.7nU/min開始取出製品。取出 製品的同時，以50ml/min供給有機溶劑於第1吸收塔1 ’並且以泵3將液體供應對象自第丨吸收塔1轉換成第2 吸收塔5後連續運轉。 藉由連續運轉60分鐘，供給3,295.8g的溶液於脫氣 塔9’藉由以空氣泵12進行減壓，餾去前述溶液中溶解 過剩的三氟化硼氣體。餾去後，自第3槽10取出，得到 〇 3,35〇g之四氟化硼酸鋰的溶液。伴隨餾去的三氟化硼氣體 之碳酸二乙酯係藉由凝結器13除去。之後，合倂原料的 三氟化硼氣體再利用。另外，維持餾去的三氟化硼氣體與 原料的三氟化硼氣體的合計供給量爲3.41 g/min。 如此操作所得之四氟化硼酸鋰之碳酸二乙酯溶液係不 溶解成分爲lOppmw以下，游離酸爲lOppmw以下，水分 爲lOppmw以下。另外，將所得之四氟化硼酸鋰之碳酸二 乙酯溶液’於40 °C下，進一步減壓以餾去碳酸二乙酯， 〇 得到白色固體。XRD (X光繞射儀）分析白色固體的結果 ，確認爲四氟化硼酸鋰。 (實施例2) 本實施例係使用圖2表示的裝置進行。分別加入 500g之市售電池級之碳酸二乙酯（水分濃度爲9ppmw) 於氟樹脂製之第2槽6，以泵7供給、循環於第2吸收塔 5之塔頂部。第2槽6係使用冷卻器8 ’使成爲20°C之恆 溫。接著’以流量0.5 L/min供給三氟化硼氣體於第2吸 -17- 201100329 收塔5之塔底部16.7分鐘，導入22.6g (第1步驟）。 接著，緩緩供給8.0g之作爲氟化物之氟化鋰於第2 槽6。氟化鋰迅速地溶解於含有三氟化硼之有機溶劑，與 有機溶劑中之三氟化硼反應。藉此得到530.6g之四氟化 硼酸鋰的溶液（第2步驟）。 進而，加入500g之碳酸二乙酯於第2槽6，進行與 前述相同的操作（第3步驟）。取出所得之四氟化硼酸鋰 的溶液中275g於第3槽10，使成爲20°C之恆溫，加入 0.3 3 5g與溶解過剩之三氟化硼化學計量等價的氟化鋰。 如此所得之四氟化硼酸鋰之碳酸二乙酯溶液係不溶解 成分爲lOppmw以下，游離酸爲lOppmw以下，水分爲 lOppmw以下。另外，將所得之四氟化硼酸鋰之碳酸二乙 酯溶液，於40 °C下，以空氣泵12進行減壓以餾去碳酸二 乙酯，得到白色固體。XRD分析白色固體的結果，確認 爲四氟化硼酸鋰。 (實施例3 ) 本實施例係使用圖2表示的裝置進行。分別加入市售 電池級之25 0g之碳酸二乙酯（水分濃度爲9ppmw)及 250g之碳酸乙嫌醋（水分濃度爲7ppmw)於氟樹脂製之 第2槽6，以泵7供給、循環於第2吸收塔5之塔頂部。 第2槽6係使用冷卻器8，使成爲2 0°C之恆溫。接著，以 流量0.5 L/min供給三氟化硼氣體於第2吸收塔5之塔底 部25.5分鐘，導入34.6g (第1步驟）。 -18- 201100329 接著，緩緩供給13,0g之作爲氟化物之氟化鋰於第2 槽6。氟化鋰迅速地溶解於含有三氟化硼之有機溶劑，與 有機溶劑中之三氟化硼反應。藉此得到457.6g之四氟化 硼酸鋰的溶液（第2步驟）。 進而，加入250g之碳酸二乙酯及25 0g之碳酸乙烯酯 於第2槽6，進行與前述相同的操作（第3步驟）。取出 所得之四氟化硼酸鋰的溶液中275g於第3槽10，使成爲 20°C之恆溫，藉由以空氣泵12進行減壓，餾去溶解過剩 的三氟化硼氣體。如此所得之四氟化硼酸鋰之碳酸二乙酯 /碳酸乙酯溶液係不溶解成分爲lOppmw以下，游離酸爲 lOppmw以下，水分爲lOppmw以下。 接著，使用如此所得之溶液，製作如圖3表示之鈕扣 型非水電解液鋰二次電池，藉由充放電試驗，評估作爲電 解液之性能。具體上以下述步驟進行。 Q 〈製作負極22〉 以9:1之重量比混合天然石墨及黏著劑之聚偏二氟 乙烯（PVdF )，加入N-甲基吡咯啶酮於其中，得到糊狀 物。將此糊狀物以電極塗布用塗布機（applicator )均勻 地塗布於22 之銅箔上。將此以120 °C真空乾燥8小時 ，以電極穿孔機得到直徑16mm之負極22。 <製作正極2 1 > 以90 : 5 : 5之重量比混合LiC〇02及助導電劑之乙炔 -19- 201100329 黑及黏著劑之PVdF，加入N-甲基吡咯啶酮於此混合物， 得到糊狀物。將此糊狀物以電極塗布用塗布機（ applicator)均勻地塗布於22/zm之銅范上。將此以120 °C真空乾燥8小時，以電極穿孔機得到直徑1 6mm之正極 21。 <製作鈕扣型非水電解液鋰二次電池> 放置正極21於正極罐24的底面，於其上方放置聚丙 烯製之多孔性分離器23後，注入實施例2調製之非水性 電解液，插入墊圈26。之後，於分離器23的上方，依序 放置負極22、隔離板27、彈簧28及負極罐25，使用鈕 扣型電池嵌合機，藉由將正極罐24之開口部向內側彎曲 以封閉，製作非水電解液鋰二次電池。接著，以0.4mA 之一定電流進行充電，電壓到達4.1 V時，4 · 1 V，1小時 定電壓充電。放電係以1.0mA之定電流進行，放電直至 電壓成3.0V。電壓若到達3.0V時，保持3.0V，1小時， 藉由充放電循環，實施充放電試驗。該結果係充放電效率 約100%，重複充放電150次循環時，充電容量未變化。 (實施例4)201100329 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a tetrafluoroborate and a device for manufacturing the same, and more particularly to a boron tetrafluoride acid which is applicable to an electrolyte of a storage element A method for producing a salt, an electrolyte containing tetrafluoroborate, and a storage element including the electrolyte. [Prior Art] As a method for producing a conventional tetrafluoroborate, for example, a method of producing lithium tetrafluoroborate by subjecting lithium carbonate to a borofluoric acid solution to obtain lithium tetrafluoroborate is exemplified. The salt produced by this method is a lithium borofluoride 17K compound represented by LiBF4 · H20, and is required to be dehydrated by heating at a temperature of 200 °C. However, since heating at 200 ° C decomposes lithium tetrafluoroborate, the purity is lowered. Moreover, thousands of ppm of water remain. Therefore, the manufacturing method is not satisfactory in terms of controllability of the reaction, © and the purity of the obtained product. In order to solve this problem, for example, Patent Document 1 listed below discloses that boron trifluoride gas is blown into a non-aqueous organic solvent for a lithium secondary battery electrolyte containing lithium fluoride, and lithium fluoride and trifluoride are used. A method of producing boron tetrafluoride borate by boron reaction. However, in the above production method, since the solubility of lithium fluoride in the organic solvent is small, the organic solvent is suspended (paste). Therefore, in the manufacturing process, it is difficult to circulate the organic solvent containing lithium fluoride, and there is a problem that it is difficult to produce a tetrafluoroborate in a continuous process. -5-201100329 Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. A method for producing a tetrafluoroborate, a solution containing a tetrafluoroborate, and a storage element including the electrolyte can be produced by a continuous process. Solution to Problem In order to solve the above-mentioned conventional problems, the inventors of the present application reviewed the method for producing a tetrafluoroborate, an electrolyte containing tetrafluoroborate, and a storage element having the electrolyte. As a result, it has been found that the present invention can be attained by the use of the following composition. That is, the method for producing a tetrafluoroborate of the present invention solves the above-mentioned problems, and has a first step of dissolving a boron trifluoride gas in an organic solvent, and adding or substituting the boron trifluoride for the above or below. a stoichiometric gasification (MFn, lanthanide metal or NH4, 1$η$3) in the organic solvent, a second step of producing a solution of the tetrafluoroborate, and by subjecting the tetrafluoroborate The solution is circulated in the first step described above, and is substituted for the third step of dissolving the boron trifluoride gas in the tetrafluoroborate solution in place of the organic solvent. -6 - 201100329 Fluoride is generally poorly soluble in organic solvents. Therefore, before the boron trifluoride gas is absorbed, if the fluoride is first added to the organic solvent, it will be in a suspended (paste) state. Therefore, when boron trifluoride is absorbed, clogging due to solid fluoride inside the apparatus causes an obstacle to operation. However, in the first step, after the boron trifluoride gas is absorbed in the organic solvent in the first step, the fluoride is added to the organic solvent in the second step. Thereby, a tetrafluoroborate represented by the following chemical reaction formula is synthesized in an organic solvent. Further, since the amount of fluoride added is equivalent to or lower than boron trifluoride, all of the fluoride is reacted with boron trifluoride. As a result, no unreacted fluoride remained, and a non-paste tetrafluoroborate solution was obtained. Thereby, the solution of the tetrafluoroborate can be circulated in the first step, and an organic solvent is taken to dissolve the boron trifluoride gas in the solution of the tetrafluoroborate (step 3). That is, in the case of the above method, various devices including an absorption tower can be used, and continuous operation can be performed to improve the productivity of the tetrafluoroborate. Ο [Chemical 1] nBF3+ MFn-> M(BF4)n (However, when Μ is n=l, when Li, Na, K, Rb, Cs, NH4 or Ag, n= 2, it is Ca, When Mg, Ba, Zn, Cu or Pb, and n = 3, it is A1 or Fe.) The organic solvent is preferably a non-aqueous organic solvent or a non-aqueous ion liquid. Thereby, boron trifluoride or tetrafluoroborate is not hydrolyzed and a hydrate of cesium trifluoride or tetrafluoroborate is produced in 201100329, and boron trifluoride can be absorbed. Further, when boron trifluoride or tetrafluoroborate is hydrolyzed, an acidic substance such as oxyfluorinated boric acid or hydrofluoric acid or boric acid or an insoluble component such as an oxyfluorinated borate or a borate is generated in the organic solvent. When an electrolyte containing such an acidic substance or an insoluble component is used in a storage element, adverse effects such as corrosion of the storage element or deterioration of electrical characteristics are caused. Therefore, as the organic solvent, it is preferred to use a water having a low water concentration. In view of the above, the water concentration of the organic solvent is preferably 100 ppm or less, more preferably 10 ppm or less, more preferably 1 ppmw or less. The first step and the third step described above can be carried out using an absorption tower. In the case of the production method of the present invention, since the boron trifluoride gas is dissolved in the solution of the organic solvent and the tetrafluoroborate, the fluoride is not added, so that it does not become a suspended (paste) state. Therefore, even if the absorption tower is used in the first step and the third step, the internal clogging is prevented and the operation can be continued. This result enhances the productivity of tetrafluoroborate. The electrolyte solution of the present invention is characterized in that the tetrafluoroborate obtained by the method for producing a tetrafluoroborate described above is characterized in order to solve the above problems. Further, the electric storage device of the present invention is characterized in that the above-described problem is solved, and the electrolytic solution described above is characterized. A lithium ion secondary battery can be cited as the electric storage device of the present invention. EFFECTS OF THE INVENTION The present invention achieves the following effects by means of the means as described above. That is, according to the present invention, the organic solvent in which the boron trifluoride gas is previously dissolved in the absorption tower is added to the reaction tank to add a stoichiometric amount of fluoride to the boron trifluoride or the like, and the two are reacted. A solution of tetrafluoride borate having no residual fluoride can be obtained. The obtained solution of the tetrafluoroborate is again supplied to the absorption tower for circulation, and after the boron tetrafluoride gas is dissolved in the tetrafluoroborate, the fluoride is reacted with boron trifluoride in the reaction vessel. That is, according to the present invention, a high purity tetrafluoroborate can be produced in a continuous manufacturing process by circulating a solution of tetrafluoroborate without unreacted fluoride or impurities. In addition, there is no need for a filtration step for removing fluoride, which is economically excellent. BEST MODE FOR CARRYING OUT THE INVENTION The embodiment of the present invention will be described below with reference to Fig. 1. Fig. 1 is an explanatory view schematically showing a manufacturing apparatus of a tetrafluoroborate hydride according to an embodiment of the present invention. However, the unnecessary portions are omitted in the description, and for the description of the valley, there is a portion in which the schema is enlarged or reduced. As shown in Fig. 1, the manufacturing apparatus of the present embodiment includes a first absorption tower 1 and a second absorption tower 5, and a first tank 2, a second tank 6, a third tank 10, and pumps 3 and 7, 11. The first cooler 4 and the second cooler 8 and the deaeration tower 9, the air pump 12, and the condenser 13. A predetermined amount of an organic solvent is placed in the first tank 2 and the second tank 6. The liquids supplied to the first tank 2 and the second tank 6 by the pumps 3 and 7 are respectively supplied to the first absorption tower 1 and the second absorption tower 5 to perform a circulation operation. Next, boron trifluoride (BF3) gas was supplied to the bottom of the second suction tower -9-201100329. Boron trifluoride can be used in 100% or in an inert gas mixture. By mixing the inert gas, the heat generation of the first absorption tower 1 and the second absorption tower 5 can be alleviated. Further, the hydrogen fluoride is not particularly limited, and examples thereof include N2, Ar, dry air, and carbon dioxide. The water in the inert gas used for dilution is based on hydrolyzed boron trifluoride or tetrafluoroborate, and the hydrate which does not produce boron trifluoride or tetrafluoroborate, and preferably has a low moisture of less than 100 ppmw. It is preferably 1 0 p P m W or less, more preferably 1 ppm W or less. The boron trifluoride gas is convectively contacted with the organic solvent in the second absorption tower 5, and is dissolved in the organic solvent (first step). The absorption of boron trifluoride in the organic solvent is removed by the first cooler 4 and the second cooler 8 provided in the circulation line, and is maintained at an appropriate operating temperature. Next, an organic solvent in which boron trifluoride gas is dissolved is supplied to the second tank 6. In the second tank 6, a fluoride which is equivalent to or less than a chemical amount of boron trifluoride is supplied. Thereby, boron trifluoride reacts with the fluoride to produce a tetrafluoroborate (second step). The following reaction formula represents the reaction of boron trifluoride with lithium fluoride. BF3 + LiF^ LiBF4 The solution of the tetrafluoroborate produced in the second tank 6 is sent out by the pump 7 through a pipe and supplied to the top of the tower of the second absorption tower 5. Supply to the tower -10- 201100329 The bottom boron trifluoride is absorbed in the second absorption tower for this tetrafluoroborate solution (step 3). Next, in the second tank 6, by continuously reacting with the fluoride, the tetrafluoroborate is raised to the desired concentration. By the cyclic operation as described above, a predetermined concentration is obtained, and a part of the solution from the pump 7 is taken out as a product. At the same time as the product is taken out, the organic solvent is supplied to the first absorption tower 1 from the outside, and the liquid supply target of the pump 3 is converted from the first absorption tower 1 to the second absorption tower 5 to carry out the continuous operation of the tetrafluoroborate solution. Production 〇. At this time, a part of the absorption liquid may be circulated to the first absorption tower 1 while the absorption liquid is supplied to the second absorption tower 5. The amount of the fluoride to be supplied to the second tank 6 is such that the fluoride which is insoluble in the organic solvent is present in a paste form. Therefore, it is preferable to use a stoichiometric amount of boron trifluoride dissolved in the organic solvent in an equivalent or less. Thereby, the clogging of the paste due to the paste can be avoided in the device. As a method of making the stoichiometric excess of boron trifluoride to fluoride, it can be realized by continuously supplying a boron trifluoride which is stoichiometrically excessive in fluoride, but since the excess trifluoroboron must be smashed A step out of the system, resulting in the loss of raw materials, is not appropriate. It is more preferable to supply the boron trifluoride and the fluoride in a stoichiometrically equivalent manner to a liquid which is preliminarily absorbed in an appropriate excess amount of boron trifluoride. Further, the solution of the tetrafluoroborate in which the excess boron trifluoride is dissolved in the second step is supplied to the top of the second absorption tower in the third step, but the portion is also supplied to the deaeration column 9. Further, the solution of the tetrafluoroborate sent to the degassing column 9 is depressurized by the air pump 12 to distill off boron trifluoride. Thereby, a solution of boron trifluoride which is stoichiometrically equivalent to fluoride is adjusted, and the product is taken out from the third tank 10. Although the stoichiometrically equivalent fluoride with excess dissolved boron trifluoride can be added to adjust the solution of tetrafluoroborate, -11 - 201100329, but in terms of continuous productivity, the excess trifluoroethylene is distilled off under reduced pressure. Boron is preferred. Further, in order to increase the efficiency of removing boron trifluoride by pressure reduction, the degassing column 9 may be provided with heater heating. The boron trifluoride exhausted is supplied to the bottom of the tower of the second absorption tower 5 by the air pump 12. Further, in the second absorption tower 5, the solution of the organic solvent and/or the tetrafluoroborate is convectively contacted, and recovered and reused. When a small amount of hydrogen fluoride is contained in the boron trifluoride used for the raw material, the solution of the boron tetrafluoride acid salt may be depressurized by the air pump 12, and the hydrogen fluoride may be distilled off, and then the hydrogen fluoride is condensed by the condenser 13 to be removed. The liquid (drain) condensed by the condenser 13 contains an organic solvent, hydrogen fluoride, or boron trifluoride, but may be directly disposed of by waste liquid treatment, or may be hydrogen fluoride or boron trifluoride if necessary. The organic solvent is recycled and reused. As the recovery method, a usual method such as distillation or extraction can be used. Thus, the present invention can continuously produce a high-purity tetrafluoroborate by circulating a solution of a tetrafluoroborate. Further, in the present invention, from the viewpoint of industrial production efficiency, it is preferable to use an absorption tower, but a method of using surface absorption or foaming is not excluded. Further, as the first absorption tower 1 and the second absorption tower 5, a tower type absorption apparatus of any one of a turbulent tower, a plate tower, a wetted tower, or the like may be used. In addition, the form of absorption can be either convection or cocurrent. In the first step and the third step, the concentration of boron trifluoride in the solution of the organic solvent or the tetrafluoroborate is preferably 15% by weight or less, more preferably 10% by weight or less, and preferably 5 parts by weight. % below is better. In organic solvent -12- 201100329 When the concentration of boron trifluoride gas is high, the organic solvent reacts with boron trifluoride, which may cause coloring, denaturation or solidification of the organic solvent. In addition, the absorption heat becomes large, and it is difficult to control the liquid temperature. In the first step and the third step, the gas-liquid contact temperature of the boron trifluoride gas and the organic solvent or the tetrafluoroborate solution is preferably -40 to 00 ° C, and is 0 to 60 ° C. good. If the gas-liquid contact temperature is less than -40 °C, the organic solvent will not work continuously due to solidification. On the other hand, if the temperature of the gas-liquid contact enthalpy exceeds i〇〇°c, the vapor pressure of boron trifluoride in the solution of the organic solvent and the tetrafluoroborate is too high, the absorption efficiency is lowered, and the organic solvent and the organic solvent are generated. The unsuitable state of the reaction of boron fluoride. The organic solvent is preferably at least one of a non-aqueous organic solvent or a non-aqueous ionic liquid. Further, as the non-aqueous organic solvent, a non-aqueous aprotic organic solvent is further preferable. Since it is not protonic and has no ability to supply hydrogen ions, the solution of the tetrafluoroborate obtained by the production method of the present invention can be directly applied to an electrolyte of a storage element such as a lithium ion secondary battery. The non-aqueous organic solvent is not particularly limited, and examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl carbonate. Ethyl ester, methyl acetate, ethyl acetate, 7-butyrolactone, acetonitrile, dimethylformamide, 1,2-dimethoxyethane, methanol, isopropanol and the like. Among these organic solvents, the tetrafluoroborate produced is not easily precipitated from the viewpoint of continuous production, that is, ethylene carbonate, propylene carbonate, dimethyl carbonate, and carbonic acid having high solubility in tetrafluoroborate. Ethyl ester 'methyl ethyl carbonate, B-13-201100329 nitrile, 1,2-dimethoxyethane is preferred. Further, these non-aqueous organic solvents may be used alone or in combination of two or more. Further, examples of the non-aqueous aprotic organic solvent include a cyclic carbonate, a chain carbonate, a carboxylate, a nitrile, a guanamine or an ether compound. These non-aqueous aprotic organic solvents may be used alone or in combination of two or more. Further, the nonaqueous ionic liquid is not particularly limited, and examples thereof include a fluoride salt or a fluoride salt such as a 4- toluene or a 4-grade. Among them, as the fourth-order ammonium cation, for example, a tetraalkylammonium cation, an imidazolium cation, a pyrazole cation, a azoidine cation, a triazole gun cation, a ruthenium iron cation, a thiazole gun cation, an oxazole cation, a pyrimidine Gun cation, pyrazine gun cation, etc. Further, as the above-mentioned class 4 scale cation, for example, a tetraalkylsecanide or the like can be exemplified. These non-aqueous ionic liquid systems may be used singly or in combination of two or more kinds, or may be dissolved in the aforementioned non-aqueous organic solvent. The above organic solvent may also be used in combination with one or more kinds of non-aqueous organic solvents and non-aqueous ionic liquids. The fluoride (MFn 'lanthanide metal or NH4, l$nS3) added as the second step is not limited to LiF, and examples thereof include NaF, KF, RbF, CsF, NH4F, AgF, CaF2, and MgF2 'BaF2'. Z11F2, CuF2, RbF2, AIF3, FeF3, and the like. These fluorides may be used alone or in combination of two or more. The reaction temperature of the fluoride and the boron trifluoride gas is preferably -50 ° C to 2 00 ° C, more preferably - l 〇 ° C ~ l 〇〇 ° C, more preferably 〇 50 ° C. If -14- 201100329 is at -5 0 °C, there is a possibility of solidification of organic solvent or precipitation of tetrafluoroborate. On the other hand, when it exceeds 200 ° C, the produced tetrafluoroborate is decomposed. With respect to the obtained tetrafluoroborate solution, the tetrafluoroborate is precipitated by concentration and/or cooling, and the tetrafluoroborate can be taken out by separation from the solvent. The obtained tetrafluoroborate solution can be used as the electrolyte of the storage element 0, or can be used by mixing one or more kinds of non-aqueous aprotic organic solvents and non-aqueous ionic liquids. Further, the boron-containing component gas used in the production of the tetrafluoroborate is, in particular, a boron trifluoride gas so as to be absorbed in the absorption liquid and recovered and reused. Examples of the absorption liquid include water, an aqueous solution of hydrofluoric acid, and hydrazine (the strontium salt contains at least one selected from the group consisting of Li, Na, K, Rb, Cs, NH4, Ag, Mg, Ca, Ba, Fe, and A1). A solution of a group of carbonates, hydroxides, halides. More specifically, water or hydrogen fluoride aqueous solution or dissolved cerium salt (M system containing at least one selected from the group consisting of Li, Na, lanthanum, Rb, Cs, NH4, Ag, Mg, Ca, Ba, etc.) may be mentioned.碳酸~80% by weight of water or aqueous hydrogen fluoride solution of a group of carbonates, hydroxides, and halides of Fe and A1. By absorbing boron trifluoride gas in the absorption liquid 'M(BF4)n (wherein, lSnS3) and/or HaBFb(OH)c-mH20 (wherein, OSaSl, 0'bS4, 0ScS3, 〇SmS8) . Thereby, even if an excessive amount of BF3 gas is used, the loss of the raw material can be suppressed. In addition, when the tetrafluoroborate is produced, -15-201100329 boron trifluoride flowing out from the second absorption tower 5 is as shown in FIG. Boron trifluoride is recovered in the first absorption tower 1 in series. The organic solvent containing boron trifluoride obtained in the first absorption tower 1 is supplied to the second absorption tower 5. Boron trifluoride which has not been completely absorbed by the first absorption tower 1 can be recovered and reused by the absorption method described above. By this, even when an excessive amount of boron trifluoride gas is used, the total amount can be used to suppress the loss of the raw material. [Embodiment] Embodiments Hereinafter, suitable embodiments of the invention will be described in detail by way of examples. However, the materials, blending amounts, and the like described in the examples and the comparative examples are not intended to limit the scope of the invention, and the description is not intended to limit the scope of the invention. (Embodiment 1) This embodiment is carried out using the apparatus shown in Fig. 1. 3 L of commercially available battery grade diethyl carbonate (water concentration: 9 ppmw) was added to the first tank 2 and the second tank 6 made of fluororesin, and then pumps 3 and 7 were used to start the respective absorption towers and tanks. Cycle operation. At this time, the flow rates of the pump 3 and the pump 7 are both lL/min. Further, in the first tank 2 and the second tank 6, the first cooler 4 and the second cooler 8 are used, respectively, and the temperature is kept constant at 20 °C. Next, boron trifluoride gas was supplied at the bottom of the tower of the second absorption tower 5 at 3.4 1 g/min. After the boron trifluoride gas was absorbed by the organic solvent for 2 minutes, lithium fluoride was supplied to the second tank 6 at 1.3 Og/min. After the supply of lithium fluoride-16-201100329 for 60 minutes, the product was taken out at 51.7 nU/min. While the product was taken out, the organic solvent was supplied to the first absorption tower 1' at 50 ml/min, and the liquid supply object was continuously converted by the pump 3 from the second absorption tower 1 to the second absorption tower 5. By continuously running for 60 minutes, 3,295.8 g of the solution was supplied to the degassing column 9' by pressure reduction by the air pump 12, and the excess boron trifluoride gas dissolved in the solution was distilled off. After distilling off, it was taken out from the third tank 10 to obtain a solution of 3,35 〇g of lithium tetrafluoroborate. The diethyl carbonate which is accompanied by the distilled boron trifluoride gas is removed by the condenser 13. Thereafter, the boron trifluoride gas of the combined raw materials is reused. Further, the total supply amount of the boron trifluoride gas to be distilled and the boron trifluoride gas of the raw material was maintained at 3.41 g/min. The diethyl carbonate solution of lithium tetrafluoroborate obtained in this manner has an insoluble content of 10 ppmw or less, a free acid of 10 ppmw or less, and a water content of 10 ppmw or less. Further, the obtained diethyl carbonate solution of lithium tetrafluoroborate was further reduced in pressure at 40 ° C to distill off diethyl carbonate, and a white solid was obtained. The result of analysis of a white solid by XRD (X-ray diffractometer) was confirmed to be lithium tetrafluoroborate. (Embodiment 2) This embodiment is carried out using the apparatus shown in Fig. 2. 500 g of commercially available battery grade diethyl carbonate (water concentration: 9 ppmw) was added to the second tank 6 made of fluororesin, and supplied by the pump 7 and circulated to the top of the tower of the second absorption tower 5. The second tank 6 was cooled to a constant temperature of 20 °C using a cooler 8'. Subsequently, boron trifluoride gas was supplied at a flow rate of 0.5 L/min for 16.7 minutes at the bottom of the second absorption tower -17-201100329, and introduced into 22.6 g (first step). Next, 8.0 g of lithium fluoride as a fluoride was gradually supplied to the second tank 6. The lithium fluoride is rapidly dissolved in an organic solvent containing boron trifluoride and reacted with boron trifluoride in an organic solvent. Thus, 530.6 g of a solution of lithium tetrafluoroborate was obtained (second step). Further, 500 g of diethyl carbonate was added to the second tank 6, and the same operation as described above was carried out (third step). 275 g of the obtained lithium tetrafluoroborate solution was taken out in the third tank 10 to maintain a constant temperature of 20 ° C, and 0.335 g of lithium fluoride equivalent to the dissolved excess boron trifluoride stoichiometric amount was added. The diethyl carbonate solution of lithium tetrafluoroborate thus obtained has an insoluble content of 10 ppmw or less, a free acid of 10 ppmw or less, and a water content of 10 ppmw or less. Further, the obtained diethyl carbonate solution of lithium tetrafluoroborate was depressurized by an air pump 12 at 40 ° C to distill off diethyl carbonate to obtain a white solid. The result of XRD analysis of a white solid was confirmed to be lithium boron fluoride. (Embodiment 3) This embodiment is carried out using the apparatus shown in Fig. 2. A commercially available battery grade of 25 g of diethyl carbonate (water concentration of 9 ppmw) and 250 g of ethyl carbonate vinegar (water concentration of 7 ppmw) were added to the second tank 6 made of fluororesin, and supplied and circulated by the pump 7. The top of the tower of the second absorption tower 5. In the second tank 6, the cooler 8 is used, and the temperature is kept constant at 20 °C. Then, boron trifluoride gas was supplied to the bottom of the second absorption tower 5 at a flow rate of 0.5 L/min for 25.5 minutes, and 34.6 g was introduced (first step). -18- 201100329 Next, 13,0 g of lithium fluoride as a fluoride was gradually supplied to the second tank 6. The lithium fluoride is rapidly dissolved in an organic solvent containing boron trifluoride and reacted with boron trifluoride in an organic solvent. Thus, 457.6 g of a solution of lithium tetrafluoroborate was obtained (second step). Further, 250 g of diethyl carbonate and 25 g of ethylene carbonate were placed in the second tank 6, and the same operation as described above was carried out (third step). 275 g of the obtained solution of lithium tetrafluoroborate was taken out in the third tank 10 to maintain a constant temperature of 20 ° C, and the pressure was reduced by the air pump 12 to distill off the excess boron trifluoride gas. The diethyl carbonate/ethyl carbonate solution of lithium tetrafluoroborate thus obtained has an insoluble content of 10 ppmw or less, a free acid of 10 ppmw or less, and a water content of 10 ppmw or less. Next, using the solution thus obtained, a button-type nonaqueous electrolyte lithium secondary battery as shown in Fig. 3 was produced, and the performance as an electrolyte was evaluated by a charge and discharge test. Specifically, the following steps are performed. Q <Preparation of the negative electrode 22> A natural graphite and an adhesive of polyvinylidene fluoride (PVdF) were mixed at a weight ratio of 9:1, and N-methylpyrrolidone was added thereto to obtain a paste. This paste was uniformly applied onto a copper foil of 22 by an applicator for electrode coating. This was dried under vacuum at 120 ° C for 8 hours, and a negative electrode 22 having a diameter of 16 mm was obtained by an electrode punch. <Production of the positive electrode 2 1 > In a weight ratio of 90:5:5, a mixture of LiC〇02 and a conductive agent acetylene-19-201100329 black and an adhesive PVdF was added, and N-methylpyrrolidone was added to the mixture. Get a paste. This paste was uniformly applied to a 22/zm copper vane by an applicator for electrode coating. This was dried under vacuum at 120 °C for 8 hours, and a positive electrode 21 having a diameter of 16 mm was obtained by an electrode punch. <Production of button-type nonaqueous electrolyte lithium secondary battery> The positive electrode 21 was placed on the bottom surface of the positive electrode can 24, and a porous separator 23 made of polypropylene was placed thereon, and then the nonaqueous electrolyte prepared in Example 2 was injected. Insert the washer 26. Then, the negative electrode 22, the separator 27, the spring 28, and the negative electrode can 25 are placed in the upper portion of the separator 23, and the opening portion of the positive electrode can 24 is bent inward by a button-type battery fitting machine to be closed. Nonaqueous electrolyte lithium secondary battery. Next, charging was performed at a constant current of 0.4 mA, and when the voltage reached 4.1 V, 4 · 1 V was charged for 1 hour. The discharge was conducted at a constant current of 1.0 mA and discharged until the voltage was 3.0V. When the voltage reached 3.0 V, it was kept at 3.0 V for 1 hour, and a charge and discharge test was performed by a charge and discharge cycle. As a result, the charge and discharge efficiency was about 100%, and when the charge and discharge were repeated for 150 cycles, the charge capacity did not change. (Example 4)
本實施例係使用圖2表示的裝置進行。分別加入 5〇〇g之市售脫水甲醇（水分濃度爲9ppmw)於氟樹脂製 之第2槽6，以泵7導入於第2吸收塔5之塔頂部，使前 述有機溶劑循環。第2槽6係使用冷卻器8，使成爲20 °C -20- 201100329 之恆溫。接著，以流量0.5 L/rnin供給三氟化硼氣體於第2 吸收塔5之塔底部25.5分鐘，導入34.6g (第1步驟）。 接著，緩緩供給1 3 · 0g之氟化鋰於第2槽6。氟化鋰 迅速地溶解於含有三氟化硼之有機溶劑，與有機溶劑中之 三氟化硼反應。藉此得到457.6g之四氟化硼酸鋰的溶液 (第2步驟）。 進而，加入500g之甲醇於第2槽6，進行與前述相 〇 同的操作（第3步驟）。取出所得之四氟化硼酸鋰的溶液 中275g於第3槽10，使成爲20°C之恆溫，以空氣泵12 進行減壓，餾去溶解過剩的三氟化硼。 如此所得之四氟化硼酸鋰之甲醇溶液係不溶解成分爲 lOppmw以下，游離酸爲i〇ppmw以下，水分爲lOppraw 以下。 接著，將所得之四氟化硼酸鋰之甲醇溶液，使成爲 60°C之恆溫，以5L/min的氮起泡，使部份甲醇蒸發，析 〇 出白色固體。過濾此溶液，將所得之白色固體，於60 °C ’ 5L/min的氮清除下，餾去甲醇。以XRD分析所得之白 色固體的結果，確認爲四氟化硼酸鋰。 (實施例5) 本實施例係使用圖2表示的裝置進行。分別加入 5 00g之混入水的市售電池級之碳酸二乙酯（水分濃度爲 5 5 Oppmw)於氟樹脂製之第2槽6，以泵7供給、循環於 第2吸收塔5之塔頂部。第2槽6係使用冷卻器8，使成 -21 - 201100329 爲20°C之恆溫。接著，以流量〇.5L/min供給三氟化硼氣 體於第2吸收塔5之塔底部17分鐘，導入22.6g (第1步 驟）。 接著，緩緩供給8.0g之作爲氟化物之氟化鋰於第2 槽6。氟化鋰迅速地溶解於含有三氟化硼之有機溶劑，與 有機溶劑中之三氟化硼反應。藉此得到5 3 0.6g之四氟化 硼酸鋰的溶液（第2步驟）。 進而，加入500g之碳酸二乙酯於第2槽6，進行與 前述相同的操作（第3步驟）。取出所得之四氟化硼酸鋰 的溶液中275 g於第3槽10，使成爲20°C之恆溫，藉由減 壓以餾去溶解過剩的三氟化硼。如此所得之四氟化硼酸鋰 之碳酸二乙酯溶液係不溶解成分爲3 Oppmw以下，游離酸 爲130ppmw以下，水分爲400ppmw以下，使用此溶液， 製作與實施例3相同的鈕扣型非水電解液鋰二次電池，藉 由充放電試驗，評估作爲電解液之性能。該結果係充放電 之初期效率誘發水分的電解。重複充放電150次循環時， 可抑制充電容量降低成20%程度。另外，發現150次循環 後之鈕扣槽略爲膨脹。 (比較例1 ) 本比較例係使用圖1表示的裝置進行。分別加入3 L 之市售電池級之碳酸二乙酯（水分濃度爲9ppmw)於氟樹 脂製之第1槽2及第2槽6後，使用泵3及7，開始於各 吸收塔及槽之循環運轉。此時，泵3及泵7的流量皆爲 -22- 201100329 lL/min。另外，第1槽2及第2槽6係分別使用冷卻器4 及8，使成爲20°C之恆溫。 接著，於第.2吸收塔5之塔底部，以3.41 g/min開始 供給三氟化硼氣體。使有機溶劑吸收三氟化硼氣體2分鐘 後，以1 .55g/min開始供給氟化鋰於第2槽6。自氟化鋰 開始供給60分鐘後，第2吸收塔5因成爲糊狀之氟化鋰 阻塞，運轉變得困難。 〇 【圖式簡單說明】 [圖1 ]槪略地表示關於本發明之實施型態、實施例1 及比較例1之四氟化硼酸鹽之製造裝置之說明圖。 [圖2]用以說明本發明實施例2~5之槪略圖。 [圖3]槪略地表示本發明之鋰二次電池之剖面圖之說 明圖。 €) 【主要元件符號說明】 1 :第1吸收塔 2 :第1槽 3、7、1 1 :泵 4 :第1冷卻器 5 :第2吸收塔 6 :第2槽 8 :第2冷卻器 9 :脫氣塔 -23- 201100329 10 :第3槽 1 2 :空氣泵 1 3 :凝結器 2 1 :正極 22 :負極 2 3 :多孔性分離器 24 :正極罐 25 :負極罐 26 :墊圈 2 7 :隔離板 2 8 :彈簧 -24This embodiment is carried out using the apparatus shown in Fig. 2. 5 〇〇g of commercially available dehydrated methanol (water concentration: 9 ppmw) was added to the second tank 6 made of fluororesin, and the pump 7 was introduced into the top of the second absorption tower 5 to circulate the organic solvent. The second tank 6 is a cooler 8 which is kept at a constant temperature of 20 ° C -20 - 201100329. Next, boron trifluoride gas was supplied to the bottom of the second absorption tower 5 at a flow rate of 0.5 L/rnin for 25.5 minutes, and introduced into 34.6 g (first step). Next, 1 3 · 0 g of lithium fluoride was gradually supplied to the second tank 6. Lithium fluoride is rapidly dissolved in an organic solvent containing boron trifluoride and reacted with boron trifluoride in an organic solvent. Thus, 457.6 g of a solution of lithium tetrafluoroborate was obtained (second step). Further, 500 g of methanol was added to the second tank 6, and the same operation as described above was carried out (third step). 275 g of the obtained solution of lithium tetrafluoroborate was taken out in the third tank 10, and the temperature was kept at a constant temperature of 20 ° C, and the pressure was reduced by an air pump 12 to distill off excess boron trifluoride. The methanol solution of lithium tetrafluoroborate thus obtained has an insoluble content of 10 ppmw or less, a free acid of i 〇 ppmw or less, and a water content of 10 Å or less. Next, the obtained methanol solution of lithium tetrafluoroborate was brought to a constant temperature of 60 ° C, and 5 L/min of nitrogen was bubbled to partially evaporate methanol to precipitate a white solid. This solution was filtered, and the obtained white solid was evaporated under nitrogen at <RTIgt;</RTI> The result of the white solid obtained by XRD analysis was confirmed to be lithium boron fluoride. (Embodiment 5) This embodiment is carried out using the apparatus shown in Fig. 2. 500 g of commercially available battery grade diethyl carbonate (water concentration of 5 5 Oppmw) was added to the second tank 6 made of fluororesin, and supplied by the pump 7 and circulated to the top of the tower of the second absorption tower 5 . In the second tank 6, the cooler 8 is used, and the temperature is 20 ° C at -21 - 201100329. Next, boron trifluoride gas was supplied to the bottom of the second absorption tower 5 at a flow rate of 55 L/min for 17 minutes, and 22.6 g was introduced (the first step). Next, 8.0 g of lithium fluoride as a fluoride was gradually supplied to the second tank 6. The lithium fluoride is rapidly dissolved in an organic solvent containing boron trifluoride and reacted with boron trifluoride in an organic solvent. Thus, a solution of 5 3 0.6 g of lithium tetrafluoroborate was obtained (second step). Further, 500 g of diethyl carbonate was added to the second tank 6, and the same operation as described above was carried out (third step). 275 g of the obtained lithium tetrafluoroborate solution was taken out in the third tank 10 to maintain a constant temperature of 20 ° C, and the excess boron trifluoride was distilled off by depressurization. The diethyl carbonate solution of lithium tetrafluoroborate thus obtained has an insoluble content of 3 Oppmw or less, a free acid of 130 ppmw or less, and a water content of 400 ppmw or less. Using this solution, the same button type nonaqueous electrolysis as in Example 3 was produced. The liquid lithium secondary battery was evaluated for its performance as an electrolytic solution by a charge and discharge test. This result is that the initial efficiency of charge and discharge induces electrolysis of moisture. When the charge and discharge were repeated for 150 cycles, the charge capacity was reduced to 20%. In addition, it was found that the button groove after 150 cycles was slightly expanded. (Comparative Example 1) This comparative example was carried out using the apparatus shown in Fig. 1 . 3 L of commercially available battery grade diethyl carbonate (water concentration: 9 ppmw) was added to the first tank 2 and the second tank 6 made of fluororesin, and then pumps 3 and 7 were used to start the respective absorption towers and tanks. Cycle operation. At this time, the flow rates of the pump 3 and the pump 7 are both -22-201100329 lL/min. Further, the first tank 2 and the second tank 6 are cooled at 20 ° C by using the coolers 4 and 8, respectively. Next, boron trifluoride gas was supplied at the bottom of the column of the second absorption tower 5 at 3.41 g/min. After the boron trifluoride gas was absorbed by the organic solvent for 2 minutes, lithium fluoride was supplied to the second tank 6 at 1.55 g/min. After the lithium fluoride was supplied for 60 minutes, the second absorption tower 5 was clogged with the paste-like lithium fluoride, and the operation became difficult. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A schematic view of a manufacturing apparatus of a tetrafluoroborate of the embodiment of the present invention, and the first embodiment and the comparative example 1 is schematically shown. Fig. 2 is a schematic view for explaining Embodiments 2 to 5 of the present invention. Fig. 3 is a schematic view showing a cross-sectional view of a lithium secondary battery of the present invention. €) [Description of main components] 1 : 1st absorption tower 2 : 1st tank 3, 7, 1 1 : Pump 4 : 1st cooler 5: 2nd absorption tower 6: 2nd tank 8: 2nd cooler 9 : Degassing tower -23- 201100329 10 : 3rd tank 1 2 : Air pump 1 3 : Condenser 2 1 : Positive electrode 22 : Negative electrode 2 3 : Porous separator 24 : Positive electrode tank 25 : Negative electrode tank 26 : Washer 2 7: Isolation plate 2 8 : Spring-24