201247937 四、指定代表圖： (一） 本案指定代表圖為：第（1)圖。 (二） 本代表圖之元件符號簡單說明： 卜電解槽； 3〜陰極； 5〜熔融鹽； 7〜導電體； 2〜二氧化矽板； 4〜二氧化矽； 6〜陽極； 8〜參考電極。 五、本案若有化學式時，請揭示最能麻發鴨徵的化 ^ 六、發明說明： 【發明所屬之技術領域】 本發明係關於矽材之製 如太陽電池的光電動勢電力 化合物的原料等的有用矽材 化方法。更詳言之，係關於例 元件、鋰電池的負極材料、矽 之製造方法。 【先前技術】 能依廉價製造具高純度石夕的石夕材之製造方法，有提 例域用第9圖所示電解裝置，在其電解槽i中所裝入 ，融鹽5中’浸潰著陰極3與陽極6(其係插入由二氧化 4構成多孔質成形體的孔中)的狀態下，使二氧化石“在 …中進行電解還原的石夕材之製造方法(例如參照專 文獻1的[巾請專利範圍1]、第1圖等h㈣材之製造 201247937 法係具有能依廉價製造具高純度矽的優點。 J曰 ® -疋’上述;5夕材之製造方法，為能持續進行二氧化矽 的電解還原’便必需在二氧化矽4的電解還原後，從電 解槽1中取屮, 極3本體，並將該陰極3更換為新的陰極， 而頗難利用使二氧化矽4連續進行電解還原而製造石夕 材0 所以，期待開發出在二氧化矽的電解還原後不需要從 電解槽中取出陰極，可藉由使二氧化石夕連續進行電解還原 而製造矽材的矽材之製造方法。 [先行技術文獻] [專利文獻] [專利文獻1]曰本專利特開2006_321 688號公報 【發明内容】 (發明所欲解決之課題） .本發明係有鑑於上述習知技術而完成，課題在於提 -在t化石夕進行電解還原I，不冑要將陰極從電解槽 中取出，可利用使二氧化石夕造綠、隹β 乳化矽運續進仃電解還原而製造矽材 的矽材之製造方法。 (解決課題之手段） 本發明係關於： (1) 一種矽材之製造方法，俜 W'社浴融鹽存在下，藉由使 二氧化碎進行電解還原而製造石夕材的 的方法，其特徵在於： 在由矽所構成的陰極上載置著-畜 者一乳化矽之狀態下，使該二 201247937 氧化矽進行電解還原； ⑺如上述⑴所記載的石夕材之製造方法， 陰極上載置著二氧化矽的方式， 、邊依在 , . 冬一氧化矽供應給陰極 上，一邊使該二氧化矽進行電解還原丨以及 法，其中 (3)如上述（1)或（2)所記載的矽材之製造方 二氧化矽係使用二氧化矽的多孔質體。 (發明效果） 可達在二氧化矽進行 中取出’藉由使二氧 的優異效果。 根據本發明的矽材之製造方法， 電解還原後，不需要將陰極從電解槽 化石夕連續進行電解還原便能製造矽材 【實施方式】 本發明的石夕材之製造方法孫知μ >+. 們心衣&刀沄係如上述，在熔融鹽存在 下，藉由使二氧化矽進行電解還原而製造矽材的方法，其 特徵在於：在由矽所構成的陰極上載置著二氧化矽之狀態 下’使該二氧化矽進行電解還原。 根據專利文獻1所記載的矽材之製造方法，具有能依 廉價製造具高純度矽的優異優點。但是，本發明者等為 開發出能較上述矽材之製造方法更有效率使二氧化矽進$ 電解還原的矽材之製造方法，而經深入鑽研，結果發現： 並非如專利文獻1所記載，在矽電極棒插入於多孔質二氧 化石夕粉末成形體中所設置孔内的的狀態下，使二氧化石夕在 熔融鹽t進行電解還原，而是當使二氧化矽載置於由矽所 構成陰極上的狀態下，使該二氧化矽進行電解還原時，即 201247937201247937 IV. Designated representative map: (1) The representative representative of the case is: (1). (b) The symbol of the symbol of this representative diagram is briefly described: Bu cell; 3~ cathode; 5~ molten salt; 7~ conductor; 2~ cerium oxide plate; 4~ cerium oxide; 6~ anode; electrode. 5. If there is a chemical formula in this case, please disclose the chemical system of the most capable duck hair. 6. Description of the invention: [Technical field of the invention] The present invention relates to a raw material for a photovoltaic material such as a photovoltaic cell of a solar cell. Useful coffin method. More specifically, it relates to an example element, a negative electrode material of a lithium battery, and a method of manufacturing ruthenium. [Prior Art] It is possible to manufacture a high-purity Shixi material by cheaply, and there is an example of an electrolysis apparatus shown in Fig. 9, which is charged in the electrolytic cell i, and is melted in the salt 5 In the state in which the cathode 3 and the anode 6 (which are inserted into the pores of the porous molded body formed by the oxidation of 4), the method for producing the stone in which the silica is "electrolyzed" is used (for example, The manufacturing method of the [1] material of the document 1 of the document 1 of the document 1 and the structure of the h (4) material of the 1st figure is the advantage of being able to manufacture high-purity yttrium at a low cost. J曰® -疋' The above; It is necessary to continue the electrolytic reduction of cerium oxide, and it is necessary to take the ruthenium from the electrolytic cell 1 after the electrolytic reduction of cerium oxide 4, and replace the cathode 3 with a new cathode, which is difficult to use. Since the cerium oxide 4 is continuously subjected to electrolytic reduction to produce the stone material 0, it is expected to develop a cathode which does not need to be taken out from the electrolytic cell after electrolytic reduction of the cerium oxide, and can be produced by continuously performing electrolytic reduction of the oxidized silica. The manufacturing method of coffin coffin. [First technical text [Patent Document] [Patent Document 1] JP-A-2006-321 688 (Summary of the Invention) The present invention has been made in view of the above-described conventional techniques, and the object is to provide In the case of electrolytic reduction I, it is possible to remove the cathode from the electrolytic cell, and it is possible to produce a coffin which is produced by the electrolysis of the cerium dioxide, the cerium oxide, and the cerium. (Means for Solving the Problem) The present invention relates to: (1) A method for producing a coffin, which is a method for producing a stone material by electrolytic reduction of cerium dioxide in the presence of a bath salt of 俜W' The second 201247937 cerium oxide is subjected to electrolytic reduction in a state in which the sputum emulsifier is placed on the cathode formed of ruthenium. (7) The method for producing the shovel material according to the above (1), the cathode is placed. The method of ruthenium dioxide is applied to the cathode, and the ruthenium oxide is supplied to the cathode, and the ruthenium dioxide is subjected to electrolytic reduction, and (3) as described in the above (1) or (2). Manufacture of coffins The ruthenium-based system uses a porous body of ruthenium dioxide. (Effect of the invention) It is possible to take out the cerium dioxide during the process of taking out 'the excellent effect of dioxane. According to the method for producing a bismuth material according to the present invention, after electrolytic reduction, It is necessary to continuously produce electrolytic material by electrolytic reduction of the cathode from the electrolytic cell fossil. [Embodiment] The method for producing the stone material of the present invention is Sun Zhi μ >+. The heart coating & the knife is as described above, in the melting A method for producing a coffin by electrolytic reduction of cerium oxide in the presence of a salt, characterized in that the cerium oxide is electrolytically reduced in a state in which cerium oxide is placed on a cathode composed of cerium. According to the method for producing a coffin described in Patent Document 1, there is an excellent advantage that a high-purity ruthenium can be produced at low cost. However, the inventors of the present invention have developed a method for producing a coffin which is more efficient in reducing the amount of ceria into electrolytic reduction than the above-described method for producing a coffin, and as a result of intensive studies, it has been found that it is not described in Patent Document 1. In the state in which the ruthenium electrode rod is inserted into the pores provided in the porous TiO2 powder molded body, the silica is subjected to electrolytic reduction in the molten salt t, but when the cerium oxide is placed on the cerium When the cerium oxide is electrolytically reduced in a state in which the ruthenium is formed on the cathode, that is, 201247937
便在一氧化矽進行電解還原後，未採行將陰極從電解 取出並更換為新的陰極之煩雜操作，只要連續供應S 夕利用該一氧化砂的電解還原，便可連續製造 發明便根據此種發現而完成。 本發明_材之製造方法中，原料係使用二氧化石夕。 I氧切係可例如：石英、二氧切砂 '非晶形二氧化石夕 二：惟本發明並不僅侷限於該等例示。該等二氧化矽之中， 就從還原速度較高的觀點，較佳係非晶形二氧化石夕。非曰 形二氧化石夕係可例如在石夕藻土等之中所含的非晶形二^ ^等。一般石夕藻土係依80〜90質量％的含有率含有非晶形二 :化矽，除此之外，尚包括有例如氧化鋁等黏土成分。矽 '、土中所含的非晶形二氧化碎，係與諸如石英等之中所含 的f $化石夕不同’因$具有容易溶解於驗水溶液中 、性質，因而在使非晶形二氧化矽溶解於鹼水溶液中之 =，藉由重複進行進行控制該水溶液的心使非晶形二氧 匕石夕析出的操作，便可調製得具有99 _質量％以上的高 ，’度非晶形二氧化石夕。 二氧化石夕的純度係就從利用使二氧化石夕進行電解還原 ^造具有高純度石夕材的觀點，純度越高越佳。二氧化石夕 雜質含有率係就從利用使二氧化石夕進行電解還原而製 Γ/、有高純度石夕材的觀點，較佳係、_卿以下、更佳係 咖以下、特佳係1卿以下、最佳係G.5卿以下。另 ，一氧化石夕中的雜質係可舉例如：鈉m銘、 n㈣m «，惟本發明並不僅侷限於該 201247937 等例示。 乳化矽通蒂係使 ， 一咿粒子 粒控下限值隸效率佳進行：氧切之祕_的觀點， 較佳係0.2" m以上、更佳係〇 5…上；而二氧化石夕粒 子的粒徑上限值係與上述下限值同樣的，就從效率佳進行 二氧化石夕之電解還原㈣點，較㈣' 以下。二氧化石夕 粒子係例如可從太平洋水泥（股）製的精製Si〇2粒子等商業 性地輕易取得。 〃 電解還原所使用的二氧化矽較佳係使用多孔質體。多 孔質體係可例如：成形為所需形狀的成形體由粒子彼此 間相凝聚或鍵結的粒狀物等。 二氧化梦的成形體形狀係可例如：圓柱、立方體、長 方體、平板、薄膜、球等，惟本發明並不僅侷限於該等例 不。二氧化矽的成形體大小並無特別的限定，就從效率佳 進行二氧化石夕之電解還原的觀點，較佳係直徑5〜30mm左 右、且厚度U 0mm左右的圓柱形狀成形體、或一邊長度為 5〜30mm左右的立方體狀或長方體狀成形體等。 二氧化矽的成形體係例如利用諸如壓縮成形等便可輕 易地製造。當二氧化矽的成形體係利用壓縮成形進行製造 時’可獲得在成形體内部存在有與表面相連通空隙的多孔 質成形體。因為該多孔質成形體係可使熔融鹽含潤至其内 4 ’因而具有可效率佳進行二氧化矽的電解還原之優點。 所以’本發明中，二氧化矽較佳係使用二氧化矽的多孔質 成形體。 201247937 二氧化#多孔質成形體係例如將二氧切粒子與適 量水進行混合’再將所獲得混合物填充於具有所需内面形 狀的成形模内，藉由施行加壓便可進行製造。另外 + _ 氧化矽的多孔質成形體係利用壓縮成形進行製造時，2從 提高所獲得多孔質成形體的機械強度觀點， 孔質成形體施行燒結。在將二氧切的多孔質成 燒結時，於使上述多孔質成形體乾燥後，便在大氣環境中 或氮氣 '氬氣等惰性氣體環境中，藉由加熱至ι〇〇〇〜ΐ5〇〇 °c左右的溫度，便可製造經燒結的多孔質成形體。 二氧化料多孔質成形體之空隙率係就從藉由使溶融 鹽渗入於其内部俾提高二氧化石夕電解還原效率的觀點，較 佳係繼以上、更佳係權以上、特佳係50%以上，就從提 南該多孔質成形體自體的機械強度，且提高利用二氧化石夕 的電解還原而生成之石々Μ &地 成之夕材的機械強度觀點，較佳係8〇%以 下、更佳係70%以下、特佳係65%以下。 二氧化矽的粒狀物粒徑係就從因熔 =粒狀物飛散，適切載置於陰極上，且降低在經還原生 1粒狀物間所發生的電氣式接觸電阻之合計值，俾提 二:氧切之電解還原效率的觀點，較佳係5〇“以上' Π:::以上、特佳係2〇0…上、最佳〜 要時門之顴^電解還原直到二氧化矽的粒狀物内部所需 較佳係3G則下、更佳係—下、特 佳係3mm以下。拌未匕 ^ 繞射式粒度分佈福Γ 石夕的粒狀物粒徑係利用雷射 儀[日機裝（股）製、商品名：Microtrac 201247937 MT33 00 1 1、溶劑：水、分散劑：無1 、 W M」進仃測定時的值。因為 在構成粒狀物的粒子間存在有空隙，m 因而二氧化矽的粒狀 物便與二氧化矽的多孔質成形體同樣 像’可使熔融鹽含潤至 其内部’因而具有可使二氧化石夕的雷 /幻電解還原能效率佳進行 的優點。所以，本發財’二氧切最好使用二氧化石夕的 粒狀物。 二氧化石夕的粒狀物係例如將二氧化石夕粒子與適量水進 行混合，再將所獲得混合物填充於具有所需内面形狀的成 形模内，施行加壓’再視需要施行粉碎便可進行製造。另 外，上述所獲得粒狀物係就從提高機械強度的觀點，較佳 係施行燒結。在上述粒狀物進行燒結時，在使上述粒狀物 乾燥後’於大氣環境中、或氮氣、氬氣等惰性氣體環境中， 加熱至1 000〜150(TC左右的溫度，藉此便可製造經燒結的 粒狀物。上述粒狀物係可在燒結後再施行粉碎的粒狀物。 又’上述粒狀物亦可利用過篩而整合粒徑。 本發明得-大特徵在於：在使二氧化石夕載置於由石夕所 構成陰極上的狀態下，於熔融鹽存在下，使二氧化矽進行 電解還原。因為本發明係採取上述操作，因而藉由使二氧 化石夕連續進行電解還原便可製造矽材，故可效率佳的製造 碎材。 本發明中，陰極係使用由矽構成的陰極。本說明書中， 上述由矽構成的陰極係指至少表面為由矽形成的陰極。所 以’上述由石夕構成的陰極係可僅由矽材構成，或者亦可為 在諸如鉬等金屬基材的表面上被覆著矽的複合體。另外， 201247937 在陰極的表面上，視需要亦可附著二氧化石夕粉末。 當陰極所使用的石夕中含有雜質的情況，當二氧化石夕進 行電解還原時，會有該雜質混入於依二氧化石夕電解還原所 =石”之可能性。所以’陰極所使用石夕材的純度，就 從提向獲得矽材純度的觀點，較佳係99 9質量％以上、更 佳係99.99質量％以上、特佳係99 999質量％以上、最佳係 99.9999質量％以上。 _載置二氧化矽的陰極之大小，係只要能在該陰極上載 〃氧化夕便可，其餘並無特別的限定。例如當二氧化石夕 係使用1個或複數個二氧化石夕成形體的情況，便選擇可使 該成形體均能載置於陰極上的大小。所以，陰極的大小最 好配合陰極上所載置二氧化石夕的大小與個數，再適當決 定。又’相關陰極的形狀亦無特別的限定，陰極的形狀係 可例如：平面形狀呈圓形或橢圓形的圓盤狀、平面形狀呈 三角形、四角形、其他多角形的板狀等，惟本發明並不僅 侷限於該等例示。 載置二氧化石夕的陰極表面係就從效率佳進行二氧化石夕 電解還原的觀點，較佳係具有與二氧化石夕間之接觸面積較 大的形狀。例如當二氧化石夕係使用具有平面狀底面的二氧 化石夕成形料，載置二氧切的陰極表面較佳係平面狀。 又，亦可在載置二氧化石夕的陰極上面形成凹凸形狀，並使 該凹木凸形狀所對應的形狀形成於二氧切的心體底面 上。當依此在陰極上面與二氧化石夕的成形體底面上設置相 互對應凹凸形狀的情況，不僅可效率佳地進行二氧化石夕之 201247937 電解還原'，且可使二氧化石夕的成形體固定於陰極的既定么 置，並具有可防止二氧化矽成形體從陰極上滑落的優點。 陰極係例如連接於導電體，再經由該導電體連接於電源。 熔融鹽所使用的鹽係可舉例如：鹼金屬“物、鹼土 族金屬函化物等金屬函化物，惟本發明並不僅偈限於該等 例示。該等金屬函化物分別可單獨使用、亦可併用2種以 上。驗金屬齒化物中，驗金屬係可例如··經 ' 納、钟、絶 等。鹼土族金屬齒化物中，鹼土族金屬係可例如：鎂、鈣、 锶、鋇等。又，構成齒化物的鹵原子係可例如：氟原子、 氣原子、漠原子、碟原子等。金屬豳化物的具體例係可舉 例如：mm氯化卸、氯化料驗金屬_化物； 氣化鎮、氣化弼、氣化链、氣化鎖等驗土族㈣心㈣ 等，惟本發明並不僅褐限於該等例示。該等金屬齒化物分 別可单獨使用、亦可併用2種以上。金屬齒化物之中，就 從氧化物離子的溶解度較高之觀點，較佳係氣化鐘、氯化 鈉、氣化鎂及氣化鈣，更佳係氯化鈣。 使二氧化石夕進行電解還原時的炼融鹽溫度，係就從提 尚·^化石夕的還原效率觀點，較佳係5〇〇。〇以上、更佳係 800 C以上，雖依照炫融鹽的種類有所不同，但就從抑制溶 融鹽揮發的觀點，通常較佳係 〇 υυ L以下、更佳係900t 以下。 ，極係可例如：碳電極、石墨電極、玻璃碳電極、肥 粒鐵系不錢陽極、硼化 卞时如 〜合庄險極#，惟本發明並 不僅侷限於該等例示。該等 寺陽極之中，就從迴避雜質混入 10 201247937 的觀點，較佳係肥粒鐵系不 極等不溶性陽極。 溶性陽極、 硼化鈦系不溶性陽 使二氧化石夕進行電解還原時的陰極電位，較佳係設定 成較源自熔融鹽的陽離子從熔融物中析出的電位更高的電 位。陰極電位係依照熔融鹽的種類而有所差異，並無法一 概性決定，通常就從避免源自炼融鹽的陽離子被還原而生 成的金屬與石夕發生相鍵結的觀點，較佳係Ο ν[對㈣ 係表示依熔融鹽之陰極極限所析出的驗金屬或驗土族金 屬；η係表示鹼金屬或鹼土族金屬的價數)]以上、更佳係 0.6Π對心⑶與„係同上述）]以上，就從提高電解還原 效率的觀點，特佳係u[對rvM(M#r^同上述）]以下。 本發明的石夕材之製造方法係例如：將電解槽内形成惰 性氣體環境之後，於陰極上載置二氧切，再將溶融鹽裝 入於該電解槽内，#由施行電解還原，便可製造碎材。此 時’當依在陰極上載置著二氧切的方式，—邊將二氧化 石夕供應給陰極上，一邊使該二氧化石夕進行電解還原時，便 可連續製造矽材，因而可大量且效率佳地製造矽材。 本發明的矽材之製造方法係例如使用如第丨圖所示電 解還原裝置便可實施。第1圖所示係本發明矽材之製造方 法所使用電解還原裝置的一實施態樣概略說明圖。 第1圖中，在電解槽1的内面底部配置二氧化石夕板2, 並於該二氧化矽板2上配置由矽構成的陰極3。電解槽i 係從避免所生成的矽中有雜質混入之觀點，較佳係利用例 如石英等形成。二氧化矽板2係屬於從提升矽材生產性的 11 201247937 觀點較佳使用的材質，但本發明即便未使用二氧化矽板2 仍可易地製造矽材。電解槽1的内部空間較佳係利用例 如氮氣、氬氣等惰性氣體進行取代。 在陰極3上載置二氧化矽4。本發明的一大特徵係如 上述，在陰極3上載置著二氧化矽4的狀態下，使二氧化 矽4進行電解還原。本發明因為採取該項操作因而即便 未如订如習知般的在電解還原後便將陰極更換為新陰極的 、'雜操作，仍可使二氧化石夕連續地電解還原因而可效率 佳地製造矽材。 第1圖所不二氧化矽4係具有顆粒形狀，惟本發明並 不因二氧切4的形狀而有所限定。另外，二氧化石夕4係 就從效率錢製切材之觀點，最好織可能增加與陰極 3間之接觸面積的方式，使接觸於陰極3。所以，最好依二 氧化矽4與陰極3進行面接觸方式，在陰極3上載置二氧 化石夕4。 解槽1的内部注人炫融鹽5，該；tg：融鹽5係為 陽極6、陰極3、與電源（未圖示）進行電氣式連接，便浸 者與陰極3相連接的導電體7與參考電極8。參考電極 係視需要才使用。參考電極 8係可使用例如白金線等。: W鹽5的溫度係可使用例 J如鉻鎳—鋁鎳熱電偶（chrome] 如嶋。_)等熱電偶（未圖示）進行測定。 本發明中，除第1圖所示電解還原裝置之外， 尚可使用例如第2圖所示電解 ,,, 疋席裝置’連續地進行二覃 化矽之電解還原。第2圖所 係本發明的矽材之製造方法 12 201247937 所使用電解還原裝置的另一實施態樣概略說明圖。 第2圖中’在電解槽1的内面底部配置著由矽構成的 陰極3電解槽1係就從避免所生成的石夕材中混入雜質之 觀點較佳係利用例如石英等形成。電解槽^的内部空間 車乂佳係利用例如氮氣、氬氣等惰性氣體進行取代。 _在陰極3上載置著二氧化矽4。當在陰極3上載置著 二氧切4之狀態下，使二氧切4進行電解還原時，藉 由二氧切4進行電解還原，便會生切材9。另外，第2 圖所不貫施態樣，藉由在陰極3上所載置的二氧化石夕4進 :電解還原而生成石夕材9之後，更進一步添加二氧化石夕4, 更隔著所生切材9在陰極3上載置著二氧化石夕〇 ^中’-氧切4係可依接觸到陰極3的方式，直接 置於陰極3上，或者亦可 材9載置於陰極3上1生=圖所不，隔著所生成碎 下部配設取出〇材9係例如在電解槽… 使用Γ二 該取出°ia進行回收。 電解…上部補充二氧化Π置:::在因為可-邊從 部所配設取出〜，回收利用在電解槽1的下 成石夕材9,因而可使二氧化石夕4的電解還原所生 可連續效率佳地製料材9。地進行電解還原，故 第2圖所示二氧化矽4係 樣的具有顆粒形狀，惟本發明：第1圖所示二氧化石夕4同 有所限定。另外，二氧切二不：二氣…的形狀而 之觀點’最好依盡可能增加虚心二效率佳地製切材9 ]之接觸面積的方 13 201247937 式，使與陰極3相接觸。所— 所以，第2圖所不貫施態樣，二 I4最好依與陰極3或所生成矽材9進行面接觸的方 陰極3或所生成矽材9上載置著二氧化矽 在電解槽1的内部中注入熔融鹽5。陽極6係如第2 圖所示，配設於電解播】 的上。卩，但未必一定要配設於電 解槽1的上部，亦可、、民、矣 方了久凊於熔融鹽5中。陰極3係經由導 電體7電氣式連接於雷调广土固_、 冤源（未圖不）。熔融鹽5的溫度係可 吏用例如鉻鎳！呂鎳熱電偶等熱電偶(未圖示)進行測定。 第2圖所示實施態樣，係與第丄圖所示實施態樣同樣 的’視需要亦可使用參考電極(未圖示）。 如以上所說明，你田势O m 使用第2圖所示電解還原裝置時，在 有裝入溶融鹽5的電解;^彳# . _ θ内，在該熔融鹽5中將陽極6 浸潰於溶融鹽中，並由石夕構成的陰極3上載置二氧切4 的狀痛下’進行二氧化石夕4的電解還原，便可效率佳地製 造石夕材9。又，因為一邊從電解槽1的下部所配設取出口 la回收所生切材9，—邊從電解槽】的上部將新的二氧 化石夕4供應給㈣鹽5,便可在陰極3上載置二氧化石夕4, 因而可連續效率佳地製造矽材9。 依如上述所製造石夕材令的金屬雜質含有率，係當諸如 太陽電池用♦等使用於要求高純度之用途時，較佳為100 質量卿（以下稱「卿」）以下、更佳為1〇卿以下、特佳 為1ΡΡΠ!以下、最佳為G.5ppfflaT、最最佳為G」卿以下。 金屬雜質係可例如：納、鎮、紹、鉀、詞、鈦、猛、鐵等， 惟本發明並不僅侷限於該等例示。 201247937 …再者，當使用依照本發明製造方法所獲得矽材，製造 半，體時，藉由將諸如棚、磷等添加物少量添加於石夕材中， 便可對碎材賦予p型半導體或η型半導體的性f。此情況， 石夕材中所含蝴與碌的合計含有率，係就從㈣作為半導體 之機能的觀點，較佳為lppm以下。 依如上述，藉由本發明製造方法所獲得的石夕材，可有 效使用為例如：太陽電池的光電動勢電力元件、 負極材料' 矽化合物的原料等。 [實施例] 其次，針對本發明根據實施例進行更詳細說明，惟本 發明並不僅侷限於該實施例。 實施例1 (1)炫融鹽之原料 溶融鹽的原料係使用將氣化4 ^ τ虱化鈣（純度：99%以上）400g 裝入石央製堆堝（内徑：85_、高 心 阿.丨20_、厚：2. 5mm)中 之後，依500°C施行1天以上的真处 ⑵二氧切 的真工“而去除水分者。After the electrolytic reduction of ruthenium oxide, the troublesome operation of taking out the cathode from the electrolysis and replacing it with a new cathode is not adopted, and as long as the continuous supply is performed, the invention can be continuously manufactured by the electrolytic reduction of the oxidized sand. Completed by discovery. In the method for producing a material according to the present invention, the raw material is sulfur dioxide. The I oxygen cleavage system can be, for example, quartz, dioxic sand, 'amorphous sulphur dioxide, s: 2. The invention is not limited to the examples. Among these cerium oxides, from the viewpoint of a high reduction rate, amorphous sulphur dioxide is preferred. The non-negative-type sulphur dioxide can be, for example, an amorphous form contained in the shizuo earth or the like. In general, the Shiyoshizao soil contains an amorphous form of bismuth according to a content of 80 to 90% by mass, and includes a clay component such as alumina.非晶', the amorphous oxidized ash contained in the soil is different from the f $fossil contained in quartz, etc. because of the ability to dissolve in the aqueous solution, the amorphous cerium oxide The = dissolved in the aqueous alkali solution, by repeating the operation of controlling the core of the aqueous solution to precipitate the amorphous dioxite, the high-order, amorphous amorphous stone can be prepared to have a mass of 99% by mass or more. Xi. The purity of the silica dioxide is preferably from the viewpoint of electrolytic reduction of the silica dioxide to produce a high-purity stone material, and the higher the purity, the better. The content of the impurity in the day of the oxidization of the cerium oxide is preferably from the viewpoint of the electrolytic reduction of the oxidized silica, and the high-purity stone material. 1 Qing below, the best is below G.5 Qing. Further, the impurity in the day of the oxidized stone may be, for example, sodium m, n (tetra) m «, but the present invention is not limited to the example of 201247937. The emulsified 矽 矽 系 使 , , 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿 咿The upper limit of the particle diameter of the particles is the same as the above lower limit value, and the electrolytic reduction (four) point of the dioxide is performed from the viewpoint of efficiency, and is less than (four)'. The silica dioxide particle system can be easily obtained commercially, for example, from purified Si 2 particles manufactured by Pacific Cement Co., Ltd.二 The cerium oxide used for electrolytic reduction is preferably a porous body. The porous system can be, for example, a shaped body formed into a desired shape, a granular material in which particles are agglomerated or bonded to each other, and the like. The shape of the shaped body of the dioxide dream can be, for example, a cylinder, a cube, a rectangular parallelepiped, a flat plate, a film, a ball, etc., but the present invention is not limited to these examples. The size of the molded body of the cerium oxide is not particularly limited, and a cylindrical shaped body having a diameter of about 5 to 30 mm and a thickness of about U 0 mm or a side is preferably used from the viewpoint of efficient electrolytic reduction of the oxidized silica. A cube-shaped or rectangular parallelepiped molded body having a length of about 5 to 30 mm. The forming system of cerium oxide can be easily produced, for example, by, for example, compression molding. When the molding system of cerium oxide is produced by compression molding, a porous molded body having voids communicating with the surface inside the molded body can be obtained. Since the porous forming system allows the molten salt to be wetted into the inner portion thereof, it has an advantage that the electrolytic reduction of the cerium oxide can be performed efficiently. Therefore, in the present invention, the cerium oxide is preferably a porous formed body of cerium oxide. 201247937 Dioxide #Peroxide molding system, for example, mixing dioxo prior particles with an appropriate amount of water. The obtained mixture is filled in a molding die having a desired inner surface shape, and can be produced by applying pressure. When the porous molding system of + yttrium oxide is produced by compression molding, 2 the porous molded body is sintered from the viewpoint of improving the mechanical strength of the obtained porous molded body. When the oxidized porous material is sintered, the porous molded body is dried, and then heated to ι 〇〇〇 ΐ 5 在 in an atmosphere or an inert gas atmosphere such as nitrogen argon. A sintered porous molded body can be produced at a temperature of about °C. The porosity of the porous material of the dioxide material is preferably from the viewpoint of improving the electrolytic reduction efficiency of the dioxide by the infiltration of the molten salt into the interior of the porous material, and is preferably more than the above, more preferably, or more than 50. % or more, from the viewpoint of the mechanical strength of the porous molded body in the south of the country, and the improvement of the mechanical strength of the sarcophagus formed by the electrolytic reduction of the oxidized silica, it is preferred that 〇% or less, more preferably 70% or less, and particularly preferably 65% or less. The particle size of the cerium oxide is scattered from the molten material, placed on the cathode, and the total value of the electrical contact resistance occurring between the reduced particles is reduced. 2: The viewpoint of electrolytic reduction efficiency of oxygen cutting is preferably 5 〇 "above" Π::: above, especially good 2 〇 0..., best ~ 时 颧 颧 ^ electrolytic reduction until cerium oxide The inner part of the granular material is preferably 3G, the lower one is better, the lower one is more than 3mm, and the other is less than 3mm. The blending is not 匕^ the diffraction type particle size distribution Fuxi Shixi's granular particle size is using a laser [Nikkiso (stock) system, trade name: Microtrac 201247937 MT33 00 1 1. Solvent: water, dispersant: no 1, WM" The value at the time of measurement. Since there is a void between the particles constituting the granules, m, the granules of cerium oxide are similar to the porous formed body of cerium oxide, so that the molten salt can be moistened into the interior thereof. The advantage of the oxidized rock ray thunder / magical reduction can be carried out efficiently. Therefore, it is preferable to use the granules of the dioxide dioxide. The granules of the cerium oxide are mixed, for example, by mixing the cerium dioxide particles with an appropriate amount of water, and then filling the obtained mixture into a forming mold having a desired inner surface shape, applying pressure, and then performing pulverization as needed. Made for manufacturing. Further, the above obtained granular material is preferably sintered from the viewpoint of improving mechanical strength. When the granules are sintered, the granules are dried, and then heated to an atmosphere of about 1,000 to 150 TC in an inert atmosphere such as nitrogen or argon. The sintered granules are produced. The granules can be pulverized after sintering, and the granules can also be sieved to integrate the particle size. The present invention is characterized in that: The cerium oxide is subjected to electrolytic reduction in the presence of a molten salt in a state in which the cerium oxide is placed on the cathode composed of the shi shi shi. Since the present invention adopts the above operation, the sulphur dioxide is continuously In the present invention, a cathode composed of ruthenium is used for the production of the ruthenium by electrolytic reduction. In the present specification, the cathode composed of ruthenium means that at least the surface is formed of ruthenium. Cathode. Therefore, the above-mentioned cathode system composed of Shi Xi may be composed only of a tantalum material, or may be a composite body coated with tantalum on the surface of a metal substrate such as molybdenum. In addition, 201247937 on the surface of the cathode, It is also possible to attach the dioxide powder to the cerium oxide. When the cathode used in the cathode contains impurities, when the dioxide is electrolytically reduced, the impurity may be mixed in the SiO2 electrolytic reduction = stone. Therefore, the purity of the stone material used in the cathode is preferably 99.9% by mass or more, more preferably 99.99% by mass or more, and particularly preferably 99.999% by mass from the viewpoint of obtaining the purity of the coffin. The above is preferably 99.9999% by mass or more. _ The size of the cathode on which the ruthenium dioxide is placed is not particularly limited as long as it can be carried on the cathode, and the rest is not particularly limited. For example, when the dioxide is used, For the case of a plurality of ore dioxide shaped bodies, the size of the shaped body can be placed on the cathode. Therefore, the size of the cathode is preferably matched with the size of the dioxide on the cathode. The number of the cathode is also appropriately determined. The shape of the cathode is not particularly limited, and the shape of the cathode may be, for example, a disk shape having a circular or elliptical shape in plan shape, a triangular shape in a planar shape, a square shape, and the like. An angled plate shape or the like, but the present invention is not limited to the above examples. The cathode surface on which the sulphur dioxide is placed is preferably from the viewpoint of efficient electrolysis of the oxidized silica dioxide. For example, when the contact area is large, for example, when the silica dioxide is used, the surface of the cathode having the planar bottom surface is preferably planar, and the surface of the cathode on which the dioce is placed is preferably flat. The concavity and convex shape is formed on the cathode of the oxidized stone, and the shape corresponding to the convex shape of the concavity is formed on the bottom surface of the dioxin-cut core body, and is thus disposed on the bottom surface of the molded body on the cathode and the cerium dioxide When the concave-convex shape is mutually corresponded, it is possible to efficiently perform the electrolytic reduction of '201247937 on the day of the dioxide, and to fix the molded body of the dioxide on the cathode, and to prevent the formation of the cerium oxide. The advantage of slipping off the cathode. The cathode is connected, for example, to a conductor, and is connected to a power source via the conductor. The salt to be used for the molten salt may, for example, be a metal complex such as an alkali metal or an alkaline earth metal complex, but the present invention is not limited to the examples. The metal complexes may be used alone or in combination. In the metal toothing test, the metal tester can be, for example, a nano, a clock, or an alloy. Among the alkaline earth metal tooth compounds, the alkaline earth metal can be, for example, magnesium, calcium, barium, strontium, etc. The halogen atom constituting the toothed compound may be, for example, a fluorine atom, a gas atom, a desert atom, a dish atom, etc. Specific examples of the metal telluride include, for example, mm chlorination, chlorination, and metallization; gasification The town, the gasification enthalpy, the gasification chain, the gasification lock, and the like, the earth-receiving group (4), the heart (4), etc., but the invention is not limited to the examples. The metal tooth materials may be used alone or in combination of two or more. Among the metal tooth compounds, from the viewpoint of high solubility of oxide ions, it is preferred to use a gasification clock, sodium chloride, magnesium gas, and calcium carbonate, and more preferably calcium chloride. The temperature of the smelting salt during electrolytic reduction is from ^The reduction efficiency of fossil eve is preferably 5 〇〇. The above, more preferably 800 C or more, although depending on the type of smelting salt, it is usually better from the viewpoint of suppressing volatilization of molten salt. 〇υυ L or less, more preferably 900t or less. The polar system can be, for example, a carbon electrode, a graphite electrode, a glassy carbon electrode, a ferrite-grained iron anode, or a boride bismuth, such as ～合庄危极#, but the invention is not only It is limited to these examples. Among the anodes of the temples, from the viewpoint of avoiding the incorporation of impurities into 10 201247937, it is preferable to use an insoluble anode such as a ferrite-based iron-based electrode. The soluble anode and the titanium boride-based insoluble cation make the oxidized stone The cathode potential at the time of electrolytic reduction is preferably set to a potential higher than the potential of the cation derived from the molten salt from the molten material. The cathode potential varies depending on the type of the molten salt, and cannot be determined in a general manner. Generally, from the viewpoint of avoiding the bond between the metal formed by the reduction of the cation derived from the smelting salt and the diarrhea, it is preferable that Ο ν [(4) represents a gold deposit precipitated by the cathode limit of the molten salt. Dependent or soil-testing metal; η is a valence of an alkali metal or an alkaline earth metal)), more preferably 0.6 Π centroid (3) and „ is the same as above), and is particularly good from the viewpoint of improving electrolytic reduction efficiency. The system u [for rvM (M#r^ the same as above)] below. In the method for producing the stone material of the present invention, for example, after an inert gas atmosphere is formed in the electrolytic cell, the dioxotomy is placed on the cathode, and the molten salt is placed in the electrolytic cell, and # electrolytic reduction is performed. Make scraps. At this time, when the dioxide is placed on the cathode, the dioxide is supplied to the cathode, and when the silica is electrolyzed, the coffin can be continuously produced. And manufacture coffins efficiently. The method for producing the coffin of the present invention can be carried out, for example, by using an electroreduction device as shown in Fig. Fig. 1 is a schematic explanatory view showing an embodiment of an electrolytic reduction apparatus used in the method for producing a coffin according to the present invention. In the first drawing, a silica stone plate 2 is placed on the bottom surface of the inner surface of the electrolytic cell 1, and a cathode 3 made of ruthenium is placed on the ruthenium dioxide plate 2. The electrolytic cell i is preferably formed by, for example, quartz or the like from the viewpoint of avoiding the incorporation of impurities into the generated ruthenium. The ceria plate 2 is a material which is preferably used from the viewpoint of improving the productivity of coffin 11 201247937, but the present invention can easily produce a coffin even without using the ceria plate 2. The internal space of the electrolytic cell 1 is preferably replaced with an inert gas such as nitrogen or argon. Cerium oxide 4 is placed on the cathode 3. A major feature of the present invention is that the cerium oxide 4 is electrolytically reduced in a state where the cerium oxide 4 is placed on the cathode 3 as described above. Since the present invention adopts this operation, even if the cathode is replaced with a new cathode after the electrolytic reduction as in the prior art, the carbon dioxide can be continuously electrolytically reduced and thus can be efficiently performed. Manufacturing coffins. The ruthenium dioxide 4 system of Fig. 1 has a particle shape, but the present invention is not limited by the shape of the dioxin 4. Further, the silica dioxide Xi 4 system is preferably in contact with the cathode 3 in order to increase the contact area with the cathode 3 from the viewpoint of efficient cutting of the material. Therefore, it is preferable to place the silica dioxide on the cathode 3 in the surface contact mode of the cathode 2 with the cathode 3. The inside of the unsinking tank 1 is filled with a smelting salt 5, and the tg: molten salt 5 is an anode 6 and a cathode 3, and is electrically connected to a power source (not shown), and the electric conductor connected to the cathode 3 is connected. 7 and reference electrode 8. The reference electrode is used as needed. For the reference electrode 8, for example, a platinum wire or the like can be used. The temperature of W salt 5 can be measured using a thermocouple (not shown) such as a chrome-nickel-aluminum-nickel thermocouple (chrome) such as 嶋. In the present invention, in addition to the electrolytic reduction apparatus shown in Fig. 1, for example, the electrolysis shown in Fig. 2 can be used, and the electroporation of the crucible is continuously performed. Fig. 2 shows a method for producing a coffin according to the present invention. 12 201247937 A schematic view of another embodiment of an electrolytic reduction device used. In the second embodiment, the cathode 3 electrolytic cell 1 which is formed of ruthenium is disposed on the bottom surface of the inner surface of the electrolytic cell 1, and is preferably formed of, for example, quartz or the like from the viewpoint of avoiding the incorporation of impurities into the formed stone material. The internal space of the electrolytic cell is replaced by an inert gas such as nitrogen or argon.二 The cerium oxide 4 is placed on the cathode 3. When the dioxo prior 4 is subjected to electrolytic reduction in a state where the dioxogen 4 is placed on the cathode 3, electrolytic reduction is performed by the dioxotomy 4, and the cut material 9 is produced. In addition, in the second embodiment, the magnet dioxide is placed on the cathode 3 by electrolysis and reduction to form the stone material 9, and then the magnet dioxide is further added. The raw material 9 is placed on the cathode 3 on the cathode 3, and the 'oxygen 4 system can be placed directly on the cathode 3 in a manner of contacting the cathode 3, or the material 9 can be placed on the cathode. 3 Upper 1 = No picture, the coffin 9 is taken out through the generated broken part, for example, in an electrolytic cell. Electrolysis...The upper part of the cerium dioxide is added::: It is taken out from the part by the detachable part, and the effluent material 9 in the electrolytic cell 1 is recycled, so that the electrolytic reduction of the oxidized stone can be made The material can be continuously and efficiently produced. Since the electrolytic reduction is carried out in the ground, the cerium oxide 4 type shown in Fig. 2 has a particle shape, but the present invention: the second embodiment shown in Fig. 1 is limited to the same. Further, the viewpoint of the shape of the second gas: the second gas is preferably made to be in contact with the cathode 3 in accordance with the formula of the contact area of the cut material 9 as much as possible. Therefore, in the second embodiment, the second I4 is preferably placed on the square cathode 3 or the formed coffin 9 which is in surface contact with the cathode 3 or the generated coffin 9 on which the ceria is placed in the electrolysis cell. The molten salt 5 is injected into the inside of 1. The anode 6 is disposed on the electrolysis broadcast as shown in Fig. 2 .卩, but it does not necessarily have to be placed in the upper part of the electrolysis tank 1, and it can be used in the molten salt 5 for a long time. The cathode 3 is electrically connected to the sag and the sputum source (not shown) via the electric conductor 7. The temperature of the molten salt 5 can be, for example, chromium nickel! A thermocouple such as a Lu Nickel thermocouple (not shown) was measured. The embodiment shown in Fig. 2 is the same as the embodiment shown in the figure, and a reference electrode (not shown) may be used as needed. As explained above, when you use the electrolytic reduction device shown in Fig. 2 in the field Om, the anode 6 is immersed in the molten salt 5 in the electrolysis containing the molten salt 5; ^彳# . _ θ In the molten salt, the cathode 3 composed of Shi Xi is placed under the sputum of the dioxin 4, and the electrolytic reduction of the oxidized stone eve 4 is carried out, whereby the slab 9 can be efficiently produced. Further, since the raw material 9 is recovered from the lower portion of the electrolytic cell 1 and the raw material 9 is recovered, the new quartz dioxide 4 is supplied from the upper portion of the electrolytic cell to the (4) salt 5, and the cathode 3 is provided. The carbon dioxide is placed on the eve 4, so that the coffin 9 can be manufactured continuously and efficiently. The metal impurity content rate of the sapphire material produced as described above is preferably 100 mass qing (hereinafter referred to as "Qing"), and more preferably when it is used for applications requiring high purity, such as for solar cells. 1 〇 以下 below, especially good for 1 ΡΡΠ! The following, the best is G.5ppfflaT, the best is below G". The metal impurities may be, for example, Na, Zhen, Shao, K, Word, Titanium, Niobium, Iron, etc., but the invention is not limited to the examples. 201247937 ... Further, when a coffin obtained by the manufacturing method of the present invention is used to manufacture a half body, a p-type semiconductor can be imparted to the shredded material by adding a small amount of an additive such as a shed or a phosphorus to the stone material. Or the nature of the n-type semiconductor f. In this case, the total content of the butterfly and the ash contained in the stone ceremonial material is preferably 1 ppm or less from the viewpoint of (4) function as a semiconductor. As described above, the stone material obtained by the production method of the present invention can be effectively used as, for example, a photovoltaic element of a solar cell, a raw material of a negative electrode material, and a raw material of a ruthenium compound. [Embodiment] Next, the present invention will be described in more detail based on the embodiments, but the present invention is not limited to the embodiment. Example 1 (1) The raw material of the molten salt of the molten salt is used to charge the gasification 4 ^ τ calcium (purity: 99% or more) 400 g into the Shiyang system stack (inner diameter: 85_, high heart)丨20_, thickness: 2. 5mm), after 500 ° C for more than 1 day of the real (2) dioxotomy of the real work "and remove the water.
電解還原時所使用的二氧化石夕係使用依二氧化石夕粉末 [太平洋水泥⑷製、精製二氧化㈣末]心，為水W ΓΓ:7者：合，再將所獲得屍合物裝入成形模内，依 1.5xl〇3kg/cm2(約 l47MPa)壓* a / 刀把行加壓，而製作外徑 12_、厚3mm的顆粒後，於轰痛 qn v A 氣衣1見中，依1 3501溫度施 订30分鐘燒結而獲得的二氧化矽顆粒。 (3 )電極 15 201247937 «極#、使❹㈣電極mPAN M職smicE(股） 陽極係使用石墨棒[Tokai Carb〇n(股）製、直徑： 5龍]。又’參考電極係使用直徑—的白金線。 (4 )電解還原操作及其結果 使用帛i圓所示電解還原裝置施行二氧切的電解還 9"二了 ：製電解槽1的内部空間流通著氬氣(純度 =5/:):俾將該電解槽1内保持呈氨氣環境。在陰極3 者田作—氧切4用之依上述所獲得二氧化石夕顆 4 “將經8阶加熱熔融的氣化㈣融鹽5(400g量）裝 入：電解槽1内，於同溫度下，依陰極電位0. 8V(對Ca2+/Ca) ::150小時恒電位電解，考慮因殘餘電流 :率降低情形’通電入相當於還原率⑽的電量。此處， 還原率係依照式： i還Λ率（/0]=[(實際進行電解時所需要的電量）/(理論上 為生成矽材所必要的電量）]xloo 計算出。電解還原係每隔約4°小時分割為4次實施，在電 解暫停時便依㈣電位靜置。電解還料的電流經時變化 係如第3圖所示。 如第3圖所示，發現隨電解的進行，還原電流會增加， 電解暫停後的再通電時，觀測到較大的還原電流。又， 還原電流係經時逐漸辦Λ 石夕的可認為隨從二氧化石夕朝 < 仃，一氧化矽與矽間的接觸面積增大，導致 效反應面積增大的緣故所致。 經目視觀察電解還原操作後的顆粒，發現其表面變化 16 201247937 為黑色多孔質體’有被還原為矽的部分，但在其内部則仍 保持二氧化矽的狀態。此現象可認為當原本表面的還原結 束，而朝顆粒内部方向進行還原時，反應會變慢，導致電 流值減少的緣故所致。 其次’電解結束後的試料利用蒸餾水施行洗淨後，利 用酸洗淨液[蒸餾水：1M鹽酸水溶液：30%過氧化氫水（容 量比）=5 : 1 : 1]施行超音波洗淨。經洗淨後，回收顆粒經 還原的部分’並調查其X射線繞射。χ射線繞射係使用χ 射線繞射裝置[Rigaku(股）製、商品名：Ultiroaiv]，利用 UKo:線，依波長（λ )15418A、電壓4〇kv、電流進 行測定。其X射線繞射圖係如第4圖所示。 由第4圖所示結果，源自二氧化石夕的繞射線較微弱， 而石夕的繞射線則明顯出1，因而可確認根據實施例卜能 使二氧化矽效率佳地還原為矽。 其次，依上述所獲得矽利用掃描式電子顯微鏡 [KEYENCE(股）製、型號：VE —88〇〇]進行觀察。、结果如第5 圖所不。> 第5圖的掃描式電子顯微鏡照片所示，依上述 所獲得石夕可確認到直栌1 啤。』置左右的針狀構造、直徑10#m 左右的柱狀構造、及由初 由粒子相凝聚的塊狀構造《又，經利 用X線分析裝置[EDAX公司製、东口么.r η ' 我 两〇口名· Genesis]施行第5 圖所示X1、X2及X3各區域元去幻 0 订弟 素刀析，^果確認到針狀與柱 狀物質均係矽。另—方 ’從塊狀部分檢測出大量的氧， 暗示含有較多的二氧化矽 , 夕由以上，可確認依如上述，藉 由施行二氧化矽的電艋罗 還原，便可形成具有針狀或柱狀構 17 201247937 造的矽。 :次，利用輝光放電質量分析調查獲得梦材中所含雜 ^3有率’結果翻含有率係未滿〇ι_、 未 滿ippm、磷含有率係未滿lppm。 乎未 實施例2 化為=續地進行二氧化石夕的還原，最好持續供應二氣 係使用第 易地持續供應二氧切的電解還原裝置， 施例1所使用者同樣的二氧化㈣ -邊施行二氧切4的 °樣的’ -备儿遭依在陰極3上載置 式，將二氧化㈣粒從電解槽1的上部投 3:弓溶融鹽5中，藉此便將二氧…供應給陰極 而使該一氣化梦4進杆雷紐、萝js 顆粒在開始之初會声浮於氣 、、。結果，二氧化矽 短暫時間後便沉殿於氣化_ : 1同樣，依"V(對Ca2Vr、Φ 然後，與實施例 紐 /Ca)電位施行58小時的作電位電 解，結果通電量係使二氧切 ：電位電 8〇%。 還原時所必要電量的約 其次，所生成的石夕從在電解槽i的下部所配設取出口 /回收’並與實施例1同樣的施行洗淨後，經調杳所生 二材：二射線繞射，結果明顯觀測到源自…的繞 方大由此現象可確認當依在陰極3上載置二氧化石夕4的 …一邊將一氧化石夕4供應給陰極3上，-邊使該二氧 夕4進盯電解還原時，可連續效率佳地製造砂材9。 18 201247937 含有2睹經利用輝光放電質量分析調查所獲得石夕材9中 3有的雜質含有率，社 ^W y r 率係未篇 、、° 3有率係未滿〇· lppro、硼含有 滿1ppm、磷含有率係未滿lPpm。 比較例1 所記= 曰本專利特開20°6—321 688號公報的「實施例1」 上”仃矽材的製造。此時，目為必需藉由使矽電極棒 附者：孔質二氧化石夕粉末成形體，而製作使石夕電極與多 質氧化矽叙末成形體相接觸的陰極，因而陰極的製作 較為麻煩，且操作煩雜。又，在二氧切進行電解還原後， 必需從電解槽中取出陰極並更換為新的陰極，0而操作煩 雜，且二氧化矽的電解還原操作必需暫時中斷。 由以上的結果得知’根據實施例1與實施例2，在對 比於比較W1之下’因為必需要使石夕電極棒上附著多孔質 一氧化矽粉末成形體的煩雜操作，因而可使二氧化矽效率 佳地電解還原。又，根據實施例丨與實施例2，將二氡化 矽連續地供應給電解槽内，便可連續地製造矽，因而得知 可效率佳地製造矽材。又，根據實施例2，得知依在陰極 上載置二氧化石夕的方式’一邊將二氧化矽供應給陰極上， 一邊使該二氧化矽進行電解還原，且可回收所生成的矽， 因而可連續效率佳地製造矽，故得知可連續大量地製造矽。 實施例3 實施例1中，除將陰極電位由〇· 8V(對Ca2+/Ca)變更為 1. 2V(對Ca2+/Ca)之外，其餘均與實施例1同樣的施行電解 還原。結果’可確認到與實施例1同樣的，能效率佳地製 19 201247937 造雜質含有率較低之矽 實施例4 實施例2中’除將陰極電位由0.8V(對Ca2 + /Ca)變更為 1.2V(對Ca2+/Ca)之外，其餘均與實施例2同樣的施行電解 還原”’α果’可確s忍到與實施例2同樣的’能效率佳地製 造雜質含有率較低之矽，且可連續效率佳地製造矽材。 實施例5 實施例1中’除將陰極電位由0. 8V(對Ca2+/Ca)變更為 0.7V(對Ca2+/Ca)，以及將電解時間由150小時變更為8〇 小時之外，其餘均與實施例丨同樣的施行電解還原。電解 還原時的電流經時變化係如第6圖所示。圖中，虛線係陰 極電位0. 7V(對Ca2+/Ca)時，進行電解還原時的電流經時變 化（實施例5)，實線係陰極電位〇.8v(對Ca2+/Ca)時，進行 電解還原時的電流經時變化（實施例1 )。 由第6圖所示結果得知，當陰極電位〇· 7V(對Ca2+/Ca) 時，電解進行時的還原電流（實施例5)，較大於陰極電位 〇_8V(對Ca27Ca)時，電解進行時的還原電流（實施例丨）， 因而陰極電位0.7V(對Ca2+/Ca)時的還原速度，係較大於陰 極電位0.8V(對Ca2+/Ca)時的還原速度。又，可確認到根據 實把例5，能與實施例1同樣的效率佳地製造雜質含有率 較低的石夕。 實施例6〜8 將實施例1所使用的二氧化矽顆粒予以粉碎，再將所 獲得粉碎物施行篩分，而獲得粒徑5〇〇//m〜lmm的二氧化矽 20 201247937 粒狀物。 接著，在實施例1中，除二氧化矽4係取代將二氧化 矽顆粒載置於陰極3上，而改為將依上述所獲得二氧化矽 粒狀物載置於陰極3上，且將陰極電位由〇8v(對Ca2+/Ca) 變更為0· 7V(對Ca2 + /Ca)(實施例6)、變更為〇. 6v(對The silica dioxide used in the electrolytic reduction is based on the core of the dioxide dioxide [Pacific cement (4), refined dioxide (four) end], the water W ΓΓ: 7: the combination, and then the obtained corpse Into the forming mold, according to 1.5xl 〇 3kg / cm2 (about l47MPa) pressure * a / knife press line, and the production of outer diameter 12_, thickness 3mm particles, after the pain qn v A airwear 1 see, according to 1 3501 temperature is applied to the cerium oxide particles obtained by sintering for 30 minutes. (3) Electrode 15 201247937 «极#, ❹(4) electrode mPAN M smicE (share) The anode is made of graphite rod [Tokai Carb〇n (stock), diameter: 5 dragon]. Further, the reference electrode is a diameter-plated platinum wire. (4) Electrolytic reduction operation and its results using electrolysis reduction apparatus shown by 帛i circle to perform electrolysis of dioxotomy 9"2: Argon gas is passed through the internal space of the electrolytic cell 1 (purity=5/:): The inside of the electrolytic cell 1 was maintained in an ammonia atmosphere. In the cathode 3, the field is used as the oxygen cutting 4, and the obtained carbon dioxide is obtained according to the above. "The gasification (four) molten salt 5 (400 g amount) which is heated and melted by 8 steps is charged into the electrolytic cell 1, in the same At the temperature, according to the cathode potential of 0. 8V (for Ca2+ / Ca) :: 150 hours of potentiostatic electrolysis, consider the residual current: the rate is reduced, the current is equivalent to the reduction rate (10). Here, the reduction rate is according to the formula : i is also the rate (/0) = [(the actual amount of electricity required for electrolysis) / (theoretically the amount of electricity necessary to generate the coffin)] xloo calculated. Electrolytic reduction is divided into about every 4 ° hour 4 times, when the electrolysis is suspended, the potential is allowed to stand at (4). The current change of the electrolyzed material is as shown in Fig. 3. As shown in Fig. 3, it is found that the reduction current increases with the progress of electrolysis. When the power is re-energized after the suspension, a large reduction current is observed. In addition, the reduction current is gradually lapsed. It can be considered that the contact area between the ruthenium oxide and the ruthenium is increased. Large, resulting in an increase in the area of the effect reaction. Visual observation of the particles after the electrolytic reduction operation The granules were found to have a surface change of 16 201247937. The black porous plastids have a portion that has been reduced to ruthenium, but remain in the ruthenium dioxide state inside. This phenomenon can be considered as when the reduction of the original surface ends and the interior of the granules When the direction is reduced, the reaction is slowed down, resulting in a decrease in the current value. Next, the sample after the completion of the electrolysis is washed with distilled water, and then washed with an acid solution [distilled water: 1 M hydrochloric acid aqueous solution: 30% hydrogen peroxide) Water (capacity ratio) = 5 : 1 : 1] Ultrasonic cleaning is performed. After washing, the reduced portion of the particles is recovered 'and the X-ray diffraction is investigated. The X-ray diffraction system uses a χ ray diffraction device [ Rigaku (stock), trade name: Ultiroaiv], measured by wavelength (λ) 15418A, voltage 4〇kv, current using UKo: line. The X-ray diffraction pattern is shown in Figure 4. As shown in the figure, the ray originating from the oxidized stone is weaker, and the ray of the eve is obviously 1, so it can be confirmed that the cerium oxide can be efficiently reduced to yttrium according to the embodiment. The above-mentioned 矽 use A scanning electron microscope [Model: VE-88〇〇, model number: VE-88〇〇] was observed. The results are shown in Fig. 5. > The scanning electron micrograph of Fig. 5 shows the stone obtained as described above. On the eve of the day, it is possible to confirm the direct beer 1 beer. The columnar structure of the left and right needles, the columnar structure of about 10#m in diameter, and the block structure which is agglomerated by the particle phase at the beginning, and the X-ray analysis device [EDAX] System, East Mouth.r η 'I am two mouths name · Genesis] Execution of Figure 5 X1, X2 and X3 areas of the area to the illusion 0 to discriminate, the fruit is confirmed to the needle and column material Both are 矽. In addition, the square 'detects a large amount of oxygen from the block portion, suggesting that it contains a large amount of cerium oxide. From the above, it can be confirmed that, as described above, by performing the electric sputum reduction of cerium oxide, a needle can be formed. Shape or columnar structure 17 201247937. : The results of the glow discharge quality analysis showed that the miscibility rate contained in the dream material was less than _ι_, less than ippm, and the phosphorus content was less than 1 ppm. In the second embodiment, the reduction of the dioxide is carried out continuously, and it is preferable to continue to supply the two gas systems. The electrolytic reduction device which continuously supplies the dioxane is continuously used, and the same oxidation of the user of the first embodiment (4) - while performing a dioxin-cut type of -2, the preparation of the cathode 3 is placed on the cathode 3, and the oxidized (four) particles are cast from the upper part of the electrolytic cell 1 to the lyophilized salt 5, thereby ... Supply to the cathode and make the gasification dream 4 into the rod, the js particles will float at the beginning of the gas. As a result, after a short period of time, the cerium oxide is ignited in the gasification _ : 1 . Similarly, the potential is electrolyzed for 58 hours according to the potential of "V2Vr, Φ, and then the Example New/Ca". Make dioxotomy: potential electric 8 〇%. The amount of electricity required for the reduction is about the next time, and the generated Shi Xi is disposed from the lower portion of the electrolytic cell i, and is taken out and recovered in the same manner as in the first embodiment. Ray diffraction, as a result, it is apparent that the winding origin from ... is large, and it can be confirmed that when the cathode 3 is placed on the cathode 4, the carbon monoxide is supplied to the cathode 3, and the side is made. When the dioxin 4 is focused on electrolytic reduction, the sand material 9 can be continuously and efficiently produced. 18 201247937 Contains 2 睹 利用 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质 杂质1 ppm, phosphorus content is less than lPpm. Comparative Example 1 Note: In the "Example 1" of the Japanese Patent Publication No. 20-6-321 688, the manufacture of the coffin is carried out. At this time, it is necessary to attach the electrode to the crucible: The dioxide is formed on the powder of the oxidized stone, and the cathode which makes the shixi electrode and the multi-type cerium oxide-formed body are brought into contact with each other, so that the preparation of the cathode is troublesome and the operation is complicated. Further, after electrolytic reduction by the dioxotomy, It is necessary to take out the cathode from the electrolytic cell and replace it with a new cathode, and the operation is troublesome, and the electrolytic reduction operation of the cerium oxide must be temporarily interrupted. From the above results, it is understood that, according to the first embodiment and the second embodiment, Comparing W1, 'Because it is necessary to make the porous iridium oxide powder shaped body adhere to the shixi electrode rod, the cerium oxide can be efficiently electrolytically reduced. Further, according to the embodiment 丨 and the embodiment 2, The crucible is continuously supplied to the electrolytic cell, and the crucible can be continuously produced, so that it is known that the crucible can be efficiently produced. Further, according to the second embodiment, it is known that the cathode is placed on the cathode. Way 'one side will The cerium oxide is supplied to the cathode, and the cerium oxide is electrolytically reduced, and the generated cerium can be recovered, so that cerium can be produced continuously and efficiently. Therefore, it has been found that cerium can be continuously produced in a large amount. In the first example, electrolytic reduction was carried out in the same manner as in Example 1 except that the cathode potential was changed from 〇·8 V (for Ca 2+ /Ca) to 1.2 V (for Ca 2+ /Ca). As a result, it was confirmed and implemented. In the same manner as in Example 1, it can be efficiently produced. 19 201247937 The impurity content is low. Example 4 In Example 2, except that the cathode potential was changed from 0.8 V (for Ca2+/Ca) to 1.2 V (for Ca2+/ Except for Ca), the same electrolytic reduction "α-fruit" as in Example 2 can be used to achieve the same efficiency as in Example 2, and it is possible to efficiently produce impurities with low impurity content and continuous efficiency. Jiadi manufactures coffins. Example 5 In Example 1, except that the cathode potential was changed from 0.8 V (for Ca 2+ / Ca) to 0.7 V (for Ca 2+ / Ca), and the electrolysis time was changed from 150 hours to 8 hrs, the others were Electrolytic reduction was carried out in the same manner as in Example 丨. The change in current over time during electrolytic reduction is shown in Fig. 6. In the figure, the dotted line is the cathode potential of 0.7 V (for Ca2+/Ca), the current during electrolytic reduction is changed with time (Example 5), and the solid line cathode potential is 8.8v (for Ca2+/Ca). The current at the time of electrolytic reduction was changed with time (Example 1). From the results shown in Fig. 6, it is found that when the cathode potential is 〇·7V (for Ca2+/Ca), the reduction current at the time of electrolysis (Example 5) is larger than the cathode potential 〇_8V (for Ca27Ca), electrolysis The reduction current at the time of the progress (Example 丨), the reduction rate at the cathode potential of 0.7 V (for Ca 2+ /Ca) was greater than the reduction rate at the cathode potential of 0.8 V (for Ca 2+ /Ca). Further, it was confirmed that, according to Example 5, the same efficiency as in Example 1 was able to produce a stone having a low impurity content. Examples 6 to 8 The cerium oxide particles used in Example 1 were pulverized, and the obtained pulverized material was sieved to obtain cerium oxide 20 having a particle diameter of 5 〇〇//m to 1 mm. 201247937 . Next, in Example 1, the cerium oxide particles are placed on the cathode 3 in addition to the cerium oxide 4 system, and the cerium oxide particles obtained as described above are placed on the cathode 3, and The cathode potential was changed from 〇8v (for Ca2+/Ca) to 0·7V (for Ca2+/Ca) (Example 6) and changed to 〇. 6v (pair)
Ca2 + /Ca)(實施例7)、或變更為〇 5v(對Ca2+/Ca)(實施例 8)，以及將電解時間由150小時變更為5〇小時（實施例6)、 變更為48小時(實施命】7)、或變更為31小時(實施例8) 之外，其餘與實施例丨同樣的施行電解還原。電解還原時 的電流經時變化係如第7圖所示。第7圖中，八係表示陰 極電位o.m對Ca2+/Ca)時的電解還原時之電流經時變： (貫施例6) ’ B係表示陰極電位06V(對Ca2+/Ca)時的電解 還原時之電流經時變化（實 n . 9 ； L係表不陰極電位 • 對Ca /Ca)時的電解還原時之電流纟 8)。 书仙·、！吁變化（實施例 由第7圖所示結果得知，陰極 、 λ 性 € 位為 0. 7V(對 /Ca)、〇· 6V(對 Ca2 + /Ca)、或 〇. 5V(對以 還眉费、ώ έ /Ca)時，因為 選原電涎較大，因而可效率佳地製造矽 位A n r u 特別係陰極電 為 UK對 Ca /Ca)或 〇·5ν(對 Ca2+/Ca) 小時為止的還原電流均較大，得知從電 J最初20 可效率佳地製造妙材。 冑解還原-期開始便 實施例9 ~ 11 依二氧化石夕粉末[太平洋水泥（股）製 末]每1 e A此1 r l 教—氧化矽粉 J母為水1.5g的比例將二者予以混 丹將所獲得混 21 201247937 合物在氬氣環境中，依135(rc溫度施行3〇分鐘燒結而獲 得二氧化矽粒狀物。藉由將所獲得二氧化矽粒狀物施行篩 分，便獲得粒徑5~7nun的二氧化矽粒狀物（實施例9)、教 徑50〇em〜lmm的二氧化矽粒狀物（實施例1〇)、及粒徑 250〜500仁m的二氧化矽粒狀物（實施例u)。 接著，在實施例1 + ’除二氧化石夕4取代將二氧化石夕 顆粒載置於陰極3上，改為將依上述所獲得粒徑5〜7咖的 二氧化矽粒狀物（實施例9)、依上述所獲得粒徑 500 //m〜lmm的二氧化矽粒狀物（實施例1〇)、或依上述所獲 得粒徑250〜500 /z m的二氧化矽粒狀物（實施例u)，載置 於陰極3上，並將陰極電位由〇·8ν(對Ca2+/Ca)變更為 0.5V(對Ca2VCa) ’以及將電解時間由15〇小時變更為〇 小時（實施例9)、變更為31小時（實施例1〇)、或變更為 44小時（實施例11)之外，其餘均與實施例i同樣的施行電 解還原。電解還原時的電流經時變化係如第8圖所示。第 8圖中，A係表不使用粒徑5〜7咖二氧化矽粒狀物時的電解 還原時之電流經時變化（實施例9)，Β係表示使用粒徑 5 0 0 β m〜1 m m二氧化矽粒狀物時的電解還原時電流經時變化 (實施例10)’ C係表示使用粒徑250〜500/z m二氧化矽粒狀 物時的電解還原時之電流經時變化（實施例丨丨）。 結果，使用依實施例9〜11所獲得二氧化矽粒狀物、特 別係依實施例10所獲得二氧化矽粒狀物時’因為還原電流 量較大’因而可效率佳地製造矽材。 另外，實施例9 ~ 11中，除將陰極電位由〇. 5 v變更為 22 201247937 0.H.2V之外，其餘均與實施例9、u 原時，仍可獲得與實施例9〜u同樣的結果，。的施行電解還 由以上的結果得知 根據本發明的矽材之 在進行二氧化石夕的雷組、萝 适方法， ’的電解還原後必需要將陰極從 出，藉由使二氧化石夕連續地電解還原便可製造石夕村。取 【圖式簡單說明】 第1圖係本發明的矽材之製造 /竹二表&方法所使用電解還 置之一實施態樣概略說明國。 、、 第2圖係本發明的石夕材之製造方法所使用電解還原裝 置之另一實施態樣概略說明圖。 第3圖係本發明的實施例丨中，電解還原時的電流經 時變化圖。 第4圖係本發明實施例1所獲得矽材的X射線繞射圖。 第5圖係本發明實施例1所獲得矽材的掃描式電子顯 微鏡照片。 第6圖係本發明的實施例5中，電解還原時的電流經 時變化圖。 第7圖係本發明實施例6〜8中，電解還原時的電流經 時變化圖。 第8圖係本發明實施例9〜11中，電解還原時的電流經 時變化圖。 第9圖係習知矽材之製造方法所使用電解還原裝置的 概略說明圖。 23 201247937 【主要元件符號說明】 1〜電解槽； 2 ~二氧化矽板； 4〜二氧化矽； 6〜陽極； 8〜參考電極； la-取出口； 3 ~陰極； 5〜熔融鹽； 7〜導電體； 9〜石夕材。 24Ca2 + /Ca) (Example 7), or changed to 〇5v (for Ca2+/Ca) (Example 8), and the electrolysis time was changed from 150 hours to 5 hours (Example 6), and changed to 48 hours. Electrolytic reduction was carried out in the same manner as in Example 之外 except that the operation was carried out at 7) or changed to 31 hours (Example 8). The current change over time during electrolytic reduction is shown in Figure 7. In Fig. 7, the eight series shows the time-dependent change of the current at the time of electrolytic reduction at the cathode potential om to Ca2+/Ca): (Example 6) 'B shows the electrolytic reduction at the cathode potential of 06 V (for Ca2+/Ca) The current at the time of the current change (real n. 9; L system shows no cathode potential • for Ca / Ca), the current during electrolytic reduction 纟 8). Book fairy,! The change is shown in the figure. The results of the example shown in Fig. 7 show that the cathode and the λ are in the range of 0.7 V (pair / Ca), 〇 · 6 V (for Ca 2 + /Ca), or 〇 5 V (for When the eyebrows, ώ έ /Ca) are large, it is possible to efficiently manufacture the A position A nru special cathode electricity for UK to Ca / Ca) or 〇 · 5ν (for Ca 2+ / Ca) The reduction current is relatively large, and it is known that the first 20 from the electric J can efficiently manufacture the wonderful material.胄 还原 - - 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋 太平洋The mixed mash 21 201247937 compound was obtained by sintering in a argon atmosphere in an argon atmosphere for 3 minutes at rc temperature to obtain cerium oxide particles. The obtained cerium oxide particles were sieved. Then, a cerium oxide particle having a particle diameter of 5 to 7 nun (Example 9), a cerium oxide particle having a diameter of 50 〇em to 1 mm (Example 1 〇), and a particle diameter of 250 to 500 Å are obtained. The cerium oxide granules (Example u). Next, in the example 1 + 'except for the dioxide dioxide 4, the cerium dioxide particles are placed on the cathode 3, and the particle size obtained according to the above is changed instead. 5 to 7 coffee cerium oxide particles (Example 9), cerium oxide particles having a particle diameter of 500 //m to 1 mm obtained as described above (Example 1), or the particle diameter obtained as described above 250~500 /zm of cerium oxide particles (Example u), placed on the cathode 3, and the cathode potential was changed from 〇·8ν (for Ca2+/Ca) to 0.5V (for Ca2VCa)' and The same operation as in Example i was carried out except that the electrolysis time was changed from 15 hrs to 〇 hours (Example 9), 31 hours (Example 1), or 44 hours (Example 11). Electrolytic reduction. The current change during electrolysis reduction is shown in Fig. 8. In Fig. 8, the A series shows the current over time during electrolytic reduction when the particle size of 5~7 coffee ceria is not used. Variation (Example 9), the lanthanide system shows that the current changes with time when electrolytic reduction is performed using a particle size of 500 Å m to 1 mm of cerium oxide (Example 10) 'C system means particle size 250~ The current at the time of electrolytic reduction in the case of 500/zm cerium oxide particles was changed with time (Example 丨丨). As a result, the cerium oxide particles obtained in Examples 9 to 11 were used, particularly according to Example 10. When the cerium oxide granules were obtained, the cerium was efficiently produced because of the large amount of reduction current. In addition, in Examples 9 to 11, the cathode potential was changed from 〇. 5 v to 22 201247937 0. The same results as in Examples 9 to u were obtained in the same manner as in Example 9 and U except for H.2V. From the above results, it is also known from the above results that the coffin according to the present invention is subjected to the sulphur dioxide and the sorghum method of the sulphur dioxide, and after the electrolytic reduction, it is necessary to remove the cathode by making the oxidized stone. On the eve of continuous electrolysis reduction, we can produce Shi Xicun. Take a brief description of the drawings. Figure 1 is a schematic illustration of the implementation of the electrolysis of the coffin of the present invention/bamboo two tables & Fig. 2 is a schematic explanatory view showing another embodiment of the electrolytic reduction apparatus used in the method for producing the stone material of the present invention. Fig. 3 is a graph showing changes in current over time during electrolytic reduction in the examples of the present invention. Fig. 4 is an X-ray diffraction diagram of a coffin obtained in Example 1 of the present invention. Fig. 5 is a scanning electron micrograph of a coffin obtained in Example 1 of the present invention. Fig. 6 is a graph showing changes in current over time during electrolytic reduction in Example 5 of the present invention. Fig. 7 is a graph showing changes in current over time during electrolytic reduction in Examples 6 to 8 of the present invention. Fig. 8 is a graph showing changes in current over time during electrolytic reduction in Examples 9 to 11 of the present invention. Fig. 9 is a schematic explanatory view showing an electrolytic reduction apparatus used in a method for producing a conventional coffin. 23 201247937 [Description of main components] 1~ electrolytic cell; 2 ~ cerium oxide plate; 4~ cerium oxide; 6~ anode; 8~ reference electrode; la-taken outlet; 3 ~ cathode; 5~ molten salt; ~ Conductor; 9 ~ Shi Xiyuan. twenty four