201001783 六、發明說明 【發明所屬之技術領域】 本發明係有關鈉蓄電池。 【先前技術】 鈉蓄電池爲，具有正極及負極之蓄電池。蓄電池之代 表物的鈉蓄電池因已實用化爲手機、筆記型電腦等之小型 電源，及可作爲電動汽車、混合式汽車等汽車用電源或分 散型電力貯藏用電源等大型電源用，故其需求逐漸增加。 但鋰蓄電池中，構成正極的複合金屬氧化物含有大量鋰等 稀少金屬元素，因此用以對應大型電源需求的增加恐有前 述原料供給疑慮。 針對可解決上述供給疑慮之蓄電池而開始檢討鈉蓄電 '池。鈉蓄電池可由供給量豐富且價廉之材料構成，故期待 其實用化後可供給大量電源。 鈉蓄電池之具體例如專利文獻1所記載，具有使用 Na、Μη 及 Co 之組成比（Na: Mn: Co)爲 0.7: 0.5: 0.5 的 原料焙燒而得之複合金屬氧化物的正極，與由鈉金屬形成 白勺負極之蓄電池。 專利文獻1 :特開2007-287661號公報（實施例 [發明內容】 發明所欲解決之課題 但先前的鈉蓄電池就蓄電池之循環性觀點，即重覆充 -5- 201001783 放電時之放電容量維持率尙不足。因此本發明之目的爲， 提供循環性比先前更優良的鈉蓄電池。 解決課題之方法 爲了解決上述課題經本發明者們專心硏究後，完成本 發明。即，本發明係提供下述發明。 <1>一種鈉蓄電池，其爲具有，含有含Na及M^M1 爲Μη、Fe、Co及Ni所成群中所選出的2種以上元素）， 且NaiM1之莫耳比爲a: l(a爲超過0.5未達1之値）的 複合金屬氧化物之正極，與含有可吸藏及脫離鈉離子的碳 材料之負極，與電解質。 <2>如前述<1>所記載的鈉蓄電池，其中另具有分 離器。 <3>如前述<2>所記載的鈉蓄電池，其中分離器 爲，具有由含有耐熱樹脂之耐熱多孔層及含有熱塑性樹脂 之多孔質薄膜層合而得的層合多孔質薄膜之分離器。 < 4 >如前述< 1 >至< 3 >中任何一項所記載的鈉蓄 電池，其中複合金屬氧化物如下述式（1)所表示，201001783 VI. Description of the Invention [Technical Field of the Invention] The present invention relates to a sodium storage battery. [Prior Art] A sodium battery is a battery having a positive electrode and a negative electrode. The sodium battery of the representative of the battery has been put into practical use as a small power source such as a mobile phone or a notebook computer, and can be used as a large power source such as an electric power source for an electric vehicle or a hybrid automobile or a power source for a distributed power storage. gradually increase. However, in the lithium secondary battery, the composite metal oxide constituting the positive electrode contains a large amount of rare metal elements such as lithium. Therefore, there is a fear that the above-mentioned raw material supply may be increased in response to an increase in the demand for a large power source. The sodium storage battery was started to be reviewed for batteries that could solve the above supply concerns. A sodium battery can be made of a material that is abundant in supply and inexpensive, and it is expected that a large amount of power can be supplied after being put into practical use. Specific examples of the sodium battery include, for example, a positive electrode obtained by calcining a raw material having a composition ratio (Na: Mn: Co) of Na, Μ, and Co of 0.7:0.5:0.5, and a sodium metal battery, and sodium. A battery in which a metal forms a negative electrode. [Patent Document 1] JP-A-2007-287661 (Embodiment) [Problems to be Solved by the Invention] However, the conventional sodium battery has a viewpoint of the cycleability of the battery, that is, the discharge capacity at the time of repeated charging -5 - 201001783 discharge The present invention has been made to provide a sodium storage battery which is more excellent in cycleability than before. A solution to the problem is solved by the present inventors, and the present invention has been completed. <1> A sodium storage battery comprising two or more elements selected from the group consisting of Μη, Fe, Co, and Ni containing Na and M^M1, and the molar ratio of NaiM1 is a: a positive electrode of a composite metal oxide having a (a is more than 0.5 and less than 1), and a negative electrode containing a carbon material capable of occluding and removing sodium ions, and an electrolyte. <2> The sodium storage battery according to the above <1>, which further has a separator. The sodium battery according to the above-mentioned <2>, wherein the separator has a separation of a laminated porous film obtained by laminating a heat resistant porous layer containing a heat resistant resin and a porous film containing a thermoplastic resin. Device. The sodium storage battery according to any one of the above-mentioned, wherein the composite metal oxide is represented by the following formula (1),
NaaM'〇2 (1) (式中，Μ1及a各自同前述）。 < 5 >如前述< 1 >至< 4 >中任何一項所記載的鈉蓄 電池，其中M1至少含有Mn。 <6>如前述 < 丨’至；5〉中任何一項所記載的鈉蓄 201001783 電池，其中Μ1爲Μη及Co。 < 7 >如前述< 1 >至< 6 >中任何一項所記載的鈉蓄 電池，其中a爲0.6以上0.9以下之値。 發明之效果 本發明可提供，能減少鋰使用量，且重覆充放電時之 放電容量維持率比先前更高，具有優良蓄電池之循環性的 鈉蓄電池，本發明對於工業上極爲有用。 實施發明之最佳形態 <本發明之鈉蓄電池> 本發明之鈉蓄電池的特徵爲，具有含有含Na及M'M1 爲Μη、Fe、Co及Ni所成群中所選出的2種以上元素），且 Na: M1之莫耳比爲a: 1 (a爲超過0.5未達1之値）的複合金 屬氧化物之正極，與含有可吸藏及脫離鈉離子的碳材料之負 極，與電解質。 <正極> 本發明中構成正極之複合金屬氧化物爲，含有Na及 M'M1爲Mn、Fe、Co及Ni所成群中所選出的2種以上 元素），且Na: M1之莫耳比爲a: l(a爲超過0.5未達1 之値）。前述複合金屬氧化物如下述式（1)所表示之物。 NaaM102 ⑴ 201001783 (Μ及a各自同前述。） 本發明中M1就提高鈉蓄電池之容量觀點，較佳爲至 少含有Μη。Μ!更佳爲Mn及Co。Mi爲Μη及C〇時， Μη: Co之莫耳比可爲〇·5: 〇·5’另外就進—步提高鈉蓄 電池之平均放電電壓，以提高電池之能量密度觀點，Mri 之比率可大於該値（例如相對於Μη及Co(莫耳），Mn(莫耳） 爲〇 . 6以上〇. 9以下）。又一較佳實施態樣爲，μ 1爲Μιι、 Fe及Ni。此時Mn : Fe : Ni之組成（莫耳比）較佳爲1 : (0.3 至 3)· (〇,〇ι 至 2)，更佳爲 1: (0_5 至 2): (〇_1 至 1.2)。 本發明中a較佳爲0.6以上0.9以下之値，又以〇.7 以上〇_9以下之値爲佳’就進一步增加鈉蓄電池之容量觀 點更佳爲0.8，即〇 _ 7 5以上0 · 8 4以下之値。 又，複合金屬氧化物中’部分的M1可被M1以外之 金屬元素取代。藉由取代，有鈉蓄電池之電池特性提升之 情況。 <複合金屬氧化物的製造方法> 本發明的複合金屬氧化物可由，藉由焙燒具有藉焙燒 本發明之可成爲複合金屬氧化物之組成的含有金屬化合物 之混合物而得。具體上可於秤取形成一定組成般含有對應 金屬元素之含有金屬化合物混合後，將所得之混合物藉由 焙燒而製造。例如具有較佳金屬元素比之一，Na : Mn : Co = 0.7 : 0_7 : 0.3所表示之金屬元素比的複合金屬氧化物 201001783 可由’ f平取Na: Μη: Co之莫耳比可爲0.7: 0.7: 〇·3的 Na2Co3、Μη02及Co304各原料後混合，將所得之混合物 藉由焙燒而製造。 作爲可製造複合金屬氧化物用之含有金屬化合物，可 使用氧化物及高溫下分解及/或氧化時可成爲氧化物之化 合物’例如氫氧化物、碳酸鹽、硝酸鹽、鹵化物、草酸 鹽。鈉化合物較佳爲Na2C03、NaHC03、Na202，就處理 性觀點更佳爲Na2C03。錳化合物較佳爲Μη02，鐵化合物 較佳爲F e 3 Ο 4 ’鎳化合物較佳爲N i Ο，鈷化合物較佳爲 Co304。又，此等含有金屬化合物可爲水合物。 混合含有金屬化合物時可使用球磨機、V型混合機、 擾样機等工業上常用之裝置。此時之混合可爲乾式混合、 濕式混合。又利用晶析法也可得一定組成的含有金屬化合 物之混合物。 焙燒上述含有金屬化合物之混合物時可如，保持於 6 0 0 °C至1 6 0 0 °C下0 · 5小時至1 〇 〇小時進行焙燒，而可得 本發明的複合金屬氧化物。較佳之焙燒溫度範圍如6 〇 〇它 至90CTC之溫度範圍，更佳爲65(TC至8 5 0。(：之溫度範圍。 所使用的含有金屬化合物之混合物爲，高溫下可分解及/ 或氧化之化合物’例如使用氫氧化物、碳酸鹽、硝酸鹽、 齒化物、草酸鹽之情況，可保持於4 0 〇 °C至1 6 0 0 t下進行 假性焙燒形成氧化物，及去除結晶水後，再進行上述焙 燒。進行假性焙燒之環境可爲惰性氣體環境、氧化性環境 或還原性環境。又假性焙燒後可粉碎。 -9- 201001783 焙燒時之環境可爲，例如氮、氬等惰性環境；空氣、 氧、含有氧之氮、含有氧之氬等氧化性環境；及含有0.1 體積％至10體積％之氫的含氫之氮、含有0.1體積％至10 體積％之氫的含氫之氬等還原性環境。爲了於強還原性環 境進行焙燒時，也可焙燒含有適量碳的含有金屬化合物之 混合物。較佳於空氣等氧化性環境下進行焙燒。 含有金屬化合物中使用適量的氟化物、氯化物等鹵化 物時，可控制所生成的複合金屬氧化物之結晶性，及構成 複合金屬氧化物的粒子之平均粒徑。此時鹵化物也具有反 應促進劑（助溶劑）之效果。助溶劑如NaF、MnF3、FeF2、 N i F 2、C o F 2、N a C 1、Μ n C 12、F e C 12、F e C 13、N i C 12、 CoCl2、Na2C03、NaHC03、NH4C1、NH4I、B203、H3B03 等，其可作爲混合物之原料（含有金屬化合物）用，或適量 加入混合物中。又，此等助溶劑可爲水合物。 又，上述所得的複合金屬氧化物較佳爲，隨意使用球 磨機或噴射磨機等進行粉碎、洗淨、分級等以調節粒度。 又，可實施2次以上焙燒。又，複合金屬氧化物之粒子表 面可實施被覆含有3丨、人1、1'丨、丫等之無機物質等的表面 處理。又’複合金屬氧化物較佳爲，結晶構造不爲隧道構造 之物。 上述所得的複合金屬氧化物可單獨，或實施被覆等表 面處理後等，作爲正極用。 <正極之製造方法> -10- 201001783 本發明之正極含有上述複合金屬氧化物。正極可 正極集電體上附載含有上述複合金屬氧化物、導電材 合劑之正極合劑而得。 導電體如，天然黑鉛、人造黑鉛、焦碳類、碳黑 材料等。黏合劑如熱塑性樹脂，具體例如，聚偏氟 (以下也稱爲「PVDF」）、聚四氟乙烯、四氟乙烯.六 丙烯•偏氟乙烯系共聚物、六氟化丙烯.偏氟乙烯系 物、四氟化乙烯•全氟乙烯醚系共聚物等氟樹脂；及 靖、聚丙烯等聚烯烴樹脂等。正極集電體可使用A1、 不銹鋼等。 將正極合劑附載於正極集電體之方法如，加壓 法’或使用有機溶劑等漿化後塗佈於正極集電體上， 後加壓等而固著之方法。漿化時係由正極活物質、 材黏㈡劑及有機丨谷劑製作辦獎。有機溶劑如，N，N _ 基胺基丙基胺、二乙基三胺等胺系；環氧乙烷、四氫 等酸系；甲基乙基酮等酮系；乙酸甲酯等酯系；二甲 釀胺、Ν -甲基-2 -吡咯烷酮等非質子性極性溶劑等。 極合劑塗佈於正極集電體之方法如，狹縫模頭塗佈法 印塗佈法、幕塗佈法、刮刀塗佈法、照相凹版塗佈法 電噴霧法等。 <負極> 本發明中構成負極之碳材料爲，可吸藏及脫離鈉 之碳材料、本發明之碳材料可爲，能吸藏及脫離鈉 由， 及黏 等碳 乙烯 氟化 共聚 聚乙 Ni、 成型 乾燥 導電 二甲 呋喃 基乙 將正 、網 、靜 離子 子的 -11 - 201001783 任何碳材料。例如天然黑鉛、人造黑鉛、焦碳類、碳黑、 熱分解碳類、碳纖維、有機高分子化合物焙燒物等碳材料 中可吸藏及脫離鈉離子之碳材料。該碳材料更具體之例 如，特開2007-03 93 1 3號公報記載的碳材料。又，碳材料 之形狀可如’天然黑鉛般薄片狀、中位碳微球般球狀、萬 鉛化碳纖維般纖維狀，或微粉末之凝聚體等。此時碳材料 也具有導電材之效果。 <負極之製造方法> 負極可由，負極集電體上附載含有上述碳材料之負極 合劑而得。必要時負極合劑可含有黏合劑、導電材，又負 極可含有碳材料及黏合劑之混合物。黏合劑如熱塑性樹 脂，具體例如，PVDF、熱塑性聚醯亞胺、羧基甲基纖維 素、聚乙烯、聚丙烯等。 負極集電體如，Cu、Ni、不銹鋼等，就難與Na形成 合金，及另加工爲薄膜之觀點較佳爲Cu。將負極合劑附 載於負極集電體之方法可同正極爲加壓成型法，或使用溶 劑等漿化後塗佈於負極集電體上，乾燥後加壓等而固著之 方法等。 <電解質> 本發明之電解質如，NaCl〇4、NaPF6、NaAsF6、 NaSbF6、NaBF4、NaCF3S03、NaN(S02CF3)2、低級脂肪族 羧酸鈉鹽、NaAlCl4等，又可使用其二種以上之混合物。 -12- 201001783 其中較佳爲使用含有氟之NaPF6、NaAsF6、NaSbF6、 NaBF4、NaCFsSO3、及NaN(S〇2CF3)2所成群中所選出的 至少1種之物。又，本發明使用上述電解質時，一般得溶 解於有機溶劑中作爲非水電解液用。 前述有機溶劑如’碳酸丙烯酯、碳酸乙烯酯、二甲基 碳酸酯、二乙基碳酸酯、乙基甲基碳酸酯、異丙基甲基碳 酸酯、伸乙烯基碳酸酯' 4 -三氟甲基-1,3 -二茂烷-2 -酮、 1,2-二（甲氧基碳醯氧基）乙烷等碳酸酯類；二甲氧基 乙烷、1，3-二甲氧基丙烷、五氟丙基甲基醚、2,2,3,3_四氟 丙基二氟甲基醚、四氫呋喃、2 -甲基四氫呋喃等醚類；甲 酸甲酯、乙酸甲酯、丁內酯等酯類；乙腈、丁腈等腈 類；N，N-二甲基甲醯胺、Ν,Ν-二甲基乙醯胺等醯胺類；3-甲基-2 -噁唑啉酮等胺基甲酸酯類；環丁楓、二甲基亞 颯、1,3-丙烷磺內酯等含硫化合物；或上述有機溶劑另導 入氟取代基之物。一般可混合使用2種以上該有機溶劑。 又，所使用的電解質可爲固體電解質。所使用的固體 電解質可如’聚環氧乙烷系高分子化合物、含有聚有機矽 氧烷鏈或聚氧化烯鏈中至少1種以上之高分子化合物等的 有機系固體電解質。又，可使用高分子化合物中保持非水 電解液，即凝膠型之物。又可使用Na2S-SiS2、Na2S-GeS2 、NaTi2(P04)3、NaFe2(P04)3、Na2(S〇4)3、Fe2(S04)2(P〇4) 、Fe2(M〇04)3等無機系固體電解質。使用此等固體電解質 時可進一步提高鈉蓄電池之安全性。又，本發明之鈉蓄電 池所使用的電解質爲固體電解質時，固體電解質也具有後 -13- 201001783 述分離器之效果，此時將不需要分離器。 <分離器> 本發明之鈉蓄電池又以另具有分離器爲佳。所使用的 分離器可如，由聚乙烯、聚丙烯等聚烯烴樹脂、氟樹脂、 含氮芳香族聚合物等材質形成，具有多孔質薄膜、不織 布、織布等形態之材料。又，可爲使用2種以上該材質之 單層或層合分離器、分離器如，特開2000-30686號公 報、特開平1 0-3 247 5 8號公報等記載的分離器、分離器之 厚度就提升電池之體積能量密度，減少內部電阻之觀點， 又以保有機械強度下盡可能薄化爲佳。分離器之厚度一般 以5至200μηι爲佳，更佳爲5至40μιη。 分離器較佳爲含有熱塑性樹脂之多孔質薄膜。蓄電池 中分離器較佳爲，具有配置於正極與負極之間，當電池內 流竄造成正極-負極間短路等之異常電流時，可遮斷電流 阻止過大電流流動（關閉）之效果。此時的關閉係指，超過 一般使用溫度時會閉塞分離器之多孔質薄膜的微細孔。關 閉後既使電池內之溫度上升至某程度高溫，也不會因該溫 度造成膜破裂，可維持關閉狀態，換言之具有高耐熱性。 該類分離器如，耐熱多孔層及多孔質薄膜層合而得的層合 多孔質薄膜等具有耐熱材料之多孔質薄膜，較佳如，含有 耐熱樹脂之耐熱多孔層及含有熱塑性樹脂之多孔質薄膜層 合而得的層合多孔質薄膜，使用該類具有耐熱材料之多孔 質薄膜的分離器，可進一步防止本發明蓄電池之熱破膜。 -14- 201001783 又耐熱多孔層可層合於多孔質薄膜雙面上。 <層合多孔質薄膜分離器> 下面將說明由層合多孔質薄膜形成的分離器。該分離 器之厚度一般爲5μιη以上40μιη以下，較佳爲20μιη以 下。又，以耐熱多孔層之厚度爲Α(μιη)，以多孔質薄膜之 厚度爲Β(μιη)時，Α/Β之値較佳爲〇」以上1以下。又， 該分離器就離子透過性之觀點，克勒法之透氣度較佳爲 50至300秒/l〇〇cc，更佳爲50至200秒/ l〇〇cc。該分離 器之空孔率一般爲30至80體積％，較佳爲40至70體積 %。 (耐熱多孔層） 層合多孔質薄膜中的耐熱多孔層較佳爲，含有耐熱樹 脂。爲了進一步提高離子透過性較佳爲，耐熱多孔層之厚 度爲Ιμηι以上ΙΟμιη以下，更佳爲Ιμπι以上5μπι以下’ 特佳爲Ιμ.ιη以上4μηι以下之薄型耐熱多孔層。又’耐熱 多孔層具有微細孔，該孔之孔徑（直徑）一般爲3μιη以下， 較佳爲1 μιη以下。另外耐熱多孔層可含有後述塡料。 又，耐熱多孔層可由無機粉末形成。 耐熱多孔層所含的耐熱樹脂如，聚醯胺、聚醯亞胺、 聚醯胺醯亞胺、聚碳酸酯、聚縮醛、聚楓、聚伸苯基硫化 物、聚醚酮、芳香族聚酯、聚醚颯、聚醚醯亞胺、就進一 步提高耐熱性觀點較佳爲聚醯胺、聚醯亞胺、聚醯胺醯亞 -15- 201001783 胺、聚醚碾、聚醚醯亞胺'更佳爲聚醯胺、聚醯亞胺、聚 醯胺醯亞胺。耐熱樹脂更佳爲芳香族聚醯胺（對位配向芳 香族聚醯胺、間位配向芳香族聚醯胺）、芳香族聚醯亞 胺、芳香族聚醯胺醯亞胺等含氮芳香族聚合物，特佳爲芳 香族聚醯胺，最佳爲對位配向芳香族聚醯胺（以下有稱爲 「對芳香族聚醯胺」）。又，耐熱樹脂可如聚-4-甲基戊烯-1、環狀烯烴系聚合物。使用此等耐熱樹脂可提高耐熱 性，即可提高熱破膜溫度。 熱破膜溫度依存於耐熱樹脂之種類，可因應使用用 途、使用目的選擇使用。一般熱破膜溫度爲160°C以上。 所使用的耐熱樹脂爲上述含氮芳香族聚合物時，可將熱破 膜溫度控制於400 °C，使用聚-4-甲基戊烯-1時可控制於 2 5 0 °C，使用環狀烯烴系聚合物時可控制3 0 0 °C。又’耐熱 多孔層係由無機粉末形成時，熱破膜溫度例如可控制於 5 0 0 °C以上。 上述對芳香族聚醯胺爲，由對位配向芳香族二胺與對 位配向芳香族二羧酸鹵化物縮合聚合而得之物，實質上係 由以芳香族環之對位或基於其之配向位（例如，4,4 '-伸聯 苯酯、1,5-萘、2,6 -萘等與相反方向同軸或平行延伸的配 向位）鍵結醯胺鍵而得之重覆單位形成。對芳香族聚醯胺 中，對位配向型或具有基於對位配向之構造的對芳香族聚 醯胺具體例如，聚（對伸苯基對苯二甲醯胺）、聚（對苯醯 胺）、聚（4,4'_苯醯苯胺對苯二甲醯胺）、聚（對伸苯基_4，V-伸聯苯基二羧酸醯胺）、聚（伸苯基-2,6-萘二羧酸醯胺）、 -16- 201001783 聚（2-氯-對伸苯基對苯二甲醯胺）、對伸 /2,6-二氯對伸苯基對苯二甲醯胺共聚物 上述芳香族聚醯亞胺較佳爲，由芳 胺縮聚合製造之全芳香族聚醯亞胺。二 均苯四甲酸二酐、3,3',4,4'-二苯基 3,3、4,4'-二苯甲酮四羧酸二酐、2,2’-雙 六氟丙烷、3,3',4,4’-聯苯基四羧酸二酐 二苯胺、對伸苯基二胺、二苯甲酮二胺 胺、3，3 '-二胺基二苯甲酮、3，3 ’ -二胺基 二胺等。又，適用可溶於溶劑之聚醯亞 如，3,3',4,4’-二苯基颯四羧酸二酐與芳 物的聚醯亞胺。 上述芳香族聚醯胺醯亞胺如，使用 香族二異氰酸酯由其縮合聚合而得之物 酐及芳香族二異氰酸酯由其縮合聚合而 羧酸之具體例如，間苯二甲酸、對苯二 二酸酐之具體例如，偏苯三酸酐等。芳 具體例如，4,4'-二苯基甲烷二異氰酸酯 異氰酸酯、2,6 -伸甲苯基二異氰酸酯、 酸酯、m-伸二甲苯基二異氰酸酯等。 耐熱多孔層含有耐熱樹脂時，耐熱 以上塡料。耐熱多孔層所含的塡料可爲 機粉末或其混合物中選出之物。構成塡 徑較佳爲Ο.Οίμιη以上Ιμιη以下。塡 苯基對苯二甲醯胺 等。 香族之二酸酐與二 酸酐之具體例如’ 颯四羧酸二酐' ^ (3,4-二羧基苯基） 等。二胺如’氧化 ' 3 , 3 '-伸甲基二苯 二苯基颯、1，5’-萘 胺，該類聚醯亞胺 香族二胺之聚縮合 芳香族二羧酸及芳 、使用芳香族二酸 得之物。芳香族二 甲酸等。又芳香族 香族二異氰酸酯之 、2,4-伸甲苯基二 鄰伸甲苯基二異氰 多孔層可含有一種 ，由有機粉末、無 料之粒子的平均粒 料之形狀如，略球 -17- 201001783 狀、板狀、柱狀、針狀、晶鬚狀、纖維狀等，可使用任何 一種粒子，但就易形成均勻孔之觀點較佳爲略球狀粒子。 略球狀粒子如，粒子之長寬比（粒子之長徑/粒子之短徑）爲 1以上1.5以下之値的粒子。粒子之長寬比可由電子顯微 鏡照片測定。 塡料用之有機粉末如，苯乙烯、乙烯酮、丙烯腈、甲 基丙烯酸甲酯、甲基丙烯酸乙酯、縮水甘油基甲基丙烯酸 酯、縮水甘油基丙烯酸酯、丙烯酸甲酯等單獨或2種以上 共聚物：聚四氟乙烯、4氟化乙烯-6氟化丙烯共聚物、4 氟化乙烯-乙烯共聚物、聚亞乙烯基氟化物等氟系樹脂； 三聚氰胺樹脂；尿素樹脂；聚烯烴；聚甲基丙烯酸酯等有 機物形成的粉末。有機粉末可單獨使用或2種以上混合使 用。此等有機粉末中就化學安定性較佳爲聚四氟乙烯粉 末。 塡料用的無機粉末如，金屬氧化物、金屬氮化物、金 屬碳化物、金屬氫氧化物、碳酸鹽、硫酸鹽等無機物形成 的粉末，其中又以由導電性較低之無機物形成的粉末爲 佳。具體例如，由氧化鋁、二氧化矽、二氧化鈦、硫酸鋇 或碳酸鈣等形成的粉末。無機粉末可單獨使用或2種以上 混合使用。此等無機粉末中就化學安定性較佳爲氧化鋁粉 末。又以構成塡料之全部粒子爲氧化鋁粒子爲佳，更佳爲 構成塡料之全部粒子爲氧化鋁粒子，且部分或全部爲略球 狀之氧化鋁粒子。又，由無機粉末形成耐熱多孔層時可使 用上述無機粉末例，必要時可混用黏合劑。 -18 - 201001783 耐熱多孔層含有耐熱樹脂時，塡料之含量會因塡料材 質之比重而異，例如構成塡料之全部粒子爲氧化鋁粒子 時’以耐熱多孔層之總量量爲100時，塡料之重量一般爲 5以上95以下，較佳爲20以上95以下，更佳爲30以上 90以下。此範圍內可依存於塡料材質之比重適當設定。 (多孔質薄膜） 層合多孔質薄膜中，多孔質薄膜較佳爲具有微細孔且 可關閉之物。此時多孔質薄膜爲，含有熱塑性樹脂。該多 孔質薄膜之厚度一般爲3至30μηι，較佳爲3至25μιη。多 孔質薄膜同上述耐熱多孔層爲，具有微細孔，且孔徑一般 爲3μπι以下，較佳爲Ιμιη以下。多孔質薄膜之空孔率— 般爲30至80體積％，較佳爲40至70體積％，非水電解 質蓄電池中，超過一般使用溫度時，多孔質薄膜會因構成 其之熱塑性樹脂軟化，而閉塞微細孔。 多孔質薄膜所含的熱塑性樹脂如，8 0至1 8 0 °C下可軟 化之物，其可由非水電解質蓄電池中不溶於電解液之物中 選擇。具體之熱塑性樹脂如’聚乙烯、聚丙烯等烯烴樹 脂、熱塑性聚胺基甲酸乙酯樹脂，又可使用其2種以上之 混合物。爲了以更低溫度軟化而關閉，熱塑性樹脂較佳爲 含有聚乙烯。聚乙烯之具體例如，低密度聚乙烯、高密度 聚乙烯、線狀聚乙烯等聚乙烯’又如分子量1〇〇萬以上之 超高分子量聚乙烯。爲了提高多孔質薄膜之突刺強度’，熱 塑性樹脂較佳爲至少含有超高分子量之聚乙烯。又，就多 -19- 201001783 孔質薄膜之製造面，熱塑性樹脂較佳爲含有由低分子_ (重量平均分子量，1萬以下）之聚烯烴形成的蠟。 又，具有不同於上述層合多孔質薄膜之耐熱材料的# 孔質薄膜如，由耐熱樹脂及/或無機粉末形成的多孔質薄 膜、聚烯烴樹脂或熱塑性聚胺基甲酸乙酯樹脂等熱塑性樹 脂薄膜中分散耐熱樹脂及/或無機粉末的多孔質薄膜。jtt 時之耐熱樹脂、無機粉末可如上述之物。 <鈉蓄電池之製造方法> 本發明之鈉蓄電池具有分離器時例如可由，依序層合 上述正極、分離器及負極後回卷得到電極群，將該電極群 收納於電池罐內，使電極群含浸由含有電解質之有機溶劑 形成的非水電解液而得。又，不具有分離器時例如可由， 依序層合正極、固體電解質及負極後回卷得到電極群，將 電極群收納於電池罐內而得。 電極群之形狀如，將該電極群之回卷軸的垂直方向切 斷時，剖面爲圓、橢圓、長圓、長方形、缺角之長方形等 形狀。又，電池形狀如，紙片型、硬幣型、圓筒型、角型 等形狀。 上述所得的鈉蓄電池可具有比先前更大的重覆充放電 時之放電容量維持率，而具有優良循環性，又可抑制負極 表面生成鈉松林石，而具有優良的電池用安定性。 【實施方式】 201001783 實施例 下面將以實施例更詳細說明本發明，但本發明非限於 此例。 製造例1 以Na. Mn: Co之莫耳比爲0.7: 0.5: 0.5方式种取 含有金屬化合物用的碳酸鈉（NazCCh :和光純藥工業股份 公司製：純度99.8%)、氧化錳（IV)(Mn02 :高純度化學硏 究所股份公司製：純度99.9%)，及四氧化三鈷（C〇3〇4 :正 同化學工業股份公司製：純度99%)後，以乾式球磨機混 合4小時’得含有金屬化合物之混合物。將所得的含有金 屬化合物之混合物塡入氧化鋁皿中，使用電爐於空氣環境 中加熱至800 °C後保持2小時，得複合金屬氧化物E1。以 複合金屬氧化物E1:導電材：黏合劑=85: 10: 5(重量比） 之組成各自秤取複合金屬氧化物E1、導電材之乙炔碳黑 (電氣化學工業股份公司製），及黏合劑之PVDF(庫雷哈股 份公司製 PolyVinylidene DiFluoridePolyflon)後，首先以 瑪瑙硏鉢、充分混合複合金屬氧化物及乙炔碳黑後，將適 量的N-甲基-2-吡咯烷酮（NMP ··東京化成工業股份公司製） 加入該混合物中，再加入P V D F持續均句混合而淤漿化。 使用塗佈輥將厚達1 ΟΟμιη之所得淤漿塗佈於集電體用的 厚40μιη之鋁箔上，放入乾燥機內，去除ΝΜΡ的同時充 分乾燥，得正極片1。以電極穿孔機將正極片1穿孔使直 徑爲1.5cm後，以手壓機充分壓合，得正極1。 -21 - 201001783 比較例1 以鋁箔朝下方式將製造例1所得的正極1置於硬幣單 元（寶泉股份公司製）之下側部分凹處後，組合非水電解液 之1M的NaClCU/碳酸丙烯酯、分離器之聚丙烯多孔質膜 (厚20 μιη)，及負極之金屬鈉（艾得里公司製），製作鈉蓄電 池1。又組裝試驗電池時係於氬環境下之工具箱內進行。 使用鈉蓄電池1以下述條件實施定電池充放電試驗。 充放電條件： 充電爲’以0.1C級速（10小時內完全充電之速度）進 行CC (恆電流：定電流）充電至4.0V。放電爲，以同該充 電速度之速度進行CC放電，至電壓1.5V後停止。其後 充放電循環爲’以同該充電速度之速度進行，同第1次循 環於充電電壓4.0V、放電電壓1.5V時停止。 該鈉蓄電池1之定電流充放電試驗結果爲，相對於第 2次循環之放電容量，第10次循環之放電容量（放電容量 維持率）爲較低的80%。 實施例1 (1)製造碳材料 氮氣流下將間苯二酚200g、甲基醇1.5L'苯甲醛 1 94g放入四口燒瓶中，冰冷下攪拌的同時滴入3 6%鹽酸 3 6.8g °結束滴液後升溫至65。(：，同溫下保溫5小時。將 水1 L加入所得的聚合反應混合物中，濾取沈澱物後，以 -22 - 201001783 水洗淨濾液至中性，再乾燥，得有機高分子化合物之四苯 基杯[4]間苯二酚（PCRA)294g。 將PCRA放入旋轉窖爐中’空氣環境下以3 00°c加熱 1小時後，以氬取代旋轉窖爐中的空氣，再以1 〇 〇 〇。〇：加熱 4小時。其次以球磨機（美諾烏製球體，28rpm，5分鐘）粉 碎，得有機高分子化合物焙燒物之碳材料C1。該粉末狀之 碳材料C1因未接觸金屬，故幾乎未含有含金屬離子之金 屬。 (2) 製造負極 以碳材料C1:黏合劑=95:5(重量比）之組成秤取碳材 料C1及黏合劑之聚偏氟乙烯（PVDF)，將黏合劑溶解於N-甲基吡喀烷酮（NMP)後，加入碳材料C1得凝膠化之物。使 用塗佈輥將厚達ΙΟΟμιη之該物塗佈於集電體用的厚ΙΟμπι 之銅箔上，放入乾燥機去除NMP的同時充分乾燥，得負極 片。以電極穿孔機將該負極片穿孔使直徑爲1 .5cm後，以手 壓機充分壓合，得負極1。 (3) 製造鈉蓄電池 以鋁箔朝下方式將製造例1所得的正極1置於硬幣單 元（寶泉股份公司製）之下側部分凹處後’組合非水電解液之 1M的NaC104/碳酸丙烯酯、分離器之聚丙烯多孔質膜（厚 20 μιη)，及負極1 ;製作鈉蓄電池2。又，組裝試驗電池時 係於氬氣下之工具箱內進行。 -23- 201001783 使用鈉蓄電池2以同比較例1之條件實施定電流充放 電試驗。該鈉蓄電池2之定電流充放電試驗結果爲’相對 於第2次循環之放電容量，第10次循環之放電容量（放電 容量維持率）爲極高之 1〇7%，故爲超過100%之値。又， 既使循環使用該鈉蓄電池2，也可得同後述鈉蓄電池4之 效果。 實施例2 (1)製造正極 以 Na: Mn: Fe: Ni 之莫耳比爲 〇·7: 0.333: 0.333: 0.3 3 3之方式秤取含有金屬化合物用的碳酸鈉（Na2C03 :和 光純藥工業股份公司製：純度99.8%)、氧化錳（IV)(Mn02 :高純度化學硏究所股份公司製：純度9 9.9 % )，氧化鐵 (11、111)( F e 3 Ο 4):高純度化學硏究所股份公司製：純度 99%)及氧化鎳（II)(NiO :高純度化學硏究所股份公司製： 純度9 9 % )，以乾式球磨機混合4小時後，得含有金屬化 合物之混合物。將所得的含有金屬化合物之混合物塡入氧 化鋁皿中，使用電爐於空氣環境中加熱至8 0 0 t：後保持2 小時’得複合金屬氧化物E 2。以複合金屬氧化物e 2 :導 電體：黏合劑==8 5 : 1 0 : 5 (重量比）之組成各自秤取複合金 屬氧化物E2、導電材之乙炔碳黑（電氣化學工業股份公司 製）’及黏合劑之 PVDF(庫雷哈股份公司製 PolyVinylidene DiFluoridePolyflon)後，首先以瑪瑙硏鉢 充分混合複合金屬氧化物及乙炔碳黑後，將適量的N—甲 -24- 201001783 基-2-吡咯烷酮（NMP :東京化成工業股份公司製）加入該混 合物中，再加入PVDF持續均勻混合而淤漿化。使用塗佈 輥將厚達ΙΟΟμιη之所得淤漿塗佈於集電體用的厚40μιη之 鋁箔上，放入乾燥機去除ΝΜΡ的同時充分乾燥，得正極 片2。以電極穿孔機將該正極片2穿孔使直徑爲1 .5cm 後，以手壓機充分壓合，得正極2。 (2)製造鈉蓄電池 以鋁箔朝下之方式將正極2置於硬幣單元（寶泉股份公 司製）之下側部分凹處後，組合非水電解液之1 Μ的NaC104/ 碳酸丙烯酯、分離器之聚丙烯多孔質膜（厚20μπ〇，及同實 施例1之負極1，製作鈉蓄電池3。又，組裝試驗電池時係 於氬環境下之工具箱內進行。 使用鈉蓄電池3以同比較例1之條件實施定電流充放 電S式驗。該鈉蓄電池3之定電流充放電試驗結果爲，相對 於第2次循環之放電容量’第次循環之放電容量（放電 容量維持率）爲1 1 1 %，又’再進行1 〇次循環（第1 1次循 環至第20次循環），結果相對於第2次循環之放電容量， 第20次循環之放電容量（放電容量維持率）爲η5 %，故均 爲超過100%之極高値。既使再重覆循環使用該鈉蓄電池 3，也可得同後述鈉蓄電池4之效果。 實施例3 (1)製造負極 -25- 201001783 以碳材料：黏合劑=95 : 5(重量比）之組成秤取有機高 分子化合物焙燒物之碳材料，及黏合劑之聚偏氟乙烯 (PVDF)，將黏合劑溶解於N-甲基吡咯烷酮（NMP)後，加 入該碳材料得淤漿化之物，使用塗佈輥將厚達100μιη之 該物塗佈於集電體用的厚10 μηα之銅箔上，放入乾燥機去 除ΝΜΡ的同時充分乾燥，得負極片。以電極穿孔機將該 負極片穿孔爲直徑1.5cm後，以手壓機充分壓合，得負極 2 ° (2)製造鈉蓄電池 以鋁箔朝下之方式將同實施例2之正極置2於硬幣單 元（寶泉股份公司製）之下側部分凹處後，組合非水電解液 之1M的NaC104/碳酸丙烯酯、分離器之聚丙烯多孔質膜 (厚20 μιη)，及負極2，製作鈉蓄電池4。又’組裝試驗電 池時係於氬環境下之工具箱內進行。 使用鈉蓄電池4以同比較例1之條件實施定電流充放 電試驗。該鈉蓄電池4之定電流充放電試驗結果爲，相對 於第2次循環之放電容量，第10次循環之放電容量（放電 容量維持率）爲108%，又再循環10次（第1 1次循環至第 2〇次循環）後，相對於第2循環之放電容量’第20次循 環之放電容量（放電容量維持率）爲10 7% ’故均爲超過 100%之極高値。 又，再以下述條件對上述循環進行20次定電流充放 電後的鈉蓄電池4實施充放電加速試驗（第2 1次循環至第 5〇〇次循環）。 -26- 201001783 充放電加速試驗條件： 充電爲，以1.0C級速（1小時內完全充電之速度）進行 CC充電至4.0V。放電爲，以同該充電速度之速度進行 CC放電至電壓1.5V後停止。重覆19次該1.0C級速的定 電流充放電試驗後，以0.1 C級速（1 〇小時內完全充電之速 度）進行CC充電至4.0V，再以同該充電速度之速度進行 CC放電至電壓1.5V後停止，而完成1次0.1C級速的定 電流充放電試驗。重覆24次（合計480次）由前述1.0C級 速1 9次及0 . 1 C級速1次組合的合計2 0次定電流充放電 試驗’而完成充放電加速試驗。 上述進行20次定電流充放電後之鈉蓄電池4的上述 充放電加速試驗結果爲，相對於第2次循環之放電容量， 第5〇〇次循環之放電容量（放電容量維持率）爲極高値之 96%。 對上述進行5 0 0次定電流充放電後之鈉蓄電池4再重 覆進行25次（合計500次）’由上述i.〇c級速19次及 〇. 1C級速1次組合的合計2〇次定電流充放電試驗，而完 成充放電加速試驗。結果相對於第2次循環之放電容量， 第1〇〇〇次循環之放電容量（放電容量維持率）爲極高値之 8 0%。 實施例4 (1)製造正極 0.3 3 3 ： 以 Na : Mn : Fe : Ni 之莫耳比爲 0.8 : 0.3 3 3 : -27- 201001783 0.333之方式砰取含有金屬化合物用的碳酸鈉（Na2c〇3 :和 光純藥工業股份公司製：純度99_8%)、氧化錳（iv)(Mn02 :高純度化學硏究所股份公司製：純度9 9.9 %)，氧化鐵 (II、III) (Fe3〇4):高純度化學硏究所股份公司製：純度 99%)及氧化鎳（II)(NiO:高純度化學硏究所股份公司製： 純度9 9 %)’以乾式球磨機混合4小時，得含有金屬化合 物之混合物。將所得的含有金屬化合物之混合物塡入氧化 鋁皿中，使用電爐於空氣環境中加熱至8 0 0 °C後保持2小 時，得複合金屬氧化物E3。以複合金屬氧化物E3:導電 材：黏合劑=85 : 10 : 5(重量比）之組成各自秤取複合金屬 氧化物E3、導電體之乙炔碳黑（電氣化學工業股份公司 製），及黏合劑之 PVDF(庫雷哈股份公司製 PolyVinylidene DiFluoridePolyflon)後，首先以瑪瑙硏鉢 充分混合複合金屬氧化物及乙炔碳黑後，將適量的N -甲 基-2-吡咯烷酮（NMP :東京化成工業股份公司製）加入該混 合物中，再加入PVDF持續均勻混合而淤漿化。使用塗佈 輥將厚達ΙΟΟμηι之所得淤漿塗佈於集電體用的厚40μηι之 鋁箔上，放入乾燥機去除Ν Μ Ρ的同時充分乾燥後得正極 片3。以電極穿孔機將該正極片3穿孔使直徑爲1.5cm 後，以手壓機充分壓合，得正極3。 (2 )製造鈉蓄電池 以鋁箔朝下之方式將正極3置於硬幣單元（寶泉股份公 司製）之下側部分凹處後，組合非水電解液之的NaC104/ 201001783 碳酸丙烯酯、分離器之聚丙烯多孔質膜（厚20μιη)，及同實 施例3之負極2，製作鈉蓄電池5。又，組裝試驗電池時係 於氬環境下之工具箱內進行。 使用鈉蓄電池5以同比較例1之條件實施定電流充放 電試驗。該鈉蓄電池5之定電流充放電試驗結果爲，相對 於第2次循環之放電容量，第1 〇次循環之放電容量（放電 容量維持率）爲極高之105%，故爲超過100%之値。又， 既使再循環使用鈉蓄電池5，也可得同前述鈉蓄電池4之 效果。 實施例5 (1) 製造正極 除了使用Na: Mn: Fe: Ni之莫耳比爲0.9: 0.333 的含有 金屬化 合物外 ，其 他同 實施例 4， 得 實施例5之複合金屬氧化物E4。以實施例5之複合金屬氧 化物E4爲鈉蓄電池用之正極物質，同實施例4得正極片 4。以電極穿孔機將該正極片4穿孔使直徑爲1.5cm後， 以手壓機充分壓合，得正極4。 (2) 製造鈉蓄電池 使用實施例5之正極4，同實施例4製作鈉蓄電池 6。又，組裝試驗電池時係於氬環境下之工具箱內進行。 使用鈉蓄電池6以同比較例1之條件實施定電流充放 電試驗。該鈉蓄電池6之定電流充放電試驗結果爲，相對於 -29- 201001783 第2次循環之放電容量，第10次循環之放電容量（放電容量 維持率）爲極高之105%，故爲超過100%之値。又’既使再 循環使用鈉蓄電池6，也可得同前述鈉蓄電池4之效果。 製造例2(製造層合多孔質薄膜） (1) 製造耐熱多孔層用塗佈液 將氯化鈣272.7g溶解於NMP4200g中’加入對苯二 胺132.9g完全溶解後，緩緩將對苯二甲酸二氯化物 2 4 3.3 g加入所得溶液進行聚合，得對芳香族聚醯胺’以 NMP稀釋後，得濃度2.0重量％之對芳香族聚醯胺。將塡 料用合計4g的第1氧化鋁粉末2g(日本艾洛吉公司製， 氧化鋁C，平均粒徑0.02μπ〇及第2氧化鋁粉末2g(住友 化學股份公司製斯密可，AA03，平均粒徑0.3μιη)加入所 得的對芳香族聚醯胺溶液1 〇〇g中，以奈米器處理3次 後，以1 0 0 0 m e s h之金網過濾，減壓下脫泡後得耐熱多孔 層用淤漿狀塗佈液。相對於對芳香族聚醯胺及氧化鋁粉末 之合計重量，氧化鋁粉末（塡料）重量爲67重量％。 (2) 製造及評估層合多孔質薄膜 所使用之多孔質薄膜爲聚乙烯製多孔質薄膜（膜厚 12μηι)，透氣度140秒/ lOOcc’平均孔徑O.lpm，空孔率NaaM'〇2 (1) (wherein Μ1 and a are the same as above). < 5 > as described above < 1 > to The sodium storage battery according to any one of the above, wherein M1 contains at least Mn. <6> as described above The sodium storage 201001783 battery according to any one of the above, wherein Μ1 is Μη and Co. < 7 > as described above < 1 > to The sodium storage battery according to any one of the above, wherein a is 0.6 or more and 0.9 or less. EFFECTS OF THE INVENTION The present invention can provide a sodium storage battery which can reduce the amount of lithium used and which has a higher discharge capacity retention rate during charge and discharge than before, and which has excellent battery cycle characteristics, and is extremely useful industrially. Best form for implementing the invention <Sodium battery according to the present invention> The sodium battery of the present invention is characterized in that it has two or more elements selected from the group consisting of 含η, Fe, Co, and Ni containing Na and M'M1, and Na: The positive electrode of the composite metal oxide having a molar ratio of M1 of a: 1 (a is more than 0.5 and less than 1), and a negative electrode containing a carbon material capable of occluding and removing sodium ions, and an electrolyte. <Positive Electrode> The composite metal oxide constituting the positive electrode of the present invention contains Na and M'M1 as two or more elements selected from the group consisting of Mn, Fe, Co, and Ni, and Na: M1 The ear ratio is a: l (a is more than 0.5 and less than 1). The composite metal oxide is represented by the following formula (1). NaaM102 (1) 201001783 (Μ and a are the same as described above.) In the present invention, M1 is preferably at least Μη from the viewpoint of increasing the capacity of the sodium storage battery. Oh! More preferably Mn and Co. When Mi is Μη and C〇, the molar ratio of Μη: Co can be 〇·5: 〇·5'. In addition, the average discharge voltage of the sodium battery is increased to improve the energy density of the battery. The ratio of Mri can be It is larger than the 値 (for example, relative to Μη and Co (mole), Mn (mole) is 〇. 6 or more 〇. 9 or less). In still another preferred embodiment, μ 1 is Μι, Fe, and Ni. At this time, the composition (mol ratio) of Mn : Fe : Ni is preferably 1: (0.3 to 3) · (〇, 〇ι to 2), more preferably 1: (0_5 to 2): (〇_1 to 1.2). In the present invention, a is preferably 0.6 or more and 0.9 or less, and more preferably 〇.7 or more and 〇9 or less. The viewpoint of further increasing the capacity of the sodium storage battery is preferably 0.8, that is, 〇_7 5 or more. 8 4 or less. Further, M1 of the 'portion in the composite metal oxide may be substituted with a metal element other than M1. By replacing, there is a case where the battery characteristics of the sodium battery are improved. <Method for Producing Composite Metal Oxide> The composite metal oxide of the present invention can be obtained by calcining a mixture containing a metal compound which can be a composition of the composite metal oxide of the present invention by calcination. Specifically, it can be produced by mixing and mixing a metal-containing compound containing a corresponding metal element in a certain composition, and then baking the obtained mixture. For example, the composite metal oxide 201001783 having a ratio of metal to element represented by Na: Mn : Co = 0.7 : 0_7 : 0.3 can be obtained by 'f taking Na: Μ: Co can have a molar ratio of 0.7: 0.7: The raw materials of Na2Co3, Μη02 and Co304 of 〇·3 were mixed, and the obtained mixture was produced by baking. As a metal-containing compound for producing a composite metal oxide, an oxide and a compound which can be an oxide when decomposed and/or oxidized at a high temperature can be used, such as hydroxide, carbonate, nitrate, halide, oxalate. . The sodium compound is preferably Na2C03, NaHC03 or Na202, and is more preferably Na2C03 from the viewpoint of handleability. The manganese compound is preferably Μη02, the iron compound is preferably F e 3 Ο 4 ', and the nickel compound is preferably N i Ο, and the cobalt compound is preferably Co304. Further, these metal-containing compounds may be hydrates. When mixing a metal compound, a device commonly used in the industry such as a ball mill, a V-type mixer, or a scrambler can be used. The mixing at this time may be dry mixing or wet mixing. Further, a mixture of metal compounds having a certain composition can be obtained by a crystallization method. The calcination of the above metal compound-containing mixture can be carried out, for example, at 60 ° C to 1 600 ° C for 0.5 hours to 1 hour, to obtain a composite metal oxide of the present invention. Preferably, the calcination temperature ranges from 6 〇〇 to 90 CTC, more preferably 65 (TC to 850). (: The temperature range. The mixture containing the metal compound is decomposable at a high temperature and/or The oxidized compound can be pseudo-calcined to form an oxide and removed by using, for example, a hydroxide, a carbonate, a nitrate, a dentate or an oxalate at 40 ° C to 1 600 Torr. After the crystallization of water, the above calcination is carried out. The environment in which the pseudo-baking is performed may be an inert gas atmosphere, an oxidizing environment or a reducing environment, and may be pulverized after pseudo-baking. -9- 201001783 The environment during roasting may be, for example, nitrogen. An inert environment such as argon; an oxidizing environment such as air, oxygen, nitrogen containing oxygen, argon containing oxygen; and hydrogen containing nitrogen containing 0.1% by volume to 10% by volume of hydrogen, containing 0.1% by volume to 10% by volume A reducing atmosphere such as hydrogen-containing argon or the like. In order to perform calcination in a strong reducing atmosphere, a mixture containing a metal compound containing an appropriate amount of carbon may be calcined, preferably in an oxidizing atmosphere such as air. When an appropriate amount of a halide such as a fluoride or a chloride is used as the compound, the crystallinity of the produced composite metal oxide and the average particle diameter of the particles constituting the composite metal oxide can be controlled. At this time, the halide also has a reaction accelerator. (Cosolvent) effect. Cosolvents such as NaF, MnF3, FeF2, N i F 2, C o F 2, N a C 1 , Μ n C 12, F e C 12, F e C 13 , N i C 12 And CoCl2, Na2C03, NaHC03, NH4C1, NH4I, B203, H3B03, etc., which may be used as a raw material (containing a metal compound) of the mixture, or may be added to the mixture in an appropriate amount. Further, these co-solvents may be hydrates. Preferably, the composite metal oxide is pulverized, washed, classified, etc. by a ball mill or a jet mill to adjust the particle size. Further, the calcination may be carried out twice or more. Further, the surface of the composite metal oxide particles may be coated. It is a surface treatment containing an inorganic substance such as 3 Å, human 1, 1 '丨, 丫, etc. Further, the composite metal oxide is preferably a structure in which the crystal structure is not a tunnel structure. The composite metal oxide obtained above may be used alone. Or implementation After the surface treatment such as coating, it is used as a positive electrode. <Manufacturing method of positive electrode> -10-201001783 The positive electrode of the present invention contains the above composite metal oxide. The positive electrode positive electrode current collector is obtained by supporting a positive electrode mixture containing the above composite metal oxide and a conductive material mixture. Electrical conductors such as natural black lead, artificial black lead, coke, carbon black materials, and the like. The binder is, for example, a thermoplastic resin, specifically, for example, polyvinylidene fluoride (hereinafter also referred to as "PVDF"), polytetrafluoroethylene, tetrafluoroethylene, hexapropylene/vinylidene fluoride copolymer, hexafluoropropylene, vinylidene fluoride. A fluororesin such as a tetrafluoroethylene or a perfluorovinyl ether copolymer; and a polyolefin resin such as Jing or polypropylene. As the positive electrode current collector, A1, stainless steel or the like can be used. The method of attaching the positive electrode mixture to the positive electrode current collector is carried out by a press method or a slurry obtained by slurrying with an organic solvent, followed by application to a positive electrode current collector, followed by pressurization or the like. In the slurrying process, the positive active material, the material (2) agent and the organic glutinous agent are produced. The organic solvent is an amine such as N,N-aminopropylamine or diethyltriamine; an acid such as ethylene oxide or tetrahydrogen; a ketone system such as methyl ethyl ketone; and an ester such as methyl acetate. An aprotic polar solvent such as dimethylamine or Ν-methyl-2-pyrrolidone. The method of applying the polarener to the positive electrode current collector is, for example, a slit die coating method, a curtain coating method, a knife coating method, a gravure coating method, an electrospray method, or the like. <Negative Electrode> The carbon material constituting the negative electrode in the present invention is a carbon material capable of occluding and desorbing sodium, and the carbon material of the present invention can be occluded and desorbed from sodium, and fluorinated copolypolymer of carbon and the like. Ethylene Ni, shaped dry conductive dimethylfuranyl b will be positive, net, static ion -11 - 201001783 any carbon material. For example, carbon materials such as natural black lead, artificial black lead, coke, carbon black, thermal decomposition carbon, carbon fiber, and organic polymer compound calcined material can absorb and remove sodium ions. More specifically, the carbon material is a carbon material described in Japanese Laid-Open Patent Publication No. 2007-03 931-3. Further, the shape of the carbon material may be, for example, a natural black lead-like flaky shape, a medium carbon microsphere-like spherical shape, a 10,000-lead carbon fiber-like fibrous shape, or a fine powder aggregate. At this time, the carbon material also has the effect of a conductive material. <Manufacturing Method of Negative Electrode> The negative electrode can be obtained by supporting a negative electrode mixture containing the above carbon material on the negative electrode current collector. If necessary, the negative electrode mixture may contain a binder, a conductive material, and the negative electrode may contain a mixture of a carbon material and a binder. The binder is, for example, a thermoplastic resin, specifically, for example, PVDF, thermoplastic polyimide, carboxymethylcellulose, polyethylene, polypropylene, or the like. The negative electrode current collector such as Cu, Ni, stainless steel or the like is difficult to form an alloy with Na, and is preferably Cu from the viewpoint of being processed into a film. The method of attaching the negative electrode mixture to the negative electrode current collector may be a pressure molding method or a method of applying a slurry such as a solvent to a negative electrode current collector, drying it, pressing it, and the like. <Electrolyte> The electrolyte of the present invention may be, for example, NaClCl 4, NaPF6, NaAsF6, NaSbF6, NaBF4, NaCF3S03, NaN(S02CF3)2, a lower aliphatic carboxylic acid sodium salt, NaAlCl4 or the like, or two or more thereof may be used. mixture. -12- 201001783 It is preferred to use at least one selected from the group consisting of NaPF6, NaAsF6, NaSbF6, NaBF4, NaCFsSO3, and NaN(S〇2CF3)2 containing fluorine. Further, when the above electrolyte is used in the present invention, it is generally dissolved in an organic solvent as a nonaqueous electrolytic solution. The aforementioned organic solvent such as 'propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, isopropyl methyl carbonate, vinyl carbonate ' 4 - trifluorocarbon Carbonic acid esters such as methyl-1,3-dipradin-2-one and 1,2-bis(methoxycarbomethoxy)ethane; dimethoxyethane, 1,3-dimethoxy Ethers such as propane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; methyl formate, methyl acetate, butane Esters such as esters; nitriles such as acetonitrile and butyronitrile; decylamines such as N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide; 3-methyl-2-oxazolinone a urethane compound; a sulfur-containing compound such as cyclopentane, dimethyl hydrazine, or 1,3-propane sultone; or a fluorine atom-containing compound introduced from the above organic solvent. Two or more kinds of these organic solvents can be generally used in combination. Also, the electrolyte used may be a solid electrolyte. The solid electrolyte to be used may be, for example, an 'polyethylene oxide-based polymer compound, or an organic solid electrolyte containing at least one polymer compound of at least one of a polyorganosiloxane chain or a polyoxyalkylene chain. Further, a non-aqueous electrolyte solution, i.e., a gel type, can be used in the polymer compound. Further, Na2S-SiS2, Na2S-GeS2, NaTi2(P04)3, NaFe2(P04)3, Na2(S〇4)3, Fe2(S04)2(P〇4), Fe2(M〇04)3, etc. can be used. Inorganic solid electrolyte. The safety of the sodium battery can be further improved by using such a solid electrolyte. Further, when the electrolyte used in the sodium battery of the present invention is a solid electrolyte, the solid electrolyte also has the effect of a separator described in the following -13-201001783, in which case a separator is not required. <Separator> The sodium battery of the present invention is preferably further provided with a separator. The separator to be used may be formed of a polyolefin resin such as polyethylene or polypropylene, a fluororesin or a nitrogen-containing aromatic polymer, and may have a material such as a porous film, a nonwoven fabric or a woven fabric. Further, a separator or a separator described in the above-mentioned Japanese Patent Application Laid-Open No. 2000-30686, No. JP-A No. 2000-3686, and the like. The thickness increases the volumetric energy density of the battery, reduces the internal resistance, and is preferably as thin as possible under mechanical strength. The thickness of the separator is generally 5 to 200 μm, more preferably 5 to 40 μm. The separator is preferably a porous film containing a thermoplastic resin. Preferably, the separator in the battery has an effect of disposing a current between the positive electrode and the negative electrode and interrupting the current to prevent excessive current from flowing (closing) when an abnormal current such as a short circuit between the positive electrode and the negative electrode is caused by flowing inside the battery. The closing at this time means that the pores of the porous film of the separator are closed when the temperature is exceeded. After the shutdown, even if the temperature inside the battery rises to a certain high temperature, the film is not broken due to the temperature, and the closed state can be maintained, in other words, it has high heat resistance. Such a separator is a porous film having a heat resistant material such as a laminated porous film obtained by laminating a heat resistant porous layer and a porous film, and preferably a heat resistant porous layer containing a heat resistant resin and a porous resin containing a thermoplastic resin. A laminated porous film obtained by laminating thin films can be further prevented from thermally rupturing the battery of the present invention by using a separator having such a porous film of a heat resistant material. -14- 201001783 The heat resistant porous layer can be laminated on both sides of the porous film. <Laminated Porous Membrane Separator> Next, a separator formed of a laminated porous film will be described. The thickness of the separator is generally 5 μm or more and 40 μm or less, preferably 20 μm or less. Further, when the thickness of the heat resistant porous layer is Α (μιη) and the thickness of the porous film is Β (μιη), the Α/Β is preferably 〇 or more and 1 or less. Further, the separator has a gas permeability of from 50 to 300 sec / l cc, more preferably from 50 to 200 sec / l cc, from the viewpoint of ion permeability. The separator has a porosity of usually 30 to 80% by volume, preferably 40 to 70% by volume. (Heat-resistant porous layer) The heat-resistant porous layer in the laminated porous film preferably contains a heat-resistant resin. In order to further improve the ion permeability, the thickness of the heat resistant porous layer is preferably Ιμηι or more and ΙΟμηη or less, more preferably Ιμπι or more and 5 μm or less. The thickness of the heat resistant porous layer is preferably Ιμ.ιη or more and 4 μηι or less. Further, the heat resistant porous layer has fine pores, and the pore diameter (diameter) of the pores is usually 3 μm or less, preferably 1 μm or less. Further, the heat resistant porous layer may contain a dip which will be described later. Further, the heat resistant porous layer may be formed of an inorganic powder. The heat resistant resin contained in the heat resistant porous layer is, for example, polyamine, polyimine, polyamidimide, polycarbonate, polyacetal, poly maple, polyphenylene sulfide, polyether ketone, aromatic Polyester, polyether oxime, polyether quinone imine, in order to further improve heat resistance, it is preferably polyamine, polyimine, polyamidopyrene-15-201001783 amine, polyether mill, polyether oxime The amine is more preferably polyamine, polyimine or polyamidimide. The heat resistant resin is more preferably a nitrogen-containing aromatic compound such as an aromatic polyamine (para-aligned aromatic polyamide or meta-oriented aromatic polyamide), an aromatic polyimine or an aromatic polyamidimide. The polymer is particularly preferably an aromatic polyamine, and is preferably a para-oriented aromatic polyamine (hereinafter referred to as "p-aromatic polyamine"). Further, the heat resistant resin may be, for example, poly-4-methylpentene-1 or a cyclic olefin polymer. The use of these heat-resistant resins improves the heat resistance and increases the thermal film rupture temperature. The thermal film rupture temperature depends on the type of heat-resistant resin and can be used depending on the intended use and intended use. Generally, the thermal film rupture temperature is 160 ° C or higher. When the heat resistant resin to be used is the above nitrogen-containing aromatic polymer, the thermal film rupture temperature can be controlled to 400 ° C, and when poly-4-methylpentene-1 is used, it can be controlled at 250 ° C, and the ring can be used. The olefin-based polymer can be controlled at 300 °C. Further, when the heat resistant porous layer is formed of an inorganic powder, the thermal film rupture temperature can be controlled, for example, at 500 ° C or higher. The above aromatic polyamine is obtained by condensation polymerization of a para-oriented aromatic diamine and a para-oriented aromatic dicarboxylic acid halide, and is substantially aligned with or based on an aromatic ring. The alignment unit (for example, 4,4 '-diphenylene ester, 1,5-naphthalene, 2,6-naphthalene, etc., or the opposite direction extending in the opposite direction or in parallel) is bonded to the amide bond to form a repeating unit. . For aromatic polyamides, para-aligned or para-oriented poly-p-polyamines, for example, poly(p-phenylene terephthalamide), poly(p-benzoguanamine) ), poly(4,4'-benzoanilide terephthalamide), poly(p-phenylene-4,V-extension biphenylamine decylamine), poly(phenylene-2) 6-naphthalene dicarboxylate amide, -16- 201001783 poly(2-chloro-p-phenylene terephthalamide), p-extension/2,6-dichloro-p-phenyl-p-phenylene terephthalate Amine Copolymer The above aromatic polyimine is preferably a wholly aromatic polyimine produced by polycondensation of an aromatic amine. Dipyrenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl 3,3,4,4'-benzophenonetetracarboxylic dianhydride, 2,2'-bis hexafluoropropane, 3,3',4,4'-biphenyltetracarboxylic dianhydride diphenylamine, p-phenylenediamine, benzophenone diamine, 3,3 '-diaminobenzophenone, 3 , 3 '-diaminodiamine, and the like. Further, a polyisoimide which is soluble in a solvent, such as 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride and an aromatic compound, is used. The above aromatic polyamidoximine, for example, a compound obtained by condensation polymerization of a quinone diisocyanate and an aromatic diisocyanate thereof are condensed and polymerized, and the carboxylic acid is specifically, for example, isophthalic acid or terephthalic acid. Specific examples of the acid anhydride include trimellitic anhydride and the like. The aryl group is specifically, for example, 4,4'-diphenylmethane diisocyanate isocyanate, 2,6-tolyl diisocyanate, acid ester, m-xylylene diisocyanate or the like. When the heat resistant porous layer contains a heat resistant resin, it is resistant to heat. The dip material contained in the heat resistant porous layer may be selected from organic powders or a mixture thereof. The constituent diameter is preferably Ο.Οίμιη or more Ιμιη below.塡 Phenyl-p-xylyleneamine and the like. Specific examples of the aromatic dianhydride and the dianhydride are, for example, 'decatetracarboxylic dianhydride' ^ (3,4-dicarboxyphenyl) and the like. Diamines such as 'oxidized' 3, 3 '-methyldiphenyldiphenyl sulfonium, 1,5'-naphthylamine, polycondensed aromatic dicarboxylic acids and aromatics of such polyamidiamine aromatic diamines, used Aromatic diacids. Aromatic dicarboxylic acid, etc. Further, the aromatic aromatic diisocyanate, 2,4-tolyldi-di-p-tolyl diisocyanate porous layer may contain a shape of an average particle of an organic powder or a material-free particle, such as a slightly spherical -17- 201001783 A shape, a plate shape, a column shape, a needle shape, a whisker shape, a fiber shape, etc., any of the particles may be used, but the viewpoint of easily forming a uniform pore is preferably a slightly spherical particle. The slightly spherical particles are, for example, particles having an aspect ratio (longitudinal diameter of the particles/short diameter of the particles) of 1 or more and 1.5 or less. The aspect ratio of the particles can be determined by electron micrographs. Organic powders for dip such as styrene, ketene, acrylonitrile, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, methyl acrylate, etc. alone or 2 Copolymers of the above type: polytetrafluoroethylene, tetrafluoroethylene-6 fluorinated propylene copolymer, 4 fluorinated ethylene-ethylene copolymer, polyvinylidene fluoride and other fluorine resin; melamine resin; urea resin; polyolefin a powder formed of an organic substance such as polymethacrylate. The organic powder may be used singly or in combination of two or more. The chemical stability of these organic powders is preferably polytetrafluoroethylene powder. a powder formed of an inorganic material such as a metal oxide, a metal nitride, a metal carbide, a metal hydroxide, a carbonate, a sulfate or the like, wherein the powder formed of a lower conductivity inorganic substance is good. Specifically, for example, a powder formed of alumina, ceria, titania, barium sulfate or calcium carbonate. The inorganic powders may be used singly or in combination of two or more. Among these inorganic powders, the chemical stability is preferably alumina powder. Further, it is preferable that all the particles constituting the mash are alumina particles, and it is more preferable that all of the particles constituting the mash are alumina particles, and some or all of them are slightly spherical alumina particles. Further, when the heat resistant porous layer is formed of an inorganic powder, the above inorganic powder may be used, and if necessary, a binder may be mixed. -18 - 201001783 When the heat-resistant porous layer contains a heat-resistant resin, the content of the material varies depending on the specific gravity of the material of the material. For example, when all the particles constituting the material are alumina particles, the total amount of the heat-resistant porous layer is 100. The weight of the dip material is generally 5 or more and 95 or less, preferably 20 or more and 95 or less, more preferably 30 or more and 90 or less. This range can be appropriately set depending on the proportion of the material of the material. (Porous film) In the laminated porous film, the porous film is preferably a material having fine pores and being closable. In this case, the porous film contains a thermoplastic resin. The thickness of the porous film is generally from 3 to 30 μm, preferably from 3 to 25 μm. The porous film has the same pore size as the heat resistant porous layer, and has a pore diameter of usually 3 μm or less, preferably Ιμηη or less. The porosity of the porous film is generally 30 to 80% by volume, preferably 40 to 70% by volume. In the nonaqueous electrolyte secondary battery, when the temperature exceeds the normal use temperature, the porous film is softened by the thermoplastic resin constituting the same. Block the micropores. The thermoplastic resin contained in the porous film is, for example, a softening agent at 80 to 180 ° C, which can be selected from those which are insoluble in the electrolyte in the nonaqueous electrolyte secondary battery. A specific thermoplastic resin such as an olefin resin such as polyethylene or polypropylene or a thermoplastic polyurethane resin may be used in combination of two or more kinds thereof. In order to be softened by softening at a lower temperature, the thermoplastic resin preferably contains polyethylene. Specific examples of the polyethylene include polyethylene such as low density polyethylene, high density polyethylene, and linear polyethylene, and ultrahigh molecular weight polyethylene having a molecular weight of not less than 10,000. In order to increase the spur strength ' of the porous film, the thermoplastic resin preferably contains at least an ultrahigh molecular weight polyethylene. Further, in the production surface of the porous film -19-201001783, the thermoplastic resin preferably contains a wax composed of a low molecular weight (weight average molecular weight, 10,000 or less) polyolefin. Further, a porous film having a heat resistant material different from the above laminated porous film, for example, a porous film formed of a heat resistant resin and/or an inorganic powder, a thermoplastic resin such as a polyolefin resin or a thermoplastic polyurethane resin A porous film in which a heat resistant resin and/or an inorganic powder is dispersed in a film. The heat resistant resin and the inorganic powder at the time of jtt can be as described above. <Manufacturing Method of Sodium Battery> When the sodium battery of the present invention has a separator, for example, the positive electrode, the separator, and the negative electrode are laminated in this order, and then the electrode group is obtained by rewinding the electrode group, and the electrode group is housed in a battery can. The electrode group is obtained by impregnating a non-aqueous electrolyte solution formed of an organic solvent containing an electrolyte. Further, when the separator is not provided, for example, the electrode group may be obtained by sequentially laminating the positive electrode, the solid electrolyte, and the negative electrode, and then rewinding the electrode group, and storing the electrode group in the battery can. When the shape of the electrode group is such that the vertical direction of the reel of the electrode group is cut, the cross section is a circle, an ellipse, an ellipse, a rectangle, or a rectangular shape without a corner. Further, the shape of the battery is, for example, a paper sheet type, a coin type, a cylinder type, or an angle type. The sodium storage battery obtained as described above can have a larger discharge capacity retention ratio at the time of repeated charge and discharge than the prior art, and has excellent cycleability, and can suppress the formation of sodium pinestone on the surface of the negative electrode, and has excellent battery stability. [Embodiment] 201001783 EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. Production Example 1 Sodium carbonate containing a metal compound (NazCCh: manufactured by Wako Pure Chemical Industries, Ltd.: purity: 99.8%) and manganese oxide (IV) were prepared by a molar ratio of Na. Mn: Co of 0.7:0.5:0.5. (Mn02: High Purity Chemical Research Institute Co., Ltd.: purity: 99.9%), and cobalt trioxide (C〇3〇4: manufactured by Zhengtong Chemical Industry Co., Ltd.: purity 99%), mixed with a dry ball mill for 4 hours a mixture of metal compounds. The obtained mixture containing the metal compound was poured into an alumina dish, and heated to 800 ° C in an air atmosphere for 2 hours to obtain a composite metal oxide E1. The composite metal oxide E1: a conductive material: a binder: 85: 10: 5 (weight ratio), each of which is a composite metal oxide E1, a conductive material of acetylene black (manufactured by Electric Chemical Industry Co., Ltd.), and bonded After PVDF (PolyVinylidene DiFluoridePolyflon, manufactured by Kuleiha Co., Ltd.), the amount of N-methyl-2-pyrrolidone (NMP · Tokyo) was first formed by agate rubbing, mixed with mixed metal oxides and acetylene black. Industrial Co., Ltd.) was added to the mixture, and PVDF was added to continue to mix and slurry. The resulting slurry having a thickness of 1 μm was applied to a 40 μm thick aluminum foil for a current collector using a coating roll, placed in a dryer, and dried while removing the crucible to obtain a positive electrode sheet 1. The positive electrode sheet 1 was perforated by an electrode punching machine to have a diameter of 1.5 cm, and then sufficiently pressed by a hand press to obtain a positive electrode 1. -21 - 201001783 Comparative Example 1 After the positive electrode 1 obtained in Production Example 1 was placed in a recess in the lower side of a coin unit (manufactured by Baoquan Co., Ltd.), the 1 M NaClCU/carbonic acid of the nonaqueous electrolyte was combined. A propylene resin, a polypropylene porous film (20 μm thick) of a separator, and a metal sodium of a negative electrode (manufactured by Adrien Co., Ltd.) were used to prepare a sodium secondary battery 1. When the test battery was assembled, it was carried out in a toolbox under an argon atmosphere. The battery charge and discharge test was carried out using the sodium battery 1 under the following conditions. Charge and discharge conditions: Charging is performed at a rate of 0.1 C (speed of full charge in 10 hours) to CC (constant current: constant current) to 4.0 V. The discharge was such that CC discharge was performed at the same speed as the charging speed, and was stopped after the voltage was 1.5 V. Thereafter, the charge and discharge cycle was performed at the same speed as the charging speed, and was stopped at the same time as the charging voltage of 4.0 V and the discharging voltage of 1.5 V. As a result of the constant current charge and discharge test of the sodium storage battery 1, the discharge capacity (discharge capacity retention ratio) at the 10th cycle was 80% lower than the discharge capacity at the second cycle. Example 1 (1) Preparation of carbon material 200 g of resorcinol and 1.5 g of methyl alcohol 1.5 L 'benzaldehyde were placed in a four-necked flask under nitrogen flow, and while stirring under ice cooling, 3 6% hydrochloric acid 3 6.8 g was added dropwise. After the drip was finished, the temperature was raised to 65. (:, keep at the same temperature for 5 hours. Add 1 L of water to the obtained polymerization mixture, filter the precipitate, wash the filtrate with -22 - 201001783 water to neutrality, and then dry to obtain an organic polymer compound. Tetraphenyl cup [4] resorcinol (PCRA) 294g. Put the PCRA in a rotary oven in an air environment and heat at 300 ° C for 1 hour, then replace the air in the rotary furnace with argon. 1 〇〇〇.〇: heating for 4 hours. Secondly, it was pulverized by a ball mill (manufactured by Minnow, 28 rpm, 5 minutes) to obtain a carbon material C1 of the organic polymer compound calcined product. The powdery carbon material C1 was not contacted. Metal, so almost no metal ion-containing metal. (2) Manufacture of negative electrode with carbon material C1: binder = 95:5 (weight ratio) composition of carbon material C1 and binder of polyvinylidene fluoride (PVDF) After dissolving the binder in N-methylpyrrolidone (NMP), the carbon material C1 is added to obtain a gelled product, and the thickness of the material is applied to the current collector using a coating roll. The copper foil of ΙΟμπι was placed in a dryer to remove NMP while being sufficiently dried to obtain a negative electrode sheet. The electrode perforator was perforated to have a diameter of 1.5 cm, and then sufficiently pressed by a hand press to obtain a negative electrode 1. (3) A sodium battery was fabricated, and the positive electrode 1 obtained in Production Example 1 was placed in a coin in an aluminum foil downward manner. Unit 1 (made by Baoquan Co., Ltd.), the lower part of the recess, '1C of non-aqueous electrolyte, 1M of NaC104/propylene carbonate, separator of polypropylene porous membrane (thickness 20 μm), and negative electrode 1; Battery 2. In addition, the test battery was assembled in a toolbox under argon gas. -23- 201001783 The sodium battery 2 was used to carry out a constant current charge and discharge test under the conditions of Comparative Example 1. The constant current charge of the sodium battery 2 The discharge test result is 'relative to the discharge capacity of the second cycle, and the discharge capacity (discharge capacity retention rate) of the 10th cycle is extremely high at 1〇7%, so it is more than 100%. Further, even the cycle The effect of the sodium battery 4 described later can also be obtained by using the sodium battery 2. Example 2 (1) The positive electrode is made of Na: Mn: Fe: Ni The molar ratio is 〇·7: 0.333: 0.333: 0.3 3 3 Method for weighing sodium carbonate containing metal compounds (Na2C03: and Pure Pharmaceutical Industry Co., Ltd.: purity 99.8%), manganese oxide (IV) (Mn02: high purity chemical research institute company: purity 9 9.9 %), iron oxide (11, 111) (F e 3 Ο 4) :High Purity Chemical Research Institute Co., Ltd.: purity 99%) and nickel (II) oxide (NiO: manufactured by High Purity Chemical Research Institute Co., Ltd.: purity 9 9 %), after mixing for 4 hours in a dry ball mill, it contains a mixture of metal compounds. The resulting metal compound-containing mixture was poured into an alumina pan and heated to 80 Torr in an air atmosphere using an electric furnace for 2 hours to obtain a composite metal oxide E 2 . The composite metal oxide e 2 :conductor: binder == 8 5 : 1 0 : 5 (weight ratio) composition of each of the composite metal oxide E2, conductive material acetylene carbon black (Electrical Chemical Industry Co., Ltd. After the PVDF (PolyVinylidene DiFluoridePolyflon, manufactured by Kuleiha Co., Ltd.), firstly mix the composite metal oxide and acetylene black with agate, and then apply an appropriate amount of N-methyl-24- 201001783. Pyrrolidone (NMP: manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the mixture, and PVDF was further added and continuously mixed to be slurried. The resulting slurry having a thickness of ΙΟΟμηη was applied onto a 40 μm thick aluminum foil for a current collector using a coating roll, and dried in a dryer to remove the crucible, thereby sufficiently obtaining a positive electrode sheet 2. The positive electrode sheet 2 was perforated with an electrode punch to have a diameter of 1.5 cm, and then sufficiently pressed by a hand press to obtain a positive electrode 2. (2) After the positive electrode 2 is placed in the recess of the lower part of the coin unit (made by Baoquan Co., Ltd.) in the manner of the aluminum foil facing downward, the NaC104/propylene carbonate of the non-aqueous electrolyte is combined and separated. A polypropylene porous membrane (thickness 20 μπ〇, and the negative electrode 1 of Example 1 was used to prepare a sodium storage battery 3. Further, the test battery was assembled in a toolbox under an argon atmosphere. The sodium battery 3 was used for comparison. The constant current charge and discharge test was carried out under the conditions of Example 1. The result of the constant current charge and discharge test of the sodium battery 3 was that the discharge capacity (discharge capacity retention rate) of the first cycle with respect to the discharge capacity of the second cycle was 1 1 1 %, and '1 more cycles (1st to 20th cycles), the discharge capacity (discharge capacity retention rate) of the 20th cycle is the discharge capacity of the 2nd cycle. Since η is 5 %, it is extremely high in excess of 100%. Even if the sodium battery 3 is reused and recycled, the effect of the sodium battery 4 described later can be obtained. Example 3 (1) Production of a negative electrode-25-201001783 Material: Adhesive = 95 : 5 (weight ratio) The carbon material of the calcined organic polymer compound and the polyvinylidene fluoride (PVDF) of the binder are mixed, and the binder is dissolved in N-methylpyrrolidone (NMP), and the carbon material is added to be slurried. The material having a thickness of 100 μm was applied to a copper foil having a thickness of 10 μηα for a current collector using a coating roller, and dried in a dryer to remove the crucible, thereby obtaining a negative electrode sheet. After the negative electrode sheet was perforated to a diameter of 1.5 cm, it was fully pressed with a hand press to obtain a negative electrode of 2 °. (2) A sodium battery was fabricated, and the positive electrode of the same example 2 was placed in a coin unit with the aluminum foil facing downward (Baoquan Co., Ltd.) After the lower side portion of the recess, a 1M NaC104/propylene carbonate of a non-aqueous electrolyte, a polypropylene porous film of a separator (thickness 20 μm), and a negative electrode 2 were combined to prepare a sodium storage battery 4. The test battery was carried out in a toolbox under an argon atmosphere. The sodium battery 4 was used to carry out a constant current charge and discharge test under the conditions of Comparative Example 1. The test results of the constant current charge and discharge test of the sodium battery 4 were relative to the second time. Cycle discharge capacity, 10th The discharge capacity (discharge capacity retention ratio) of the cycle was 108%, and after 10 cycles (the 1st cycle to the 2nd cycle), the discharge capacity of the 20th cycle with respect to the discharge capacity of the 2nd cycle (The discharge capacity retention rate) is 10% 7%. Therefore, the sodium battery 4 after the above-mentioned cycle is subjected to constant current charge and discharge for 20 times under the following conditions is subjected to a charge and discharge acceleration test (second time). 1 cycle to the 5th cycle) -26- 201001783 Charge and discharge acceleration test conditions: Charging is performed, and CC charging is performed to 4.0V at a rate of 1.0 C (speed of full charge within 1 hour). The discharge is such that the CC discharge is performed at a speed of the charging speed to a voltage of 1.5 V and then stopped. After repeating the constant current charge and discharge test of the 1.0 C-speed for 19 times, the CC was charged to 4.0 V at a rate of 0.1 C (the speed of full charge in 1 〇 hours), and CC discharge was performed at the same speed as the charging speed. After the voltage was 1.5V, it was stopped, and the constant current charge and discharge test of 0.1C class speed was completed once. The charge and discharge acceleration test was completed 24 times (total 480 times) from the total of 10 times of the above-mentioned 1.0 C-speed and 19 C-speed combination of 20 constant current charge and discharge tests. As a result of the above-described charge and discharge acceleration test of the sodium battery 4 after the constant current charge and discharge of 20 times, the discharge capacity (discharge capacity retention rate) of the fifth cycle was extremely high with respect to the discharge capacity of the second cycle. 96%. The sodium battery 4 after the above-described 500-time constant current charge and discharge was repeatedly repeated 25 times (total 500 times). The total of the combination of the above-mentioned i.〇c-speed 19 times and 〇.1C-level speed 1 time combination 2 The current is subjected to a constant current charge and discharge test, and the charge and discharge acceleration test is completed. As a result, with respect to the discharge capacity of the second cycle, the discharge capacity (discharge capacity retention ratio) of the first cycle was extremely high, 80%. Example 4 (1) Production of a positive electrode 0.3 3 3 : A sodium carbonate (Na2c〇) containing a metal compound was taken in a molar ratio of Na:Mn:Fe:Ni of 0.8:0.3 3 3 : -27- 201001783 0.333 3: Wako Pure Chemical Industries Co., Ltd.: purity 99_8%), manganese oxide (iv) (Mn02: high purity chemical research institute company: purity 9 9.9 %), iron oxide (II, III) (Fe3〇4 ): High Purity Chemical Research Institute Co., Ltd.: 99% purity) and nickel (II) oxide (NiO: High Purity Chemical Research Institute, Ltd.: purity 9 9 %) 'mixed in a dry ball mill for 4 hours, containing a mixture of metal compounds. The obtained metal compound-containing mixture was poured into an alumina crucible, and heated to 80 ° C in an air atmosphere for 2 hours to obtain a composite metal oxide E3. The composite metal oxide E3: a conductive material: a binder = 85 : 10 : 5 (weight ratio), each of which is obtained by weighing a composite metal oxide E3, an acetylene black of an electrical conductor (manufactured by Electric Chemical Industry Co., Ltd.), and bonding After PVDF (PolyVinylidene DiFluoridePolyflon) manufactured by Kuleiha Co., Ltd., firstly mix the complex metal oxide and acetylene black with agate, and then apply an appropriate amount of N-methyl-2-pyrrolidone (NMP: Tokyo Chemical Industry Co., Ltd.) The company was added to the mixture, and then PVDF was added to continue to uniformly mix and slurry. The resulting slurry having a thickness of μμηι was applied to an aluminum foil having a thickness of 40 μm for a current collector using a coating roller, and placed in a dryer to remove the crucible and sufficiently dried to obtain a positive electrode sheet 3. The positive electrode sheet 3 was perforated with an electrode punch to have a diameter of 1.5 cm, and then sufficiently pressed by a hand press to obtain a positive electrode 3. (2) NaC104/201001783 propylene carbonate and separator which are combined with a non-aqueous electrolyte after the positive electrode 3 is placed in the recess of the lower part of the coin unit (made by Baoquan Co., Ltd.) in a manner that the aluminum foil is facing downward. A polypropylene porous film (thickness 20 μm) and a negative electrode 2 of the same manner as in Example 3 were used to prepare a sodium storage battery 5. Further, the test battery was assembled in a toolbox under an argon atmosphere. A constant current charge and discharge test was carried out using the sodium battery 5 under the conditions of Comparative Example 1. As a result of the constant current charge and discharge test of the sodium battery 5, the discharge capacity (discharge capacity retention rate) of the first cycle is extremely high 105% with respect to the discharge capacity of the second cycle, so it is more than 100%. value. Further, even if the sodium battery 5 is recycled, the effect of the sodium battery 4 described above can be obtained. Example 5 (1) Production of positive electrode A composite metal oxide E4 of Example 5 was obtained in the same manner as in Example 4 except that a metal compound containing a Na: Mn:Fe:Ni molar ratio of 0.9:0.333 was used. The composite metal oxide E4 of Example 5 was used as a positive electrode material for a sodium storage battery, and a positive electrode sheet 4 was obtained in the same manner as in Example 4. The positive electrode sheet 4 was perforated with an electrode punch to have a diameter of 1.5 cm, and then sufficiently pressed by a hand press to obtain a positive electrode 4. (2) Production of sodium battery The sodium battery 6 was produced in the same manner as in Example 4 using the positive electrode 4 of Example 5. Moreover, the test battery was assembled in a toolbox under an argon atmosphere. A constant current charge and discharge test was carried out using the sodium battery 6 under the conditions of Comparative Example 1. The result of the constant current charge and discharge test of the sodium battery 6 is that the discharge capacity (discharge capacity retention rate) of the 10th cycle is extremely high 105% with respect to the discharge capacity of the second cycle of -29-201001783, so it exceeds 100% of the total. Further, even if the sodium battery 6 is recirculated, the effect of the sodium battery 4 described above can be obtained. Production Example 2 (Production of Laminated Porous Film) (1) 272.7 g of calcium chloride was dissolved in NMP 4200 g by applying a coating liquid for a heat-resistant porous layer. 'After adding 132.9 g of p-phenylenediamine, the solution was gradually dissolved. Formic acid dichloride 2 4 3.3 g was added to the obtained solution to carry out polymerization, and the aromatic polyamine was diluted with NMP to obtain a concentration of 2.0% by weight of the aromatic polyamine. 2 g of the first alumina powder in a total amount of 2 g (manufactured by Japan Ai Luoji Co., Ltd., alumina C, average particle diameter 0.02 μπ〇, and second alumina powder 2 g (Smith Co., Ltd., AA03, The average particle diameter of 0.3 μm was added to the obtained aromatic polyamine solution in 1 〇〇g, treated with a nanomachine for 3 times, filtered through a gold mesh of 1 000 mesh, and defoamed under reduced pressure to obtain heat-resistant porous. The slurry was applied as a slurry, and the weight of the alumina powder (grain) was 67% by weight based on the total weight of the aromatic polyamide and the alumina powder. (2) Manufacture and evaluation of the laminated porous film The porous film used is a porous film made of polyethylene (film thickness: 12 μm), and has a gas permeability of 140 sec/100 cc' average pore diameter O.lpm, and a porosity.
5 0%)。將上述聚乙烯製多孔質薄膜固定於厚1〇〇μη1之 PET薄膜上，使用鐵斯達產業股份公司製棒塗機，將耐熱 多孔層用淤漿狀塗佈液塗佈於該多孔質薄膜上。將PET -30- 201001783 薄膜上塗佈該多孔質薄膜之物一起浸漬於弱溶劑之水中， 析出對芳香族聚醯胺多孔質膜（耐熱多孔層）後，乾燥溶劑 自剝除PET薄膜，得層合耐熱多孔層及多孔質薄膜而得 之層合多孔質薄膜。層合多孔質薄膜之厚爲16 μιη，對芳 香族聚醯胺多孔質膜（耐熱多孔層）之厚爲4μιη。層合多孔 質薄膜之透氣度爲1 8 0秒/ 1 0 0 c c，空孔率爲5 0 %。使用掃 描型電子顯微鏡（SEM)觀察層合多孔質薄膜中耐熱多孔層 之剖面，結果具有0.03μιη至 0·06μηι之較小微細孔及 Ο.ίμηι至Ιμιη之較大微細孔。評估層合多孔質薄膜之方法 如下述（A )至（C )。 (A) 測定厚度 層合多孔質薄膜之厚度、多孔質薄膜之厚度係依JIS 規格（K7 1 3 0- 1 992)測定。又，耐熱多孔層之厚度爲，由層 合多孔質薄膜之厚度減去多孔質薄膜之厚度而得的値。 (B) 使用古勒法測定透氣度 層合多孔質薄膜之透氣度係基於JIS P8117，使用安 田精機製作所股份公司製數據計時式古勒式密度計測定。 (C) 空孔率 將所得層合多孔質薄膜樣品切成長1 0 cm之正方形 後’測定重量W(g)及厚度D(Cm)。求取樣品中各層之重 量（Wi)(g))後’由 Wi及各層之材質的真比重（真比重 -31 - 201001783 i(g/cm3)求取各層之體積，再以下式求取空孔率（體積％)。 空孔率（體積％) = 100><{1-(\¥1/真比重1+W2/真比重 2 + .. + Wn/真比重 n)/(10xl0xD)} 上述實施例中因所使用的分離器爲製造例所得之層合 多孔質薄膜，故可得更進一步防止熱破膜之鈉蓄電池。 【圖式簡單說明】 [圖1 ]表示鈉蓄電池（比較例1、實施例1)之充放電試 驗時之各循環中之放電容量維持率之圖。 -32-50%). The polyethylene porous film was fixed on a PET film having a thickness of 1 μμη1, and a slurry coating liquid for a heat resistant porous layer was applied to the porous film using a bar coater manufactured by Tista Industry Co., Ltd. on. The film coated with the porous film on the PET-30-201001783 film was immersed in water of a weak solvent to precipitate a porous polyurethane porous film (heat resistant porous layer), and then the PET film was peeled off from the dried solvent. A porous film obtained by laminating a heat resistant porous layer and a porous film. The thickness of the laminated porous film was 16 μm, and the thickness of the aromatic aromatic polyimide film (heat resistant porous layer) was 4 μm. The laminated porous film had a gas permeability of 180 ° / 1 0 0 c c and a porosity of 50%. The cross section of the heat resistant porous layer in the laminated porous film was observed using a scanning electron microscope (SEM), and as a result, it was small micropores of 0.03 μm to 0·06 μm and large pores of Ο.ίμηι to Ιμιη. The method of evaluating the laminated porous film is as follows (A) to (C). (A) Measurement of Thickness The thickness of the laminated porous film and the thickness of the porous film were measured in accordance with JIS standard (K7 1 30 - 1 992). Further, the thickness of the heat resistant porous layer is 値 which is obtained by subtracting the thickness of the porous film from the thickness of the laminated porous film. (B) Measurement of gas permeability by the Gule method The gas permeability of the laminated porous film was measured by a data-timed Gülle densitometer manufactured by Yasuda Seiki Co., Ltd. based on JIS P8117. (C) Porosity The obtained laminated porous film sample was cut into a square of 10 cm to measure the weight W (g) and the thickness D (Cm). After obtaining the weight (Wi)(g) of each layer in the sample, 'the true specific gravity of the material of Wi and each layer (the true specific gravity -31 - 201001783 i (g/cm3) is used to obtain the volume of each layer, and then the following formula is taken. Porosity (% by volume). Porosity (% by volume) = 100><{1-(\¥1/true specific gravity 1+W2/true specific gravity 2 + .. + Wn/true specific gravity n)/(10xl0xD) In the above embodiment, the separator used is a laminated porous film obtained in the production example, so that a sodium battery which can further prevent thermal rupture can be obtained. [Simplified Schematic] [Fig. 1] shows a sodium battery (Comparative) Example 1 shows the discharge capacity retention rate in each cycle during the charge and discharge test of Example 1). -32-