200948721 六、發明說明： 【發明所屬之技術領域】 本發明關於複合金屬氧化物及鈉蓄電池。 【先前技術】 複合金屬氧化物係用作爲蓄電池的正極活性物質。於 蓄電池之中，鋰蓄電池在作爲攜帶式電話或筆記型個人電 © 腦等的小型電源係已經實用化，再者，由於可使用作爲電 動汽車、混合動力汽車等的汽車用電源或分散型電力儲存 電源等的大型電源，其需求係正在增大。然而，於鋰蓄電 池中，其正極活性物質的原料係含有許多鋰等的稀有金屬 元素，爲了對應於大型電源的需要之增大，而掛念前述原 料的供給。 相對於此’作爲可解決上述供給掛念的蓄電池，進行 鈉蓄電池的檢討。鈉蓄電池係供給量豐富而且可由廉價的 材料所構成’藉由將其實用化，可期待能大量供給大型電 源。 -而且’作爲鈉蓄電池用的正極活性物質，專利文獻1 中具體地記載將Na、Μη及Co的組成比（N a: Mn: Co)爲 0.7:0.5:0.5的原料煅燒而得之正極活性物質。 [專利文獻1]2〇〇7_2 8766 1號公報（實施例】） 【發明內容】 發明所欲解決的問題 -5- 200948721 然而，藉由使用上述正極活性物質，雖然可以減少鋰 使用量，但是於使用該正極活性物質的鈉蓄電池中，重複 充放電時的放電容量維持率不能說是充分。本發明之目的 爲提供可減少鋰的使用量，而且與以往相比，重複充放電 後的放電容量維持率大的鈉蓄電池，及可用作爲其正極活 性物質的複合金屬氧化物。 解決問題的手段 本發明們爲了解決上述問題，重複精心硏究，而達成 本發明。即，本發明係提供下述發明。 <1> 一種複合金屬氧化物，其特徵係包含Na及 此處，Μ1表示從Μη、Fe、Co及Ni所組成族群所選出的 3種以上之元素），NaiM1的莫耳比爲a:l(此處，a係超過 〇·5未達1的範圍之値）。 <2> —種複合金屬氧化物，其特徵係以下式（1)所示200948721 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a composite metal oxide and a sodium storage battery. [Prior Art] A composite metal oxide is used as a positive electrode active material of a secondary battery. Among the batteries, the lithium battery has been put into practical use as a small power source such as a portable telephone or a notebook type personal computer. In addition, since it can be used as an electric power source or a distributed power source for an electric vehicle or a hybrid vehicle. The demand for large power supplies such as power supplies is increasing. However, in the lithium secondary battery, the raw material of the positive electrode active material contains a large amount of rare metal elements such as lithium, and the supply of the raw material is missed in order to increase the demand for a large power source. On the other hand, as a battery that can solve the above-mentioned supply problem, a review of the sodium battery is performed. The sodium battery is abundant in supply and can be made of inexpensive materials. By using it in practical use, it is expected that a large amount of power can be supplied in a large amount. In addition, as a positive electrode active material for a sodium battery, Patent Document 1 specifically describes a positive electrode active obtained by calcining a raw material having a composition ratio (N a : Mn: Co) of Na, Μη, and Co of 0.7:0.5:0.5. substance. [Patent Document 1] 2〇〇7_2 8766 1 (Embodiment) [Explanation] The problem to be solved by the invention-5-200948721 However, by using the above positive electrode active material, although the amount of lithium used can be reduced, In the sodium secondary battery using the positive electrode active material, the discharge capacity retention rate at the time of repeated charge and discharge cannot be said to be sufficient. It is an object of the present invention to provide a sodium storage battery which can reduce the amount of lithium used and which has a large discharge capacity retention rate after repeated charge and discharge, and a composite metal oxide which can be used as a positive electrode active material. Means for Solving the Problems In order to solve the above problems, the present invention has achieved the present invention by repeating careful research. That is, the present invention provides the following invention. <1> A composite metal oxide characterized by comprising Na and wherein Μ1 represents three or more elements selected from the group consisting of Μη, Fe, Co and Ni), and the molar ratio of NaiM1 is a: l (here, a is more than 〇·5 does not reach the range of 1). <2> A composite metal oxide characterized by the following formula (1)
NaaM^z (1) (此處，Μ1及a各自具有與前述相同的定義）。 <3>如前述<1>或<2>記載的複合金屬氧化物， 其中M1至少包含Μη。 <4>如前述<3>記載的複合金屬氧化物，其中Μ1 • Μη的莫耳比爲i:b(此處，Μ1具有與前述相同的定義’ 200948721 b係0.2以上且未達1之値）。 <5>如<1>〜<4>中任一項記載的複合金屬氧化 物，其中M1表示Mn、Fe及Ni。 <6>如<1>〜<5>中任一項記載的複合金屬氧化 物，其中a係0.6以上0.9以下的範圍之値。 <7>—種鈉蓄電池用正極活性物質，其含有前述<1 >〜<6>中任一項記載的複合金屬氧化物。 〇 <8> —種鈉蓄電池用正極，其含有前述<7>記載的 正極活性物質。 <9> 一種鈉蓄電池，其具有前述<8>記載的正極。 <1〇>如前述<9>記載的鈉蓄電池，其更具有隔板 〇 <11>如前述<1〇>記載的鈉蓄電池，其中隔板係具 有由含有耐熱樹脂的耐熱多孔層與含有熱塑性樹脂的多孔 質薄膜所層合而成的積層多孔質薄膜之隔板。 發明的效果 依照本發明，可提供能減少鋰的使用量，而且與以往 相比，重複充放電時的放電容量維持率大的鈉蓄電池，及 可用作爲其正極活性物質的複合金屬氧化物。本發明係工 業上極有用的。 【實施方式】 實施發明的最佳形態 200948721 <本發明的複合金屬氧化物> 本發明的複合金屬氧化物之特徵爲包含Na及M1(此 處，M1表示從Mn、Fe、Co及Ni所組成族群所選出的3 種以上之元素），Na:!^1的莫耳比爲a:l(此處，a係超過 0.5未達1的範圍之値）。 又，本發明的複合金屬氧化物例如是以下式（1)所示者 (此處，M1及a各自具有與前述相同的定義）。 於本發明的複合金屬氧化物之1個態樣中，Μ1係至 少包含Μη。此時，Μ1 : Μη的莫耳比較佳爲l:b(此處， M1具有與前述相同的定義，b係0·2以上且未達1之値） 。又，於Μ1至少包含Μη及Ni時，從可更提高所得到的 鈉蓄電池之平均放電電壓，提高電池的能量密度之觀點來 〇 看係較宜。於M1表示Mn、Fe及Ni時，即不含有稀有金 屬元素的Co時’也可得到本發明的優異效果而更佳。於 M1表示Mn、Fe及Ni時’較佳的Mn : Fe : Ni之組成（莫 耳比）爲 1:(0.3 〜3):(0.01 〜2)，更佳爲 1:(0.5 〜2):(0.1 〜 1.2)。 又’於更提高本發明的效果之意思中，a較佳爲0.6 以上0.9以下的範圍之値，更佳爲〇·7以上〇.9以下的範 圍之値’特佳爲0.8左右，即0.75以上0.84以下的範圍 -8- 200948721 之値。 於本發明的複合金屬氧化物中，Μ1的一部分可被Μ1 以外的金屬元素所取代。藉由取代，可提高鈉蓄電池的電 池特性。 <本發明的複合金屬氧化物之製造方法> 本發明的複合金屬氧化物係可藉由煅燒含金屬的化合 〇 物之混合物來製造’該混合物具有能藉由煅燒而成爲本發 明的複合金屬氧化物之組成。具體的，以成爲指定組成的 方式’秤量及混合含有對應的金屬元素之含金屬的化合物 後，煅燒所得到的混合物來製造。例如，具有較佳的金屬 兀素比之一個的 Na:Mn:Fe:Ni = 0.7:0.333:0.333:0.333 所示 的金屬元素比之複合金屬氧化物，係可藉由以Na:Mn:Fe:Ni 的莫耳比成爲0.7:0.333:0.333:0.333的方式，秤量Na2C03 、Μη02及Fe304的各原料，將彼此混合，煅燒所得到的 © 混合物而製造。 作爲可用於製造本發明的複合金屬氧化物之含金屬的 化合物，可使用氧化物以及高溫分解及/或氧化時可成爲 氧化物的化合物，例如氫氧化物 '碳酸鹽、硝酸鹽、鹵化 物、草酸鹽。作爲鈉化合物，較佳爲Na2C03、NaHC03、 Na202，從操作性的觀點來看，更佳爲Na2C03。作爲鍤化 合物，較佳爲Μη02，作爲鐵化合物，較佳爲Fe304，作爲 鎳化合物，較佳爲NiO，作爲鈷化合物，較佳爲C〇304。 又，此等含金屬的化合物亦可爲水合物。 -9- 200948721 於含金屬的化合物之混合中，可使用球磨機、V型混 合機、攪拌機等工業上通常使用的裝置。此時的混合可爲 乾式混合、濕式混合的任一者。又，藉由晶析法，亦可得 到指定組成之含金屬的化合物之混合物。 藉由煅燒上述含金屬的化合物之混合物，例如藉由在 600°C〜1 600°C的溫度範圍保持0.5小時〜100小時而煅燒 ，可得到本發明的複合金屬氧化物。例如，較佳的煅燒溫 度範圍係600°C〜900°C的溫度範圍，更佳爲650°C〜85(TC 0 的溫度範圍。作爲含金屬的化合物之混合物，使用高溫可 分解及/或氧化的化合物，例如氫氧化物、碳酸鹽、硝酸 鹽、鹵化物、草酸鹽時，可在400 °C〜1600 °C的溫度範圍 保持及進行焙燒，成爲氧化物，或在去除結晶水後，亦可 進行上述煅燒。進行焙燒的環境，可爲惰性氣體環境、氧 化性環境或還原性環境中任一者。又，亦可在焙燒後進行 粉碎。 作爲煅燒時的環境，例如可爲氮氣、氬氣等的惰性環 0 境；空氣、氧氣、含氧的氮氣、含氧的氳氣等之氧化性環 境，及含有0.1體積％〜10體積％的氫之含氫的氮氣、含 有0.1體積％〜10體積％的氫之含氫的氬氣等之還原性環 境的任一者。爲了在強還原性的環境下進行煅燒，可使含 金屬的化合物之混合物含有適量的碳進行煅燒。較佳爲在 空氣等的氧化性環境中進行煅燒。 作爲含金屬的化合物，可藉由使用適量的氟化物、氯 化物等鹵化物來控制所生成的複合金屬氧化物之結晶性、 -10- 200948721 構成複合金屬氧化物的粒子之平均粒徑。於此情況下，鹵 化物亦有達成作爲反應促進劑（助熔劑）的任務。作爲助熔 齊!ί，例如可舉出 NaF、MnF3、FeF2、NiF2、CoF2、NaCl、 MnCl2、FeCh、FeCl3、NiCl2、CoCl2、Na2C03、NaHC03 、：NH4C1、NH4I、B203、H3B03等，可以將此等當作混合 物的原料（含金屬的化合物），或適量添加到混合物中而使 用。又，此等助熔劑亦可爲水合物。 © 使用本發明的複合金屬氧化物當作鈉蓄電池用正極活 性物質時，較佳爲對如上述所得之複合金屬氧化物，任意 地使用球磨機或噴磨機等，進行粉碎、洗淨、分級等，以 調節粒度。又，亦可進行2次以上的煅燒。而且，也可進 行以含有Si、Al、Ti、Y等的無機物質來被覆複合金屬氧 化物之粒子表面等的表面處理。再者，本發明的複合金屬 氧化物之結晶構造較佳爲不是隧道構造。 本發明的複合金屬氧化物係可單獨或施予被覆等的表 © 面處理等，用作爲鈉蓄電池用正極活性物質。該正極活性 物質含有本發明的複合金屬氧化物。若使用本發'明的複合 金屬氧化物於鈉蓄電池，則所得到的鈉蓄電池，與以往相 比，重複充放電時的放電容量維持率大。又，依照本發明 ，亦可減小所得到的鈉蓄電池之內部電阻，減小充放電時 的過電壓。若可以減小充放電時的過電壓，則可更提高蓄 電池的大電流放電特性。又，也可提高將蓄電池過度充電 時的電池之安定性。 -11 - 200948721 <本發明的鈉蓄電池用正極及其製造方法> 本發明的鈉蓄電池用正極係含有本發明的正極活性物 質所成。本發明的鈉蓄電池用正極係可將含有本發明的正 極活性物質、導電材及黏結劑的正極混合劑擔持於正極集 電體上而製造。 作爲導電材，可舉出天然石墨、人造石墨、焦炭類、 碳黑等的碳材料等。作爲黏結劑，可舉出熱塑性樹脂，具 體地可舉出聚偏二氟乙烯（以下亦稱爲「PVDF」）、聚四氟 0 乙烯、四氟乙烯•六氟丙烯·偏二氟乙烯系共聚物、六氟 丙烯·偏二氟乙烯系共聚物、四氟乙烯•全氟乙烯醚系共 聚物等的氟樹脂，以及聚乙烯、聚丙烯等的聚烯烴樹脂等 。作爲正極集電體，可使用Al、Ni、不銹鋼等。 作爲在正極集電體上擔持正極混合劑的方法，可舉出 加壓成型方法，或用有機溶劑等來糊化，塗佈在正極集電 體上，乾燥後加壓等而固著的方法。於糊化時，製造由正 極活性物質、導電材、黏結劑、有機溶劑所成的漿體。作 〇 爲有機溶劑，可舉出N，N-二甲胺基丙胺、三乙胺等的胺系 :環氧乙烷、四氫呋喃等的醚系；甲基乙基酮等的酮系； 醋酸甲酯等的酯系；二甲基乙醯胺、N·甲基-2-吡咯烷酮 等的非質子性極性溶劑等。作爲對正極集電體塗佈正極混 合劑的方法，例如可舉出縫模塗佈法、篩網塗佈法、簾幕 塗佈法、刮刀塗佈法、凹槽輥塗佈法、靜電噴霧法等。 <本發明的鈉蓄電池> -12- 200948721 本發明的鈉蓄電池具有本發明的鈉蓄電池用正極。本 發明的鈉蓄電池，例如可藉由依順序層合及捲繞本發明的 鈉蓄電池用正極、隔板及在負極集電體上擔持負極混合劑 所成的負極，而得到電極群，將此電極群收納在電池罐內 ，使由含有電解質的有機溶劑所成的電解液浸漬電極群而 製造。 作爲此處的電極群之形狀，例如在與捲繞此電極群的 Ο 軸成垂直的方向中切斷時，截面可爲由圓、橢圓、長圓、 長方形、去角的長方形等所成的形狀。又，作爲電池的形 狀，例如可舉出紙型、硬幣型、圓筒型、四方型等的形狀 <本發明的鈉蓄電池-負極> 作爲本發明的鈉蓄電池所可用的負極，可使用含有負 極活性物質的負極混合劑擔持於負極集電體者、可吸藏· © 脫離鈉金屬或鈉合金等的鈉離子之電極。作爲負極活性物 質’可舉出能吸藏·脫離鈉離子的天然石墨、人造石墨、 焦炭類、碳黑、熱分解碳類、碳纖維、有機高分子化合物 鍛燒體等的碳材料。作爲碳材料的形狀，例如可爲如天然 石墨的薄片狀、如仲碳（mesoearbon)微珠的球狀、如石墨 化碳纖維的纖維狀、或微粉末的凝聚體等之任一者。此處 ’碳材料亦有達成作爲導電材的任務之情況。 . 又’作爲負極活性物質，亦可使用以比正極還低的電 位可吸藏·脫離鈉離子的氧化物、硫化物等的硫屬化合物 -13- 200948721 作爲負極混合劑，可視需要含有黏結劑、導電材。因 此，本發明的鈉蓄電池之負極係可含有負極活性物質及黏 結劑的混合物而成。作爲黏結劑，可舉出熱塑性樹脂，具 體地可舉出PVDF、熱塑性聚醯亞胺、羧甲基纖維素、聚 乙烯、聚丙烯等。 作爲負極集電體，可舉出Cu、Ni、不銹鋼等，從難 以製作與鈉的合金之點、容易加工成薄膜之點來看，較佳 0 爲Cu。作爲使負極集電體擔持負極混合劑的方法，可舉 出與正極的情況同樣地，加壓成型方法、用溶劑等來糊化 而塗佈在負極集電體上，乾燥後進行加壓等而固著的方法 等。 <本發明的鈉蓄電池-隔板> 作爲本發明的鈉蓄電池所可用的隔板，例如可使用由 聚乙烯、聚丙烯等的聚烯烴樹脂、氟樹脂、含氮芳香族聚 © 合物等的材質所成的具有多孔質薄膜、不織布、織布等的 形態之材料。又，亦可爲使用2種以上的此等材質之單層 或積層隔板。作爲隔板，例如可舉出特開2000-30686號 公報、特開平10-324758號公報等中記載的隔板。隔板的 厚度，從能提高電池的體積能量密度，減小內部電阻之點 來看，只要能保持機械強度，則愈薄愈佳。隔板的厚度一 般較佳爲5〜200 μηι左右，更佳爲5〜40 μιη左右。 隔板較佳爲具有含熱塑性樹脂的多孔質薄膜。於蓄電 -14- 200948721 池中，隔板係配置在正極與負極之間，較佳爲在由於正 極-負極間的短路等原因而在電池內有異常電流流動時， 達成遮斷電流，阻止過大電流的流動（關閉）之任務。此處 ，關閉係在超過通常的使用溫度時，藉由閉塞隔板的多孔 質薄膜之微細孔而爲者。而且在關閉後，即使電池內的溫 度上升到某一程度的高溫爲止，該溫度也不會導致破膜， 可維持關閉的狀態，換言之較佳爲耐熱性高者。作爲該隔 ❹ 板，可舉出由耐熱多孔層與多孔質薄膜所層合而成的積層 多孔質薄膜等之具有耐熱材料的多孔質薄膜，較佳爲由含 有耐熱樹脂的耐熱多孔層與含有熱塑性樹脂的多孔質薄膜 所層合而成的積層多孔質薄膜，藉由使用如此具有耐熱材 料的多孔質薄膜當作隔板，可進一步防止本發明的蓄電池 之熱破膜。此處，耐熱多孔層亦可層合在多孔質薄膜的兩 面。 © <本發明的鈉蓄電池-隔板-積層多孔質薄膜隔板> 以下，說明由耐熱多孔層與多孔質薄膜所層合而成的 積層多孔質薄膜所成的隔板。此處，隔板的厚度通常爲 5μιη以上40μιη以下，較佳爲20μιη以下。又，以耐熱多 孔層的厚度當作Α(μιη)，以多孔質薄膜的厚度當作Β(μιη) 時，Α/Β的値較佳爲0.1以上1以下。再者，從離子穿透 性的觀點來看，於此隔板的葛雷（Gurley)法之透氣度中， 透氣度較佳爲 50〜300秒/ l〇〇cc，更佳爲 50〜200秒 /lOOcc。此隔板的空孔率通常爲3〇〜80體積％，較佳爲40 -15- 200948721 〜70體積％。 (耐熱多孔層） 於積層多孔質薄膜中，耐熱多孔層較佳爲含有耐熱樹 脂。爲了更提高離子穿透性，耐熱多孔層的厚度較佳爲 Ιμιη以上ΙΟμιη以下，更佳爲Ιμηι以上5μιη以下，特佳爲 Ιμιη以上4μιη以下的薄耐熱多孔層。又，耐熱多孔層具有 微細孔，該孔的尺寸（直徑）通常爲3μιη以下，較佳爲Ιμιη 以下。再者，耐熱多孔層亦可含有後述的塡料。又，耐熱 多孔層可由無機粉末所形成。 作爲耐熱多孔層所含有的耐熱樹脂，可舉出聚醯胺、 聚醯亞胺、聚醯胺醯亞胺、聚碳酸酯、聚縮醛、聚砸、聚 苯硫醚、聚醚酮、芳香族聚酯、聚醚碾、聚醚醯亞胺，從 更提高耐熱性的觀點來看，較佳爲聚醯胺、聚醯亞胺、聚 醯胺醯亞胺、聚醚楓、聚醚醯亞胺，更佳爲聚醯胺、聚醯 亞胺、聚醯胺醯亞胺。尤更佳爲耐熱樹脂係芳香族聚醯胺 (對位取代芳香族聚醯胺、間位取代芳香族聚醯胺）、芳香 族聚醯亞胺、芳香族聚醯胺醯亞胺等之含氮芳香族聚合物 ’尤更佳爲芳香族聚醯胺’特佳爲對位取代芳香族聚醯胺 (以下亦稱爲「對位芳族聚醯胺」）。又，作爲耐熱樹脂， 亦可舉出聚-4 -甲基戊烯_1、環狀烯烴系聚合物。藉由使用 此等耐熱樹脂，可提高耐熱性’即提高熱破膜溫度。NaaM^z (1) (here, Μ1 and a each have the same definition as described above). The composite metal oxide according to the above <1> or <2>, wherein M1 contains at least Μη. <4> The composite metal oxide according to the above <3>, wherein the molar ratio of Μ1 • Μη is i:b (here, Μ1 has the same definition as described above] 200948721 b is 0.2 or more and less than 1 After that)). The composite metal oxide according to any one of <1>, wherein M1 represents Mn, Fe, and Ni. The composite metal oxide according to any one of <1>, wherein a is in the range of 0.6 or more and 0.9 or less. And a composite metal oxide according to any one of the above-mentioned items, wherein the composite metal oxide according to any one of <1> to <6> is contained. 〇 <8> A positive electrode for a sodium battery, which comprises the positive electrode active material described in the above <7>. <9> A sodium storage battery comprising the positive electrode according to the above <8>. The sodium battery according to the above-mentioned <1>, wherein the separator has a heat-resistant resin, wherein the separator has a heat-resistant resin. A separator of a laminated porous film in which a heat resistant porous layer and a porous film containing a thermoplastic resin are laminated. According to the present invention, it is possible to provide a sodium storage battery which can reduce the amount of lithium used, and which has a large discharge capacity retention ratio during repeated charge and discharge, and a composite metal oxide which can be used as a positive electrode active material. The invention is extremely useful in the industry. [Embodiment] The best mode for carrying out the invention 200948721 <Composite metal oxide of the present invention> The composite metal oxide of the present invention is characterized by comprising Na and M1 (here, M1 represents from Mn, Fe, Co and Ni) The molar ratio of Na:!^1 is a: l (here, a is more than 0.5 in the range of less than 1). Further, the composite metal oxide of the present invention is, for example, represented by the following formula (1) (herein, M1 and a each have the same definitions as described above). In one aspect of the composite metal oxide of the present invention, the Μ1 system contains at least Μη. At this time, 莫1 : 莫η is preferably a l:b (here, M1 has the same definition as described above, and b is 0 or more and less than 1). Further, when Μ1 contains at least Μη and Ni, it is preferable from the viewpoint of further increasing the average discharge voltage of the obtained sodium storage battery and increasing the energy density of the battery. When M1 represents Mn, Fe and Ni, i.e., Co which does not contain a rare metal element, the excellent effect of the present invention can be obtained, and it is more preferable. When M1 represents Mn, Fe and Ni, the composition of the preferred Mn:Fe:Ni (Mohr ratio) is 1: (0.3 to 3): (0.01 to 2), more preferably 1: (0.5 to 2). :(0.1 ~ 1.2). Further, in the meaning of further improving the effect of the present invention, a is preferably in the range of 0.6 or more and 0.9 or less, more preferably in the range of 〇·7 or more and 9.9 or less, particularly preferably about 0.8, that is, 0.75. Above the range of 0.84 below -8- 200948721. In the composite metal oxide of the present invention, a part of the ruthenium 1 may be substituted with a metal element other than Μ1. By substituting, the battery characteristics of the sodium battery can be improved. <Production Method of Composite Metal Oxide of the Present Invention> The composite metal oxide of the present invention can be produced by calcining a mixture of metal-containing compound ruthenium. The mixture has a composite which can be obtained by calcination. The composition of the metal oxide. Specifically, the metal-containing compound containing the corresponding metal element is weighed and mixed in a manner of a predetermined composition, and then the obtained mixture is fired and produced. For example, a metal element having a preferred metal halogen ratio of one such as Na:Mn:Fe:Ni = 0.7:0.333:0.333:0.333 is a composite metal oxide by Na:Mn:Fe The molar ratio of Ni was 0.7:0.333:0.333:0.333, and each of the raw materials of Na2C03, Μη02, and Fe304 was weighed and mixed with each other to obtain a mixture of the obtained ©. As the metal-containing compound which can be used in the production of the composite metal oxide of the present invention, an oxide and a compound which can become an oxide upon pyrolysis and/or oxidation, such as hydroxide 'carbonate, nitrate, halide, Oxalate. The sodium compound is preferably Na2C03, NaHC03 or Na202, and more preferably Na2C03 from the viewpoint of workability. The ruthenium compound is preferably Μη02, the iron compound is preferably Fe304, the nickel compound is preferably NiO, and the cobalt compound is preferably C〇304. Further, these metal-containing compounds may also be hydrates. -9- 200948721 In the mixing of the metal-containing compound, a commercially available device such as a ball mill, a V-type mixer, or a mixer can be used. The mixing at this time may be either dry mixing or wet mixing. Further, a mixture of metal-containing compounds having a specified composition can also be obtained by crystallization. The composite metal oxide of the present invention can be obtained by calcining a mixture of the above metal-containing compound, for example, by heating at a temperature ranging from 600 ° C to 1 600 ° C for 0.5 hours to 100 hours. For example, a preferred calcination temperature range is from 600 ° C to 900 ° C, more preferably from 650 ° C to 85 (temperature range of TC 0 . As a mixture of metal-containing compounds, high temperature is decomposable and/or When an oxidized compound such as a hydroxide, a carbonate, a nitrate, a halide or an oxalate is maintained at a temperature ranging from 400 ° C to 1600 ° C, it is calcined to form an oxide or after removing crystal water. The calcination may be carried out. The environment in which the calcination is carried out may be any of an inert gas atmosphere, an oxidizing atmosphere or a reducing atmosphere, or may be pulverized after calcination. As an environment for calcination, for example, nitrogen may be used. An inert atmosphere of argon or the like; an oxidizing atmosphere of air, oxygen, oxygen-containing nitrogen, oxygen-containing helium, and the like, and a hydrogen containing nitrogen containing 0.1% by volume to 10% by volume of hydrogen, containing 0.1 volume Any one of a reducing environment such as argon gas containing hydrogen in a volume of from 10% by volume to 10% by volume. In order to carry out calcination in a strong reducing atmosphere, a mixture of metal-containing compounds may be calcined by containing an appropriate amount of carbon. Good for Calcination is carried out in an oxidizing atmosphere such as air. As a metal-containing compound, crystallinity of the resulting composite metal oxide can be controlled by using an appropriate amount of a halide such as fluoride or chloride, and -10-200948721 constitutes a composite The average particle diameter of the particles of the metal oxide. In this case, the halide also has a task as a reaction accelerator (flux). As a fluxing aid, for example, NaF, MnF3, FeF2, NiF2 are mentioned. CoF2, NaCl, MnCl2, FeCh, FeCl3, NiCl2, CoCl2, Na2C03, NaHC03, :NH4C1, NH4I, B203, H3B03, etc., can be used as a raw material of the mixture (metal-containing compound), or an appropriate amount is added to the mixture. Further, the flux may be a hydrate. When the composite metal oxide of the present invention is used as a positive electrode active material for a sodium storage battery, it is preferably used arbitrarily for the composite metal oxide obtained as described above. A ball mill, a jet mill, or the like is pulverized, washed, classified, etc. to adjust the particle size. Alternatively, it may be calcined twice or more. Further, it may be made to contain Si or A. l. The inorganic material such as Ti or Y is coated with a surface treatment of the surface of the composite metal oxide, etc. Further, the crystal structure of the composite metal oxide of the present invention is preferably not a tunnel structure. It can be used as a positive electrode active material for sodium batteries, either alone or by application, such as coating, etc. The positive electrode active material contains the composite metal oxide of the present invention, and the composite metal oxide of the present invention is used in sodium. In the battery, the obtained sodium storage battery has a larger discharge capacity retention rate when the charge and discharge are repeated than in the related art. Further, according to the present invention, the internal resistance of the obtained sodium storage battery can be reduced, and the charge and discharge can be reduced. Overvoltage. If the overvoltage at the time of charge and discharge can be reduced, the large current discharge characteristics of the battery can be further improved. Moreover, the stability of the battery when the battery is overcharged can also be improved. -11 - 200948721 <The positive electrode for sodium battery of the present invention and the method for producing the same> The positive electrode for a sodium storage battery of the present invention comprises the positive electrode active material of the present invention. The positive electrode for a sodium storage battery of the present invention can be produced by supporting a positive electrode mixture containing the positive electrode active material, the conductive material and the binder of the present invention on a positive electrode current collector. Examples of the conductive material include carbon materials such as natural graphite, artificial graphite, cokes, and carbon black. The binder is a thermoplastic resin, and specific examples thereof include polyvinylidene fluoride (hereinafter also referred to as "PVDF"), polytetrafluoroethylene, tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride copolymerization. A fluororesin such as a hexafluoropropylene/vinylidene fluoride copolymer or a tetrafluoroethylene/perfluorovinyl ether copolymer, or a polyolefin resin such as polyethylene or polypropylene. As the positive electrode current collector, Al, Ni, stainless steel or the like can be used. The method of supporting the positive electrode mixture on the positive electrode current collector may be a pressure molding method, or may be gelatinized with an organic solvent or the like, applied to the positive electrode current collector, dried, and then fixed by pressurization or the like. method. At the time of gelatinization, a slurry composed of a positive electrode active material, a conductive material, a binder, and an organic solvent is produced. Examples of the organic solvent include amines such as N,N-dimethylaminopropylamine and triethylamine: ethers such as ethylene oxide and tetrahydrofuran; and ketones such as methyl ethyl ketone; An ester system such as an ester; an aprotic polar solvent such as dimethylacetamide or N-methyl-2-pyrrolidone. Examples of the method of applying the positive electrode mixture to the positive electrode current collector include a slit die coating method, a screen coating method, a curtain coating method, a knife coating method, a gravure coating method, and an electrostatic spray. Law and so on. <Sodium battery of the present invention> -12- 200948721 The sodium battery of the present invention has the positive electrode for a sodium storage battery of the present invention. In the sodium battery of the present invention, for example, an electrode group can be obtained by laminating and winding a positive electrode for a sodium storage battery of the present invention, a separator, and a negative electrode obtained by supporting a negative electrode mixture on a negative electrode current collector. The electrode group is housed in a battery can, and is produced by impregnating an electrode group with an electrolytic solution made of an organic solvent containing an electrolyte. The shape of the electrode group herein may be a shape formed by a circle, an ellipse, an ellipse, a rectangle, a chamfered rectangle, or the like, for example, when it is cut in a direction perpendicular to the Ο axis of the wound electrode group. . In addition, the shape of the battery is, for example, a paper type, a coin type, a cylinder type, a square shape, or the like. "Sodium battery-negative electrode of the present invention" As a negative electrode usable for the sodium storage battery of the present invention, it can be used. The negative electrode mixture containing the negative electrode active material is supported by the negative electrode current collector, and can be occluded. © An electrode that removes sodium ions such as sodium metal or sodium alloy. Examples of the negative electrode active material include natural graphite, artificial graphite, coke, carbon black, pyrolytic carbon, carbon fiber, and organic polymer compound calcined body which can absorb and remove sodium ions. The shape of the carbon material may be, for example, a flake shape of natural graphite, a spherical shape such as mesoearbon microbeads, a fibrous form such as graphitized carbon fibers, or an aggregate of fine powders. Here, 'carbon materials also have the task of achieving a conductive material. Further, as the negative electrode active material, a chalcogen compound such as an oxide or a sulfide which can be occluded or desorbed from a sodium ion at a potential lower than that of the positive electrode can be used as a negative electrode mixture, and a binder can be optionally used. , conductive materials. Therefore, the negative electrode of the sodium secondary battery of the present invention may contain a mixture of a negative electrode active material and a binder. The binder may, for example, be a thermoplastic resin, and specific examples thereof include PVDF, thermoplastic polyimide, carboxymethylcellulose, polyethylene, and polypropylene. Examples of the negative electrode current collector include Cu, Ni, and stainless steel. From the viewpoint that it is difficult to produce an alloy with sodium and it is easy to process into a film, it is preferable that 0 is Cu. In the same manner as in the case of the positive electrode, a pressure molding method, a method of gelatinizing a solvent, and the like, and applying it to a negative electrode current collector, drying and then applying pressure The method of fixing and the like. <Sodium battery-separator of the present invention> As the separator usable for the sodium storage battery of the present invention, for example, a polyolefin resin such as polyethylene or polypropylene, a fluororesin, or a nitrogen-containing aromatic polymer can be used. A material having a form such as a porous film, a nonwoven fabric, or a woven fabric formed by a material such as the like. Further, a single layer or a laminated separator of two or more of these materials may be used. For example, the separators described in JP-A-2000-30686, JP-A-10-324758, and the like can be used. The thickness of the separator is preferably as thin as long as the mechanical strength can be maintained from the viewpoint of increasing the volumetric energy density of the battery and reducing the internal resistance. The thickness of the separator is generally preferably from about 5 to about 200 μηη, more preferably from about 5 to about 40 μm. The separator preferably has a porous film containing a thermoplastic resin. In the storage battery-14-200948721, the separator is disposed between the positive electrode and the negative electrode. It is preferable to prevent the current from being interrupted when an abnormal current flows in the battery due to a short circuit between the positive electrode and the negative electrode. The task of flowing (off) the current. Here, when the shutdown is performed at a temperature exceeding the normal use temperature, the pores of the porous film of the separator are closed. Further, even after the shutdown, even if the temperature in the battery rises to a certain high temperature, the temperature does not cause film rupture, and the closed state can be maintained, in other words, the heat resistance is preferably high. The porous separator having a heat-resistant material such as a laminated porous film obtained by laminating a heat-resistant porous layer and a porous film is preferably a heat-resistant porous layer containing a heat-resistant resin and containing the porous separator. In the laminated porous film in which the porous film of the thermoplastic resin is laminated, by using a porous film having such a heat-resistant material as a separator, thermal rupture of the battery of the present invention can be further prevented. Here, the heat resistant porous layer may be laminated on both sides of the porous film. [Sodium battery-separator-layered porous film separator of the present invention] Hereinafter, a separator made of a laminated porous film in which a heat resistant porous layer and a porous film are laminated will be described. Here, the thickness of the separator is usually 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 regarded as Α (μιη) and the thickness of the porous film is regarded as Β (μιη), the Α/Β 値 is preferably 0.1 or more and 1 or less. Further, from the viewpoint of ion permeability, the gas permeability of the Gurley method of the separator is preferably 50 to 300 sec / l cc, more preferably 50 to 200. Seconds / lOOcc. The porosity of the separator is usually from 3 〇 to 80 vol%, preferably from 40 -15 to 200948721 to 70 vol%. (Heat-resistant porous layer) In the laminated porous film, the heat-resistant porous layer preferably contains a heat-resistant resin. In order to further improve the ion permeability, the thickness of the heat resistant porous layer is preferably Ιμηη or more and ΙΟμηη or less, more preferably Ιμηι or more and 5 μm or less, and particularly preferably 薄μηη or more and 4 μηη or less. Further, the heat resistant porous layer has fine pores, and the size (diameter) of the pores is usually 3 μm or less, preferably Ιμηη or less. Further, the heat resistant porous layer may contain a dip material to be described later. Further, the heat resistant porous layer may be formed of an inorganic powder. Examples of the heat resistant resin contained in the heat resistant porous layer include polyamine, polyimine, polyamidimide, polycarbonate, polyacetal, polyfluorene, polyphenylene sulfide, polyether ketone, and aromatic. The group polyester, the polyether mill, and the polyether oximine are preferably polyamine, polyimine, polyamidamine, polyether maple, polyether oxime from the viewpoint of further improving heat resistance. The imine is more preferably polyamine, polyimine or polyamidimide. More preferably, it is a heat-resistant resin-based aromatic polyamine (para-substituted aromatic polyamine, meta-substituted aromatic polyamide), aromatic polyimide, aromatic polyamidimide, etc. The nitrogen-aromatic polymer is more preferably an aromatic polyamine. It is preferably a para-substituted aromatic polyamine (hereinafter also referred to as "para-aramid"). Further, examples of the heat resistant resin include poly-4-methylpentene-1 and a cyclic olefin polymer. By using these heat-resistant resins, heat resistance can be improved, that is, the thermal film-breaking temperature can be increased.
熱破膜溫度係依賴於耐熱樹脂的種類，可按照使用場 面、使用目的來選擇使用。通常，熱破膜溫度爲l6〇t：W 200948721 上。作爲耐熱樹脂’使用上述含氮芳香族聚合物時可將熱 破膜溫度控制在400 °C左右，而且使用聚-4-甲基戊烯-1時 可將熱破膜溫度控制在250 °C左右，使用環狀烯烴系聚合 物時可將熱破膜溫度控制在300 °C左右。又，於耐熱多孔 層由無機粉末所成時，亦可能將熱被膜溫度例如控制在 5〇0°C以上。 上述對位芳族聚醯胺係由對位取代芳香族二胺與對位 〇 取代芳香族二羧醯鹵的縮合聚合而得者，醯胺鍵係由芳香 族環的對位或按照其的取代位置（例如4,4 伸聯苯基、 1，5 -萘、2,6 -萘等般的在相反方向同軸或平行地延長的取 代位置）所鍵結的重複單位所實質上而成者。作爲對位芳 族聚醯胺，可例示具有對位取代型或按照對位取代型的構 造之對位芳族聚醯胺，具體地如聚（對伸苯基對苯二甲醯 胺）、聚（對苯甲醯胺）、聚（4,4’_苯甲醯苯胺對苯二甲醯胺） 、聚（對伸苯基-4,4’-伸聯苯基二羧醯胺）、聚（對伸苯基-® 2,6-萘二羧醯胺）、聚（2-氯-對伸苯基對苯二甲醯胺）、對伸 苯基對苯二甲醯胺/2,6-二氯對伸苯基對苯二甲醯胺共聚物 等。 作爲上述芳香族聚醯亞胺，較佳爲由芳香族的二酸酐 與二胺的縮聚合所製造的全芳香族聚醯亞胺。作爲二酸酐 的具體例，可舉出均苯四酸二酐、3，3’，4,4’-二苯基颯四羧 酸二酐、3,3’，4,4’-二苯甲酮四羧酸二酐、2,2’·雙（3,4-二 羧基苯基）六氟丙烷、3，3’，4,4’-聯苯基四羧酸二酐等。作 爲二胺，可舉出氧基二苯胺、對苯二胺、二苯甲酮二胺、 -17- 200948721 3,3’-亞甲基二苯胺、3,3’-二胺基二苯甲酮、3,3，_二胺基 二苯基諷、1，5’-萘二胺等。又，可合適地使用溶劑可溶的 聚醯亞胺。作爲如此的聚醯亞胺，例如可舉出3,3，，4,4，- 二苯基碾四羧酸二酐與芳香族二胺的聚縮合物之聚醯亞胺 〇 作爲上述芳香族聚醯胺醯亞胺，可舉出使用芳香族二 羧酸及芳香族二異氰酸酯，由此等的縮合聚合所得者，使 用芳香族二酸酐及芳香族二異氰酸酯，由此等的縮合聚合 所得者。作爲芳香族二羧酸的具體例，可舉出間苯二甲酸 、對苯二甲酸等。又，作爲芳香族二酸酐的具體例，可舉 出偏苯三酸酐等。作爲芳香族二異氰酸酯的具體例，可舉 出4,4’-二苯基甲烷二異氰酸酯、2,4·伸甲苯二異氰酸酯、 2,6-伸甲苯二異氰酸酯、鄰伸甲苯二異氰酸酯、間二甲苯 二異氰酸酯等。 於耐熱多孔層含有耐熱樹脂時，耐熱多孔層可含有1 種以上的塡料。耐熱多孔層所可含有的塡料係可從有機粉 末、無機粉末或此等的混合物之任一者所選出。構成塡料 的粒子之平均粒徑較佳爲0.01 μιη以上Ιμιη以下。塡料的 形狀例如可爲略球狀、板狀、柱狀、針狀、鬚晶狀、纖維 狀等，亦可以使用任一種粒子，但從容易形成均勻的孔來 看，較佳爲略球狀粒子。作爲略球狀粒子，可舉出粒子的 縱橫比（粒子的長徑/粒子的短徑）爲1以上1.5以下的範圍 之値的粒子。粒子的縱橫比係可藉由電子顯微鏡照相來測 定。 -18- 200948721 作爲當作塡料的有機粉末，例如可舉出由苯乙烯、乙 烯基酮、丙烯腈、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲 基丙烯酸縮水甘油酯、丙烯酸縮水甘油酯、丙烯酸甲酯等 的單獨或2種類以上的共聚物，聚四氟乙烯、四氟乙烯-六氟丙烯共聚物、四氟乙烯-乙烯共聚物、聚偏二氟乙烯 等的氟系樹脂，蜜胺樹脂，尿素樹脂，聚烯烴，聚甲基丙 烯酸酯等的有機物所成的粉末。有機粉末係可單獨使用， 也可混合2種以上來使用。於此等有機粉末之中，從化學 安定性之點來看，較佳爲聚四氟乙烯粉末。 作爲當作塡料的無機粉末，例如可舉出由金屬氧化物 、金屬氮化物、金屬碳化物、金屬氫氧化物、碳酸鹽、硫 酸鹽等的無機物所成的粉末，於此等之中，較宜使用由導 電性低的無機物所成的粉末。若具體地例示，可舉出由氧 化鋁、矽石、二氧化鈦、硫酸鋇或碳酸鈣等所成的粉末。 無機粉末係可單獨使用，也可混合2種以上來使用。於此 ^ 等無機粉末之中，從化學安定性之點來看，較佳爲氧化鋁 粉末。較佳爲構成塡料的粒子皆係氧化鋁粒子，更佳爲構 成塡料的粒子皆係氧化鋁粒子，且其一部分或全部爲略球 狀的氧化鋁粒子。附帶一提，於耐熱多孔層由無機粉末所 形成時，可使用上述例示的無機粉末，視需要可與黏結劑 混合使用。 於耐熱多孔層含有耐熱樹脂時，塡料的含量亦取決於 塡料材質之比重，例如於構成塡料的粒子皆係氧化鋁粒子 時，若以耐熱多孔層的總重量當作1 00，則塡料的重量通 -19- 30 200948721 常爲5以上95以下，較佳爲20以上95以下，更佳爲 以上90以下。此等範圍係可依賴於塡料材質的比重來 宜設定。 (多孔質薄膜） 於積層多孔質薄膜中，多孔質薄膜較佳爲具有微細 ，進行關閉。於此情況下，多孔質薄膜含有熱塑性樹脂 此多孔質薄膜的厚度通常爲3〜30μπι，更佳爲3〜25μιη 多孔質薄膜係與上述耐熱多孔層同樣地，具有微細孔， 孔的尺寸通常爲3μιη以下，較佳爲Ιμιη以下。多孔質 膜的空孔率通常30〜80體積％，較佳爲40〜70體積％ 於非水電解質蓄電池中，當超過通常的使用溫度時，多 質薄膜係可藉由構成它的熱塑性樹脂之軟化而將微細孔 塞。 作爲多孔質薄膜所含有的熱塑性樹脂，可舉出在80 180°C軟化者，可選擇不溶解在非水電解質蓄電池的電 液中者。具體地，作爲熱塑性樹脂，可舉出聚乙烯、聚 烯等的聚烯烴樹脂、熱塑性聚胺甲酸酯樹脂，可使用此 之2種以上的混合物。爲了在更低溫軟化使關閉，作爲 塑性樹脂，較佳爲含有聚乙烯。作爲聚乙烯，具體地可 出低密度聚乙烯、高密度聚乙烯、線狀聚乙烯等的聚乙 ，亦可舉出分子量爲100萬以上的超高分子量聚乙烯。 了更提高多孔質薄膜的突刺強度，熱塑性樹脂較佳爲至 含有超高分子量聚乙烯。又，於多孔質薄膜的製造方面 適 孔 其 薄 〇 孔 閉 解 丙 等 熱 舉 烯 爲 少 中 -20- 200948721 ，熱塑性樹脂亦較佳爲含有由低分子量（重量平均分子量1 萬以下）的聚烯烴所成的蠟。 又’作爲具有與上述積層多孔質薄膜不同的耐熱材料 之多孔質薄膜’可舉出由耐熱樹脂及/或無機粉末所成的 多孔質薄膜，或耐熱樹脂及/或無機粉末分散在聚烯烴樹 脂或熱塑性聚胺甲酸酯樹脂等的熱塑性樹脂薄膜中之多孔 質薄膜。此處，作爲耐熱樹脂、無機粉末，可舉出上述者 ❹ <本發明的鈉蓄電池-電解液或固體電解質> 於本發明的鈉蓄電池所可用的電解液中，作爲電解質 ，可舉出 NaC104 、 NaPF6 、 NaAsF6 、 NaSbF6 、 NaBF4 、 NaCF3S03、NaN(S02CF3)2、低級脂肪族羧酸鈉鹽、 NaAlCl4等，可使用此等的2種以上之混合物。於此等之 中，較佳爲使用含有從含氟的NaPF6、NaAsF6、NaSbF6、 ® NaBF4、NaCF3S03及NaN(S02CF3)2所組成族群所選出的 至少1種。 於本發明的鈉蓄電池所可用的電解液中，作爲有機溶 劑，例如可使用碳酸伸丙酯、碳酸伸乙酯、碳酸二甲酯、 碳酸二乙酯、碳酸乙基甲酯、碳酸異丙基甲酯、碳酸伸乙 烯酯、4-三氟甲基-1，3-二噁茂烷-2-酮、1,2-二（甲氧基羰 氧基）乙烷等的碳酸酯類；1,2-二甲氧基乙烷、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 -甲基四氫呋喃等的醚類；甲酸甲酯、乙酸 -21 - 200948721 甲酯、γ-丁內酯等的酯類；乙腈、丁腈等的腈類；N，n-二 甲基甲醯胺、Ν,Ν-二甲基乙醯胺等的醯胺類；3 -甲基-2-噁 唑烷酮等的胺基甲酸酯類；環丁諷、二甲亞颯、1，3-丙磺 酸內酯等的含硫化合物；或在上述有機溶劑中更導入有氟 取代基者。通常地，作爲有機溶劑，混合此等之中的二種 以上。 又，代替前述電解液，亦可使用固體電解質。作爲固 體電解質，例如可使用聚環氧乙烷系的高分子化合物、含 @ 有聚有機矽氧烷鏈或聚氧化烯鏈的至少一種以上之高分子 化合物等的有機系固體電解質。又，亦可用使高分子化合 物中保持有非水電解質溶液的所謂凝膠型者。又，可使用 Na2S-SiS2、Na2S-GeS2、NaTi2(P〇4)3、NaFe2(P04)3、 Na2(S04)3、Fe2(S04)2(P04)、Fe2(M〇04)3 等的無機系固體 電解質。使用此等固體電解質，可更提高安全性。又，於 本發明的鈉蓄電池中，使用固體電解質時，固體電解質亦 有達成隔板的任務之情況，於該情況下，亦未必需要隔板 U [實施例] 以下藉由實施例來更詳細說明本發明，惟本發明完全 不受此等所限定。再者，只要沒有特別預先指明，則充放 電試驗用的電極及蓄電池的製作方法、以及粉末X射線繞 射的測定方法係如下述。 -22- 200948721 (1)電極（正極）的製作 以正極活性物質：導電材：黏結劑=85 :10:5(重量比） 的組成之方式，分別秤量當作正極活性物質的複合金屬氧 化物、當作導電材的乙炔黑（電氣化學工業股份公司製）、 及當作黏結劑的PVDF(股份公司Kureha製，PolyVinylidene DiFluoride Polyflon)。然後，首先於瑪瑙硏鉢中充分混合 複合金屬氧化物與乙炔黑，於此混合物中適加添加N-甲 〇 基-2-吡咯烷酮（NMP :東京化成工業股份公司製），再添加 PVDF，接著混合到成爲均勻，進行漿體化。使用塗佈機 ，將所得到的漿體以1〇〇 μπι的厚度塗佈到集電體的厚度 4 0μιη之鋁箔上，將其置入乾燥機內，邊去除ΝΜΡ，邊充 分乾燥，而得到電極片。藉由電極冲壓機，將此電極片冲 壓成直徑1.5cm後，以手壓機來充分壓著，而得正極。 (2) 電池的製作 ® 於硬幣型電池（寶泉股份公司製）的下側部分之凹處， 使鋁箔朝下而配置正極，然後組合當作電解液的1M之 NaC104/碳酸伸丙酯、當作隔板的聚丙烯多孔質薄膜（厚度 20μιη)、及當作負極的金屬鈉（Andrich公司製），以製作電 池。再者，電池的組裝係在氬氣環境的手套箱內進行。 (3) 粉末X射線繞射測定 測定係使用股份公司Rigaku製的粉末X射線繞射測 定裝置RINT2500TTR型，在以下的條件下進行： -23- 200948721 X射線：CuKa 電壓—電流：40kV-140mA 測定角度範圍：2Θ=10〜60。 步距：0.02° 掃描速度：4° /分鐘 比較例 l(Na:Mn:Co = 〇.7:0.50:0.50)The thermal film rupture temperature depends on the type of the heat resistant resin, and can be selected according to the use surface and the purpose of use. Usually, the thermal film rupture temperature is l6〇t: W 200948721. When the above nitrogen-containing aromatic polymer is used as the heat resistant resin, the thermal film rupture temperature can be controlled to about 400 ° C, and the thermal film rupture temperature can be controlled to 250 ° C when poly-4-methylpentene-1 is used. When the cyclic olefin polymer is used, the thermal film rupture temperature can be controlled to about 300 °C. Further, when the heat resistant porous layer is formed of an inorganic powder, the temperature of the hot film may be controlled, for example, to 5 °C or more. The above-mentioned para-aromatic polyamine is obtained by condensation polymerization of a para-substituted aromatic diamine and a para-derivative-substituted aromatic dicarboxylic acid halide, and the indole bond is coordinated by an aromatic ring or according thereto. Substituting positions (for example, 4,4 exophenyl, 1,5-naphthalene, 2,6-naphthalene, etc., in the opposite direction, the position of the substitution in the opposite direction or the parallel extension) . As the para-aromatic polyamine, a para-aromatic polyamine having a para-substitution type or a para-substitution type, specifically, poly(p-phenylene terephthalamide), Poly(p-benzamide), poly(4,4'-benzamide-p-xylyleneamine), poly(p-phenylene-4,4'-extended biphenylguanidinium), Poly(p-phenylene® 2,6-naphthalenedicarbamide), poly(2-chloro-p-phenylene terephthalamide), p-phenylene terephthalamide/2, 6-Dichloro-p-phenyl-p-xylyleneamine copolymer and the like. The aromatic polyimine is preferably a wholly aromatic polyimine produced by polycondensation of an aromatic dianhydride and a diamine. Specific examples of the dianhydride include pyromellitic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, and 3,3',4,4'-diphenylene. Ketone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and the like. Examples of the diamine include oxydiphenylamine, p-phenylenediamine, benzophenone diamine, -17-200948721 3,3'-methylenediphenylamine, and 3,3'-diaminobiphenyl. Ketone, 3,3,-diaminodiphenyl pyrene, 1,5'-naphthalenediamine, and the like. Further, a solvent-soluble polyimine can be suitably used. As such a polyimine, for example, a polycondensed product of a polycondensate of 3,3,4,4,-diphenyltricarboxylic dianhydride and an aromatic diamine is mentioned as the above aromatic The polyamidoximine may be an aromatic dicarboxylic acid or an aromatic diisocyanate, and an aromatic dianhydride or an aromatic diisocyanate may be used as a result of condensation polymerization. . Specific examples of the aromatic dicarboxylic acid include isophthalic acid and terephthalic acid. Further, specific examples of the aromatic dianhydride include trimellitic anhydride and the like. Specific examples of the aromatic diisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4·toluene diisocyanate, 2,6-toluene diisocyanate, ortho-toluene diisocyanate, and m-bis. Toluene diisocyanate or the like. When the heat resistant porous layer contains a heat resistant resin, the heat resistant porous layer may contain one or more kinds of pigments. The tanning material which can be contained in the heat resistant porous layer can be selected from any of organic powder, inorganic powder or a mixture of these. The average particle diameter of the particles constituting the dip is preferably 0.01 μm or more and Ιμηη or less. The shape of the dip material may be, for example, a slightly spherical shape, a plate shape, a column shape, a needle shape, a whisker shape, a fiber shape, or the like, and any of the particles may be used. However, from the viewpoint of easily forming a uniform pore, it is preferable to slightly move the ball. Shaped particles. Examples of the spheroidal particles include particles having an aspect ratio of the particles (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 measured by electron microscopy. -18- 200948721 Examples of the organic powder to be used as the dip material include styrene, vinyl ketone, acrylonitrile, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, and glycidol acrylate. a copolymer of two or more types of esters, methyl acrylate or the like, a fluorine-based resin such as polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer or polyvinylidene fluoride, A powder of organic matter such as melamine resin, urea resin, polyolefin, polymethacrylate or the like. The organic powder may be used singly or in combination of two or more. Among these organic powders, polytetrafluoroethylene powder is preferred from the viewpoint of chemical stability. Examples of the inorganic powder to be used as the pigment include powders derived from inorganic substances such as metal oxides, metal nitrides, metal carbides, metal hydroxides, carbonates, and sulfates. It is preferred to use a powder composed of an inorganic material having low conductivity. Specific examples thereof include powders made of alumina, vermiculite, titania, barium sulfate or calcium carbonate. The inorganic powder may be used singly or in combination of two or more. Among the inorganic powders such as these, from the viewpoint of chemical stability, alumina powder is preferred. Preferably, the particles constituting the mash are all alumina particles, and more preferably the particles constituting the mash are all alumina particles, and some or all of them are slightly spherical alumina particles. Incidentally, when the heat resistant porous layer is formed of an inorganic powder, the above-exemplified inorganic powder may be used, and if necessary, it may be used in combination with a binder. When the heat-resistant porous layer contains a heat-resistant resin, the content of the material depends on the specific gravity of the material of the material. For example, when the particles constituting the material are all alumina particles, if the total weight of the heat-resistant porous layer is regarded as 100, The weight of the dip material is -19- 30 200948721. It is usually 5 or more and 95 or less, preferably 20 or more and 95 or less, and more preferably 90 or less. These ranges can be set depending on the specific gravity of the material of the material. (Porous Film) In the laminated porous film, the porous film is preferably fine and closed. In this case, the porous film contains a thermoplastic resin. The thickness of the porous film is usually 3 to 30 μm, more preferably 3 to 25 μm. The porous film has micropores in the same manner as the heat resistant porous layer, and the size of the pores is usually 3 μm or less, preferably Ιμηη or less. The porosity of the porous membrane is usually 30 to 80% by volume, preferably 40 to 70% by volume in the nonaqueous electrolyte secondary battery. When the temperature exceeds the usual use temperature, the porous film can be formed by the thermoplastic resin constituting it. Soften and plug the fine pores. The thermoplastic resin contained in the porous film may be a softener which is softened at 80 to 180 ° C, and may be selected from those which do not dissolve in the electrolyte of the nonaqueous electrolyte secondary battery. Specifically, the thermoplastic resin may be a polyolefin resin such as polyethylene or polyolefin or a thermoplastic polyurethane resin, and a mixture of two or more of these may be used. In order to soften it at a lower temperature, it is preferable to contain polyethylene as a plastic resin. Specific examples of the polyethylene include polyethylene glycol such as low density polyethylene, high density polyethylene, and linear polyethylene, and an ultrahigh molecular weight polyethylene having a molecular weight of 1,000,000 or more. Further, the spur strength of the porous film is further increased, and the thermoplastic resin preferably contains ultrahigh molecular weight polyethylene. Further, in the production of a porous film, it is suitable for the pores of the porous film to be closed, and the like, such as propylene, is a low-molecular weight (weight average molecular weight of 10,000 or less). a wax formed from an olefin. Further, 'a porous film having a heat resistant material different from the laminated porous film' may be a porous film made of a heat resistant resin and/or an inorganic powder, or a heat resistant resin and/or an inorganic powder dispersed in a polyolefin resin. Or a porous film in a thermoplastic resin film such as a thermoplastic polyurethane resin. Here, examples of the heat-resistant resin and the inorganic powder include the above-mentioned sodium battery-electrolyte or solid electrolyte of the present invention. In the electrolyte solution usable in the sodium battery of the present invention, examples of the electrolyte include electrolytes. NaC104, NaPF6, NaAsF6, NaSbF6, NaBF4, NaCF3S03, NaN(S02CF3)2, a lower aliphatic carboxylic acid sodium salt, NaAlCl4, etc., a mixture of two or more of these may be used. Among these, at least one selected from the group consisting of fluorine-containing NaPF6, NaAsF6, NaSbF6, ® NaBF4, NaCF3S03, and NaN(S02CF3)2 is preferably used. In the electrolytic solution usable in the sodium storage battery of the present invention, as the organic solvent, for example, propyl carbonate, ethyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or isopropyl carbonate can be used. a carbonate such as a methyl ester, a vinyl carbonate, a 4-trifluoromethyl-1,3-dioxan-2-one or a 1,2-bis(methoxycarbonyloxy)ethane; , 2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran ' 2 - An ether such as methyltetrahydrofuran; an ester of methyl formate, acetate-21 - 200948721 methyl ester or γ-butyrolactone; a nitrile such as acetonitrile or butyronitrile; N,n-dimethylformamide; Terpenes such as hydrazine, hydrazine-dimethylacetamide, urethanes such as 3-methyl-2-oxazolidinone; cyclamate, dimethyl hydrazine, 1,3-propane sulfonate A sulfur-containing compound such as an acid lactone; or a fluorine-substituted compound further introduced into the above organic solvent. Usually, two or more of these are mixed as an organic solvent. Further, a solid electrolyte may be used instead of the above electrolyte solution. As the solid electrolyte, for example, a polyethylene oxide-based polymer compound or an organic solid electrolyte containing at least one polymer compound having a polyorganosiloxane chain or a polyoxyalkylene chain can be used. Further, a so-called gel type in which a nonaqueous electrolyte solution is held in a polymer compound can also be used. Further, Na2S-SiS2, Na2S-GeS2, NaTi2(P〇4)3, NaFe2(P04)3, Na2(S04)3, Fe2(S04)2(P04), Fe2(M〇04)3, etc. may be used. Inorganic solid electrolyte. The use of such solid electrolytes can further improve safety. Further, in the sodium battery of the present invention, when a solid electrolyte is used, the solid electrolyte also has a task of achieving a separator. In this case, the separator U is not necessarily required. [Examples] Hereinafter, the examples will be described in more detail. The invention is described, but the invention is not limited at all. Further, the electrode and the battery for charging and discharging test, and the method for measuring powder X-ray diffraction are as follows, unless otherwise specified. -22- 200948721 (1) Preparation of the electrode (positive electrode) The composite metal oxide used as the positive electrode active material was weighed in the form of a positive electrode active material: a conductive material: a binder: 85:10:5 (weight ratio). Acetylene black (made by Electric Chemical Industry Co., Ltd.) as a conductive material, and PVDF (PolyVinylidene DiFluoride Polyflon, manufactured by Kureha Co., Ltd.) as a binder. Then, the mixed metal oxide and acetylene black are first sufficiently mixed in an agate crucible, and N-formyl-2-pyrrolidone (NMP: manufactured by Tokyo Chemical Industry Co., Ltd.) is added to the mixture, and PVDF is added, followed by PVDF. Mix until homogeneous and slurry. Using a coater, the obtained slurry was applied to an aluminum foil having a thickness of 40 μm of a current collector at a thickness of 1 μm, and placed in a dryer to be sufficiently dried while removing the crucible. Electrode sheet. This electrode sheet was pressed into a diameter of 1.5 cm by an electrode punching machine, and then sufficiently pressed by a hand press to obtain a positive electrode. (2) Preparation of the battery 于 In the recess of the lower part of the coin-type battery (made by Baoquan Co., Ltd.), the positive electrode is placed with the aluminum foil facing downward, and then 1 M of NaC104/propylene carbonate as the electrolyte is combined. A polypropylene porous film (thickness: 20 μm) as a separator and metal sodium (manufactured by Andrich) as a negative electrode were used to produce a battery. Furthermore, the assembly of the battery was carried out in a glove box in an argon atmosphere. (3) Powder X-ray diffraction measurement is performed using the powder X-ray diffraction measuring device RINT2500TTR manufactured by Rigaku Co., Ltd. under the following conditions: -23- 200948721 X-ray: CuKa voltage-current: 40kV-140mA Angle range: 2Θ=10~60. Step: 0.02° Scanning speed: 4° / minute Comparative example l (Na:Mn:Co = 〇.7:0.50:0.50)
(1) 複合金屬氧化物的製造 Q 以Na:Mn:Co的莫耳比成爲0.7:0.50:0.50的方式秤量 當作含金屬的化合物之碳酸鈉（Na2C03 :和光純藥工業股 份公司製：純度99.8%)、氧化錳（IV)(Mn02 :股份公司高 純度化學硏究所製：純度99.9%)、及四氧化三鈷（Co3〇4: 正同化學工業股份公司製：純度99%)，藉由乾式球磨機 混合4小時而得到含金屬的化合物之混合物。將所得到之 含金屬的化合物之混合物塡充於氧化鋁船中，使用電爐在 空氣環境中加熱，於800°C保持2小時而得到比較例1之 Q 複合金屬氧化物C1。第1圖中顯示比較例1的複合金屬 氧化物C1之粉末X射線繞射圖形。 (2) 作爲鈉蓄電池的正極活性物質之充放電性能評價 使用比較例1的複合金屬氧化物C1當作鈉蓄電池用 的正極活性物質，製作電池，在以下的條件下實施恆定電 流充放電試驗。 -24- 200948721 充放電條件： 充電係以0.1C速率（10小時完全充電的速度）進行 CC(C〇nstant current :定電流）充電直到4.0V爲止。放電 係以與該充電速度同樣的速度，進行CC放電，在電壓 1-5V時截止。下一個循環以後之充電、放電係以與該充電 速度同樣的速度進行，與第1循環同樣地，在充電電壓 4-0V、放電電壓1.5V時截止。 © 此電池在重複10個循環的充放電後，相對於第1循 環的放電容量而言，第10循環的放電容量維持率爲76% 實施例 l(Na:Mn:Co:Ni = 0.7:0.495:0.495:0.0 1，式（1)中的 M1 係 Mn、Co 及 Ni，a 係 0.7。而且，b 係 0.495) (1)複合金屬氧化物的製造 以 Na:Mn:Co:Ni 的莫耳比成爲 0.7:0.495:0.495:0.01 的方式，秤量當作含金屬的化合物之碳酸鈉（Na2C03 :和 光純藥工業股份公司製：純度99.8%)、氧化錳（IV)(Mn02 :股份公司高純度化學硏究所製：純度9 9.9%)、四氧化三 鈷（C〇304 :正同化學工業股份公司製：純度99%)、及氧 化鎳（II)(NiO :股份公司高純度化學硏究所製：純度99%) ，藉由乾式球磨機混合4小時而得到含金屬的化合物之混 合物。將所得到之含金屬的化合物之混合物塡充於氧化鋁 船中，使用電爐在空氣環境中加熱，於800 °C保持2小時 而得到實施例1之複合金屬氧化物E1。第2圖中顯示實 -25- 200948721 施例1的複合金屬氧化物El之粉末X射線繞射圖形。 (2)作爲鈉蓄電池的正極活性物質之充放電性能評價 使用實施例1的複合金屬氧化物E1當作鈉蓄電池用 的正極活性物質，製作電池，於與比較例1之場合同樣的 條件下，實施恆定電流充放電試驗。此電池在重複1〇個 循環的充放電後，相對於第1循環的放電容量而言，第1〇 循環的放電容量維持率爲109%。 實施例 2 (Na:Mn:Co:Ni = 0.7:0.45:0.45 :0.10，式（1)中的 M1 係 Mn、Co 及 Ni，a 係 0.7。而且，b 係 0_45) (1) 複合金屬氧化物的製造 除了以 Na:Mn:Co:Ni 的莫耳比成爲 0.7:0.45:0.45:0.1 0 的量來使用含金屬的化合物以外，與實施例1同樣地，得 到實施例2的複合金屬氧化物E2。第3圖中顯示實施例2 的複合金屬氧化物E2之粉末X射線繞射圖形。 (2) 作爲鈉蓄電池的正極活性物質之充放電性能評價 使用實施例2的複合金屬氧化物E2當作鈉蓄電池用 的正極活性物質，製作電池，於與比較例1之場合同樣的 條件下，實施恆定電流充放電試驗。此電池在重複10個 循環的充放電後，相對於第1循環的放電容量而言，第1〇 循環的放電容量維持率爲89°/。。 200948721 實施例 3(Na:Mn:Co:Ni = 0.7:0.3 3 3:0.3 3 3:0.3 3 3，式（1)中的 Μ1 係 Μη、Co 及 Ni，a 係 0·7。而且，b 係 0.33 3) (1) 複合金屬氧化物的製造 除了以 Na:Mn:Co:Ni 的莫耳比成爲 0.7:0.3 33:0.333:0.333 的量來使用含金屬的化合物以外，與實施例1同樣地，得 到實施例3的複合金屬氧化物E3。第4圖中顯示實施例3 的複合金屬氧化物E3之粉末X射線繞射圖形。 (2) 作爲鈉蓄電池的正極活性物質之充放電性能評價 使用實施例3的複合金屬氧化物E3當作鈉蓄電池用 的正極活性物質，製作電池，於與比較例1之場合同樣的 條件下，實施恆定電流充放電試驗。此電池在重複10個 循環的充放電後，相對於第1循環的放電容量而言，第10 循環的放電容量維持率爲90%。 實施例 4(Na:Mn:Fe:Ni = 0_7:0.3 3 3:0.3 3 3:0.3 3 3，式（1)中的 M1 係 Mn、Fe 及 Ni’ a 係 0.7。而且，b 係 0.333) (1)複合金屬氧化物的製造 以 Na: Mn :Fe:Ni 的莫耳比成爲 0.7:0.333:0.333:0.333 的方式’秤量當作含金屬的化合物之碳酸鈉（Na2C03 :和 光純藥工業股份公司製：純度99.8%)、氧化錳（IV)(Mn02 :股份公司高純度化學硏究所製：純度99.9°/。）、氧化鐵（II 、III)(Fe304 :股份公司高純度化學硏究所製：純度99%)、及 氧化鎳（II)(NiO :股份公司高純度化學硏究所製：純度 -27- 200948721 9 9 %)，藉由乾式球磨機混合4小時而得到含金屬的化合物 之混合物。將所得到之含金屬的化合物之混合物塡充於氧 化鋁船中，使用電爐在空氣環境中加熱’於800°C保持2 小時而得到實施例4的複合金屬氧化物E4。 (2)作爲鈉蓄電池的正極活性物質之充放電性能評價 使用實施例4的複合金屬氧化物E4當作鈉蓄電池用 的正極活性物質，製作電池，於與比較例1之場合同樣的 條件下，實施恆定電流充放電試驗。此電池在重複10個 循環的充放電後，相對於第1循環的放電容量而言，第10 循環的放電容量維持率爲83%。 實施例 5(Na:Mn:Fe:Co = 0.7:0.3 33:0.333:0.3 3 3，式（1)中的 M1 係 Mn、Fe 及 Co，a 係 0.7。而且 b 係 0.333) (1)複合金屬氧化物的製造 以 Na:Mn:Fe:Co 的莫耳比成爲 0.7:0.333:0.333:0.333 的方式，秤量當作含金屬的化合物之碳酸鈉（Na2C03 :和 光純藥工業股份公司製：純度99.8%)、氧化錳（IV)(Mn02 :股份公司高純度化學硏究所製：純度9 9.9%)、氧化鐵 (II、III)(Fe3〇4 :股份公司高純度化學硏究所製：純度 9 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%) ’藉由乾式球磨機混合4小時而得到含金屬的 化合物之混合物。將所得到之含金屬的化合物之混合物塡 充於氧化鋁船中’使用電爐在空氣環境中加熱，於800艺 200948721 保持2小時而得到實施例5的複合金屬氧化物E 5。 (2)作爲鈉蓄電池的正極活性物質之充放電性能評價 使用實施例5的複合金屬氧化物E5當作鈉蓄電池用 的正極活性物質，製作電池，於與比較例1之場合同樣的 條件下，實施恆定電流充放電試驗。此電池在重複10個 循環的充放電後，相對於第1循環的放電容量而言，第10 〇 循環的放電容量維持率爲78%。 實施例 6(Na:Mn:Fe:Co:Ni = 0.7:0.25:0_25:0.25:0.25，式（1) 中的M1係Mn、Fe、Co及Ni，a係0.7。而且b係0.25) (1)複合金屬氧化物的製造 以 Na:Mn:Fe:Co:Ni 的莫耳比成爲 0.7:0.25:0.25:0.25:0.25 的方式，秤量當作含金屬的化合物之碳酸鈉（Na2C03 :和 光純藥工業股份公司製：純度99.8%)、氧化錳（IV)(Mn02 © :股份公司高純度化學硏究所製：純度9 9.9 %)、氧化鐵 (II、III)(Fe304 :股份公司高純度化學硏究所製：純度 99%)、四氧化三鈷（C 〇3 04 :正同化學工業股份公司製：純 度99%)、及氧化鎳（II)(NiO :股份公司高純度化學硏究所 製：純度9 9 °/〇 ’藉由乾式球磨機混合4小時而得到含金 屬的化合物之混合物。將所得到之含金屬的化合物之混合 物塡充於氧化鋁船中，使用電爐在空氣環境中加熱，於 8 0 0 °C保持2小時而得到實施例6的複合金屬氧化物E6。 -29- 200948721 (2)作爲鈉蓄電池的正極活性物質之充放電性能評價 使用實施例6的複合金屬氧化物E6當作鈉蓄電池用 的正極活性物質，製作電池，於與比較例1之場合同樣的 條件下，實施恆定電流充放電試驗。此電池在重複10個 循環的充放電後，相對於第1循環的放電容量而言，第10 循環的放電容量維持率爲8 8%。 實施例 7(Na:Mn:Fe:Ni = 0.8:0.3 3 3:0.3 3 3:0.3 3 3，式（1)中的 ◎ M1 係 Mn、Fe 及 Ni，a 係 0.8。而且，b 係 0.333) (1) 複合金屬氧化物的製造 以 Na:Mn:Fe:Ni 的莫耳比成爲 0.8:0.333:0.333:0.333 的方式，秤量當作含金屬的化合物之碳酸鈉（Na2C03 :和 光純藥工業股份公司製：純度99.8%)、氧化錳（IV)(Mn02 :股份公司高純度化學硏究所製：純度99.9%)、氧化鐵 (II、III)(Fe304 :股份公司高純度化學硏究所製：純度 99%)、及氧化鎳（II)(NiO :股份公司高純度化學硏究所製 Q :純度99%)，藉由乾式球磨機混合4小時而得到含金屬 的化合物之混合物。將所得到之含金屬的化合物之混合物 塡充於氧化鋁船中，使用電爐在空氣環境中加熱，於 8 00 °C保持2小時而得到實施例7的複合金屬氧化物E7。 (2) 作爲鈉蓄電池的正極活性物質之充放電性能評價 使用實施例7的複合金屬氧化物E7當作鈉蓄電池用 的正極活性物質，製作電池，於與比較例1之場合同樣的 -30- 200948721 條件下’實施恆定電流充放電試驗。此電池在重複10個 循環的充放電後，相對於第1循環的放電容量而言，第1〇 循環的放電容量維持率爲93%。 實施例 8(Na:Mn:Fe:Ni = 0.9:0.3 33:0.3 3 3:0.3 3 3，式（1)中的 M1 係 Mn、Fe 及 Ni’ a 係 〇.9。而且，b 係 0.333) (1)複合金屬氧化物的製造 © 以 Na: Mn: Fe: Ni 的莫耳比成爲 0.9: 0.333: 0.333 :0.333的方式’秤量當作含金屬的化合物之碳酸鈉 (Na2C03 :和光純藥工業股份公司製：純度99.8%)、氧化 錳（IV)(Mn02 :股份公司高純度化學硏究所製：純度 99.9%)、氧化鐵（II、III)(Fe304 :股份公司高純度化學硏 究所製：純度99%)、及氧化鎳（II)(NiO :股份公司高純度 化學硏究所製：純度99%)，藉由乾式球磨機混合4小時 而得到含金屬的化合物之混合物。將所得到之含金屬的化 〇 合物之混合物塡充於氧化鋁船中，使用電爐在空氣環境中 加熱，於800°C保持2小時而得到實施例8的複合金屬氧 化物E 8。 (2)作爲鈉蓄電池的正極活性物質之充放電性能評價 使用實施例8的複合金屬氧化物E8當作鈉蓄電池用 的正極活性物質，製作電池，於與比較例1之場合同樣的 條件下，實施恆定電流充放電試驗。此電池在重複1〇個 循環的充放電後，相對於第1循環的放電容量而言’第10 -31 - 200948721 循環的放電容量維持率爲88%。 實施例 9(Na:Mn:Fe:Ni = 0.7:0.38:0_3 8:0.24，式（1)中的 μ1 係 Mn、Fe 及 Ni，a 係 0.7。而且，b 係 0·38) (1) 複合金屬氧化物的製造 以 Na:Mn:Fe:Ni 的莫耳比成爲 0.7: 0.38: 0.38: 0.24 的方式’秤量當作含金屬的化合物之碳酸鈉（Na2C03 :和 光純藥工業股份公司製：純度99.8%)、氧化猛（IV)(Mn02 :股份公司高純度化學硏究所製：純度99，9%)、氧化鐵 (II、III)(Fe304 :股份公司高純度化學硏究所製：純度 99%)、及氧化鎳（II)(NiO :股份公司高純度化學硏究所製 :純度99%)，藉由乾式球磨機混合4小時而得到含金屬 的化合物之混合物。將所得到之含金屬的化合物之混合物 塡充於氧化鋁船中，使用電爐在空氣環境中加熱，於 8 00 °C保持2小時而得到實施例9的複合金屬氧化物E9。 (2) 作爲鈉蓄電池的正極活性物質之充放電性能評價 使用實施例9的複合金屬氧化物E9當作鈉蓄電池用 的正極活性物質，製作電池，於與比較例1之場合同樣的 條件下，實施恆定電流充放電試驗。此電池在重複10個 循環的充放電後，相對於第1循環的放電容量而言，第10 循環的放電容量維持率爲93%。 實施例 10(Na:Mn:Fe:Ni = 0.7:0.42:0.42:0.1 6，式（1)中的 M1 200948721 係 Μη、Fe 及 Ni，a 係 0.7。而且，b 係 0.42) (1) 複合金屬氧化物的製造 以 Na:Mn:Fe:Ni 的莫耳比成爲 0.7:0.42:0.42:0.16 的 方式’秤量當作含金屬的化合物之碳酸鈉（Na2C〇3 :和光 純藥工業股份公司製：純度99.8%)、氧化錳（IV)(Mn〇2: 股份公司高純度化學硏究所製：純度99.9%)、氧化鐵（II 、III)(Fe304:股份公司高純度化學硏究所製：純度99%) D 、及氧化鎳（II)(NiO :股份公司高純度化學硏究所製：純 度9 9%)，藉由乾式球磨機混合4小時而得到含金屬的化 合物之混合物。將所得到之含金屬的化合物之混合物塡充 於氧化鋁船中，使用電爐在空氣環境中加熱，於800。(：保 持2小時而得到實施例1〇的複合金屬氧化物E10。 (2) 作爲鈉蓄電池的正極活性物質之充放電性能評價 使用實施例10的複合金屬氧化物E10當作鈉蓄電池 © 用的正極活性物質，製作電池，於與比較例1之場合同樣 的條件下，實施恆定電流充放電試驗。此電池在重複10 個循環的充放電後，相對於第1循環的放電容量而言，第 1〇循環的放電容量維持率爲84%。 實施例 ll(Na:Mn:Fe:Ni = 〇.7:0.46:0.46:0.08，式（1)中的 Μι 係 Μη、Fe 及 Ni，a 係 0.7。而且，b 係 0.46) (1)複合金屬氧化物的製造 以 Na:Mn:Fe:Ni 的莫耳比成爲 0.7:0.46:0.46:0.08 的 -33- 200948721 方式’秤量當作含金屬的化合物之碳酸鈉（Na2C03 :和光 純藥工業股份公司製：純度99.8%)、氧化錳（IV)(Mn02 : 股份公司高純度化學硏究所製：純度9 9.9%)、氧化鐵（II 、III)(Fe304 :股份公司高純度化學硏究所製：純度99%) 、及氧化鎳（II)(NiO :股份公司高純度化學硏究所製：純 度99%)，藉由乾式球磨機混合4小時而得到含金屬的化 合物之混合物。將所得到之含金屬的化合物之混合物塡充 於氧化鋁船中，使用電爐在空氣環境中加熱，於800 °C保 持2小時而得到實施例1 1的複合金屬氧化物E 1 1。 (2)作爲鈉蓄電池的正極活性物質之充放電性能評價 使用實施例11的複合金屬氧化物E11當作鈉蓄電池 用的正極活性物質，製作電池，於與比較例1之場合同樣 的條件下，實施恆定電流充放電試驗。此電池在重複10 個循環的充放電後，相對於第1循環的放電容量而言，第 10循環的放電容量維持率爲90%。 製造例（積層多孔質薄膜的製造） (1)耐熱多孔層用塗佈液的製造 於4200克NMP中溶解272.7克氯化鈣後，添加 13 2.9克對苯二胺，使完全溶解。於所得到的溶液中，徐 徐地添加243.3克對苯二甲醯二氯，進行聚合而得到對位 芳族聚醯胺，再以NMP稀釋，得到濃度2·0重量％的對位 芳族聚醯胺溶液。於1 〇〇克所得到的對位芳族聚醯胺溶液 200948721 中，添加及混合2克第1氧化鋁粉末（日本Aerosil公司製 ，氧化鋁C，平均粒徑0.02μιη)及2克第2氧化鋁粉末（住 友化學股份公司製Smikolandam, ΑΑ03，平均粒徑〇.3μιη) 當作塡料，計添加4克，以超微粒化裝置處理3次，再以 1000網目的金屬網來過濾過，於減壓下脫泡，而製造耐熱 多孔層用漿體狀塗佈液。相對於對位芳族聚醢胺及氧化鋁 粉末的合計重量而言，氧化鋁粉末（塡料）的重量爲67重量 ❹ ％。 (2)積層多孔質薄膜的製造及評價 作爲多孔質薄膜，使用聚乙烯製多孔質薄膜（膜層 12μιη，透氣度 140秒/100cc，平均孔徑 Ο.ίμιη，空孔率 50%)。於厚度ΙΟΟμηι的PET薄膜之上，固定上述聚乙烯 製多孔質薄膜，藉由Tester產業股份公司製桿塗機，在該 多孔質薄膜之上塗佈耐熱多孔層用漿體狀塗佈液。使PET 〇 薄膜上的所塗佈的該多孔質薄膜成爲一體，照原樣地浸漬 在弱溶劑的水中，析出對位芳族聚醯胺多孔質膜（耐熱多 孔層）後，使溶劑乾燥，剝離PET薄膜，得到由耐熱多孔 層與多孔質薄膜所層合的積層多孔質薄膜。積層多孔質薄 膜的厚度爲16 μιη，對位芳族聚醯胺多孔質膜（耐熱多孔層） 的厚度爲4μιη。積層多孔質薄膜的透氣度爲180秒/lOOcc ，空孔率爲50%。以掃描型電子顯微鏡（SEM)來觀察積層 多孔質薄膜的耐熱多孔層之截面，可知具有〇.〇3 μιη〜 0.0 6μιη左右的比較小之微細孔及0.1 μιη〜1 μιη左右的比較 -35- 200948721 大之微細孔。再者，積層多孔質薄膜的評價係如以下（A) 〜（C )地進行。 (A) 厚度測定 積層多孔質薄膜的厚度、多孔質薄膜的厚度，係依照 JIS規格（K7 1 30- 1 992)來測定。又，耐熱多孔層的厚度係 使用由積層多孔質薄膜的厚度扣除多孔質薄膜的厚度後之 値。 ❹ (B) 葛雷法的透氣度測定 積層多孔質薄膜的透氣度係根據JIS P81 17，以股份 公司安田精機製作所製的數位計時器式葛雷式透氣度測定 儀來測定。 (C) 空孔率 將所得到的積層多孔質薄膜之樣品切成一邊長度 〇 10cm的正方形，測定重量W(克）及厚度D(cm)。求得樣品 中的各層之重量（Wi(克）），由 Wi與各層的材質之真比重（ 真比重i(g/cm3))來求得各層的體積，藉由下式求得空孔率 (體積％)。 空孔率（體積％)= 100x{l-(Wl/真比重1+W2/真比重2+ · _ + Wn/真比重 n)/(l〇xl〇xD)} -36- 200948721 於上述實施例中，作爲隔板，若使用製造例所得之積 層多孔質薄膜，則可得到能更防止熱破膜的鈉蓄電池。 【圖式簡單說明】 第1圖係複合金屬氧化物C1的粉末X射線繞射圖形 〇 第2圖係複合金屬氧化物E1的粉末X射線繞射圖形 ❹ 第3圖係複合金屬氧化物E2的粉末X射線繞射圖形 〇 第4圖係複合金屬氧化物E3的粉末X射線繞射圖形 -37-(1) Production of a composite metal oxide Q: Sodium carbonate which is a metal-containing compound is weighed in such a manner that the molar ratio of Na:Mn:Co is 0.7:0.50:0.50 (Na2C03: manufactured by Wako Pure Chemical Industries, Ltd.: purity) 99.8%), manganese oxide (IV) (Mn02: manufactured by the company's High Purity Chemical Research Institute: purity 99.9%), and cobalt trioxide (Co3〇4: manufactured by Zhengtong Chemical Industry Co., Ltd.: purity 99%), by dry type The ball mill was mixed for 4 hours to obtain a mixture of metal-containing compounds. A mixture of the obtained metal-containing compound was placed in an alumina boat, heated in an air atmosphere using an electric furnace, and kept at 800 ° C for 2 hours to obtain a Q composite metal oxide C1 of Comparative Example 1. Fig. 1 shows a powder X-ray diffraction pattern of the composite metal oxide C1 of Comparative Example 1. (2) Evaluation of charge and discharge performance of the positive electrode active material of the sodium battery The composite metal oxide C1 of Comparative Example 1 was used as a positive electrode active material for a sodium battery, and a battery was fabricated, and a constant current charge and discharge test was carried out under the following conditions. -24- 200948721 Charge and discharge conditions: The charging system performs CC (C〇nstant current) charging at a rate of 0.1 C (10 hours of full charge) until 4.0 V. The discharge is performed at the same speed as the charge rate, and is discharged at a voltage of 1-5 V. The charging and discharging after the next cycle are performed at the same speed as the charging speed, and are turned off at the charging voltage of 4-0 V and the discharging voltage of 1.5 V in the same manner as in the first cycle. © After the battery was repeatedly charged and discharged for 10 cycles, the discharge capacity retention rate of the 10th cycle was 76% with respect to the discharge capacity of the first cycle. Example 1 (Na:Mn:Co:Ni = 0.7:0.495) :0.495:0.0 1, M1 in the formula (1) is Mn, Co and Ni, and the a system is 0.7. Further, b is 0.495) (1) Preparation of the composite metal oxide is a molar of Na:Mn:Co:Ni The ratio is 0.7:0.495:0.495:0.01, and the amount of sodium carbonate is used as a metal-containing compound (Na2C03: manufactured by Wako Pure Chemical Industries, Ltd.: purity: 99.8%), manganese oxide (IV) (Mn02: high purity of the company) Chemical research institute: purity 9 9.9%), cobalt trioxide (C〇304: manufactured by Zhengtong Chemical Industry Co., Ltd.: purity 99%), and nickel (II) oxide (NiO: manufactured by the company's high-purity chemical research institute: The purity was 99%) and a mixture of metal-containing compounds was obtained by mixing in a dry ball mill for 4 hours. A mixture of the obtained metal-containing compound was placed in an alumina boat, heated in an air atmosphere using an electric furnace, and maintained at 800 ° C for 2 hours to obtain a composite metal oxide E1 of Example 1. Fig. 2 shows a powder X-ray diffraction pattern of the composite metal oxide El of the embodiment -25-200948721. (2) Evaluation of the charge and discharge performance of the positive electrode active material of the sodium battery. The composite metal oxide E1 of the first embodiment was used as a positive electrode active material for a sodium battery, and a battery was produced under the same conditions as in the case of Comparative Example 1. A constant current charge and discharge test was performed. After the battery was repeatedly charged and discharged for one cycle, the discharge capacity retention rate of the first cycle was 109% with respect to the discharge capacity of the first cycle. Example 2 (Na:Mn:Co:Ni = 0.7:0.45:0.45:0.10, M1 in the formula (1) is Mn, Co and Ni, a is 0.7. Moreover, b is 0-45) (1) Composite metal oxidation Production of the composite material of Example 2 was carried out in the same manner as in Example 1 except that the metal-containing compound was used in an amount of 0.7:0.45:0.45:0.1 0 in terms of a molar ratio of Na:Mn:Co:Ni. E2. The powder X-ray diffraction pattern of the composite metal oxide E2 of Example 2 is shown in Fig. 3. (2) Evaluation of the charge and discharge performance of the positive electrode active material of the sodium battery. The composite metal oxide E2 of the second embodiment was used as a positive electrode active material for a sodium battery, and a battery was produced under the same conditions as in the case of Comparative Example 1. A constant current charge and discharge test was performed. After the battery was repeatedly charged and discharged for 10 cycles, the discharge capacity retention rate of the first cycle was 89 °/ with respect to the discharge capacity of the first cycle. . 200948721 Example 3 (Na:Mn:Co:Ni = 0.7:0.3 3 3:0.3 3 3:0.3 3 3 , Μ1 in the formula (1) is Μη, Co and Ni, a is 0·7. Moreover, b (3) The production of the composite metal oxide is the same as in the first embodiment except that the molar ratio of Na:Mn:Co:Ni is 0.7:0.3 33:0.333:0.333. The composite metal oxide E3 of Example 3 was obtained. The powder X-ray diffraction pattern of the composite metal oxide E3 of Example 3 is shown in Fig. 4. (2) Evaluation of charge and discharge performance of the positive electrode active material of the sodium battery. The composite metal oxide E3 of Example 3 was used as a positive electrode active material for a sodium battery, and a battery was produced. Under the same conditions as in the case of Comparative Example 1, A constant current charge and discharge test was performed. After the battery was repeatedly charged and discharged for 10 cycles, the discharge capacity retention rate of the 10th cycle was 90% with respect to the discharge capacity of the first cycle. Example 4 (Na:Mn:Fe:Ni = 0_7:0.3 3 3:0.3 3 3:0.3 3 3 , M1 in the formula (1) is Mn, Fe and Ni' a is 0.7. Moreover, b is 0.333) (1) Production of composite metal oxides Sodium carbonate as a metal-containing compound was weighed in such a manner that the molar ratio of Na:Mn:Fe:Ni was 0.7:0.333:0.333:0.333 (Na2C03: Wako Pure Chemical Industries Co., Ltd. Company system: purity 99.8%), manganese oxide (IV) (Mn02: manufactured by the company's high-purity chemical research institute: purity 99.9 ° /.), iron oxide (II, III) (Fe304: high-purity chemical research company Prepared: purity 99%), and nickel (II) oxide (NiO: manufactured by the company's high-purity chemical research institute: purity -27- 200948721 99%), obtained by mixing in a dry ball mill for 4 hours to obtain metal-containing compounds a mixture. The obtained metal-containing compound mixture was placed in an alumina boat and heated in an air atmosphere at 800 ° C for 2 hours to obtain a composite metal oxide E4 of Example 4. (2) Evaluation of charge and discharge performance of the positive electrode active material of the sodium battery using the composite metal oxide E4 of Example 4 as a positive electrode active material for a sodium battery, and producing a battery under the same conditions as in the case of Comparative Example 1, A constant current charge and discharge test was performed. After the battery was repeatedly charged and discharged for 10 cycles, the discharge capacity retention rate of the 10th cycle was 83% with respect to the discharge capacity of the first cycle. Example 5 (Na:Mn:Fe:Co = 0.7:0.3 33:0.333:0.3 3 3 , M1 in the formula (1) is Mn, Fe and Co, a is 0.7, and b is 0.333) (1) Composite In the production of metal oxides, sodium carbonate is used as a metal-containing compound in a molar ratio of Na:Mn:Fe:Co to 0.7:0.333:0.333:0.333 (Na2C03: manufactured by Wako Pure Chemical Industries, Ltd.: purity) 99.8%), manganese oxide (IV) (Mn02: manufactured by the company's High Purity Chemical Research Institute: purity 9.9%), iron oxide (II, III) (Fe3〇4: manufactured by the company's high-purity chemical research institute: Purity: 9 9%), and tri-cobalt trioxide (C〇3〇4: manufactured by Zheng Chemical Industry Co., Ltd.: purity: 99%) 'A mixture of metal-containing compounds was obtained by mixing in a dry ball mill for 4 hours. The obtained mixture of the metal-containing compound was filled in an alumina boat. The mixture was heated in an air atmosphere using an electric furnace, and maintained at 800 Art 200948721 for 2 hours to obtain a composite metal oxide E 5 of Example 5. (2) Evaluation of the charge and discharge performance of the positive electrode active material of the sodium battery. The composite metal oxide E5 of Example 5 was used as a positive electrode active material for a sodium battery, and a battery was produced under the same conditions as in the case of Comparative Example 1. A constant current charge and discharge test was performed. After the battery was repeatedly charged and discharged for 10 cycles, the discharge capacity retention rate of the 10th cycle was 78% with respect to the discharge capacity of the first cycle. Example 6 (Na: Mn: Fe: Co: Ni = 0.7: 0.25: 0-25: 0.25: 0.25, M1 in the formula (1) is Mn, Fe, Co, and Ni, and the a system is 0.7. And b is 0.25) ( 1) Production of composite metal oxide Sodium carbonate (Na2C03: and pure light) is used as a metal-containing compound in such a manner that the molar ratio of Na:Mn:Fe:Co:Ni is 0.7:0.25:0.25:0.25:0.25. Pharmaceutical Industry Co., Ltd.: purity 99.8%), manganese oxide (IV) (Mn02 ©: High Purity Chemical Research Institute of the company: purity 9.9%), iron oxide (II, III) (Fe304: high purity company Chemical research institute: purity 99%), cobalt trioxide (C 〇 3 04: manufactured by Zhengtong Chemical Industry Co., Ltd.: purity 99%), and nickel (II) oxide (NiO: manufactured by the company's high-purity chemical research institute: Purity 9 9 ° / 〇 'mixed by a dry ball mill for 4 hours to obtain a mixture of metal-containing compounds. The mixture of the obtained metal-containing compounds was filled in an alumina boat and heated in an air atmosphere using an electric furnace. The composite metal oxide E6 of Example 6 was obtained by maintaining at 80 ° C for 2 hours. -29- 200948721 (2) As a positive electrode active material of a sodium storage battery The battery was produced by using the composite metal oxide E6 of Example 6 as a positive electrode active material for a sodium battery, and a constant current charge and discharge test was carried out under the same conditions as in Comparative Example 1. The battery was repeated. After 10 cycles of charge and discharge, the discharge capacity retention rate of the 10th cycle was 88% with respect to the discharge capacity of the first cycle. Example 7 (Na:Mn:Fe:Ni = 0.8:0.3 3 3: 0.3 3 3:0.3 3 3 , in the formula (1), M1 is Mn, Fe and Ni, and a is 0.8. Further, b is 0.333) (1) Production of composite metal oxide is Na:Mn:Fe:Ni The molar ratio of 0.8 to 0.333:0.333:0.333 is measured as a metal-containing compound of sodium carbonate (Na2C03: manufactured by Wako Pure Chemical Industries, Ltd.: purity: 99.8%), manganese oxide (IV) (Mn02: shares) The company's high-purity chemical research institute: purity 99.9%), iron oxide (II, III) (Fe304: high-purity chemical research institute of the company: purity 99%), and nickel (II) oxide (NiO: joint stock company Q obtained by High Purity Chemical Research Institute: purity 99%), obtained by mixing in a dry ball mill for 4 hours to obtain a metal-containing compound A mixture of the obtained metal-containing compound was placed in an alumina boat, heated in an air atmosphere using an electric furnace, and kept at 800 ° C for 2 hours to obtain a composite metal oxide E7 of Example 7. (2) Evaluation of charge and discharge performance of the positive electrode active material of the sodium battery The composite metal oxide E7 of Example 7 was used as a positive electrode active material for a sodium battery, and a battery was produced. The same -30- as in the case of Comparative Example 1 was used. Under the conditions of 200948721, the constant current charge and discharge test was carried out. After the battery was repeatedly charged and discharged for 10 cycles, the discharge capacity retention rate of the first cycle was 93% with respect to the discharge capacity of the first cycle. Example 8 (Na:Mn:Fe:Ni = 0.9:0.3 33:0.3 3 3:0.3 3 3 , M1 in the formula (1) is Mn, Fe and Ni' a system 9.9, and b system 0.333 (1) Manufacture of composite metal oxide © Sodium carbonate as a metal-containing compound in the form of a molar ratio of Na: Mn:Fe: Ni to 0.9: 0.333: 0.333: 0.333 (Na2C03: Wako Pure Chemicals) Industrial Co., Ltd.: purity 99.8%), manganese oxide (IV) (Mn02: high-purity chemical research institute of the company: purity 99.9%), iron oxide (II, III) (Fe304: high-purity chemical research company A purity of 99%) and nickel (II) oxide (NiO: manufactured by the company's High Purity Chemical Research Institute: purity: 99%) were mixed by a dry ball mill for 4 hours to obtain a mixture of metal-containing compounds. The obtained mixture of the metal-containing ruthenium compound was placed in an alumina boat, heated in an air atmosphere using an electric furnace, and maintained at 800 ° C for 2 hours to obtain a composite metal oxide E 8 of Example 8. (2) Evaluation of charge and discharge performance of the positive electrode active material of the sodium battery. The composite metal oxide E8 of Example 8 was used as a positive electrode active material for a sodium battery, and a battery was produced under the same conditions as in the case of Comparative Example 1. A constant current charge and discharge test was performed. After the battery was repeatedly charged and discharged for one cycle, the discharge capacity retention rate of the 10th - 31 - 200948721 cycle was 88% with respect to the discharge capacity of the first cycle. Example 9 (Na:Mn:Fe:Ni = 0.7:0.38:0_3 8:0.24, μ1 in the formula (1) is Mn, Fe and Ni, and the a system is 0.7. Moreover, b is 0·38) (1) The production of the composite metal oxide is based on the molar ratio of Na:Mn:Fe:Ni to 0.7: 0.38: 0.38: 0.24. Purity: 99.8%), oxidized (IV) (Mn02: manufactured by the company's High Purity Chemical Research Institute: purity 99.9%), iron oxide (II, III) (Fe304: manufactured by the company's high-purity chemical research institute: The purity was 99%), and nickel (II) oxide (NiO: manufactured by the company's High Purity Chemical Research Institute: purity: 99%) was mixed by a dry ball mill for 4 hours to obtain a mixture of metal-containing compounds. A mixture of the obtained metal-containing compound was placed in an alumina boat, heated in an air atmosphere using an electric furnace, and kept at 800 ° C for 2 hours to obtain a composite metal oxide E9 of Example 9. (2) Evaluation of charge and discharge performance of the positive electrode active material of the sodium battery. The composite metal oxide E9 of Example 9 was used as a positive electrode active material for a sodium battery, and a battery was produced under the same conditions as in the case of Comparative Example 1. A constant current charge and discharge test was performed. After the battery was repeatedly charged and discharged for 10 cycles, the discharge capacity retention rate of the 10th cycle was 93% with respect to the discharge capacity of the first cycle. Example 10 (Na:Mn:Fe:Ni = 0.7:0.42:0.42:0.1 6, M1 in the formula (1) 200948721 is Μη, Fe and Ni, a is 0.7. Moreover, b is 0.42) (1) Composite In the production of metal oxides, sodium carbonate is used as a metal-containing compound in the manner that the molar ratio of Na:Mn:Fe:Ni is 0.7:0.42:0.42:0.16 (Na2C〇3: manufactured by Wako Pure Chemical Industries, Ltd.) : purity: 99.8%), manganese oxide (IV) (Mn〇2: manufactured by the company's high-purity chemical research institute: purity: 99.9%), iron oxide (II, III) (Fe304: manufactured by the company's high-purity chemical research institute) : purity: 99%) D, and nickel (II) oxide (NiO: manufactured by the company's High Purity Chemical Research Institute: purity of 9 9%), and a mixture of metal-containing compounds was obtained by mixing in a dry ball mill for 4 hours. The resulting mixture of metal-containing compounds was filled in an alumina boat and heated in an air atmosphere at 800. (: The composite metal oxide E10 of Example 1 was obtained for 2 hours. (2) Evaluation of charge and discharge performance of the positive electrode active material of the sodium storage battery The composite metal oxide E10 of Example 10 was used as the sodium storage battery. The positive electrode active material was used to produce a battery, and a constant current charge and discharge test was carried out under the same conditions as in the case of Comparative Example 1. After the battery was repeatedly charged and discharged for 10 cycles, the discharge capacity of the first cycle was the same as that of the first cycle. The discharge capacity retention rate of the 1 〇 cycle was 84%. Example ll (Na:Mn:Fe:Ni = 〇.7:0.46:0.46:0.08, Μι system Μη, Fe and Ni, a system in the formula (1) 0.7. Moreover, b is 0.46) (1) The production of the composite metal oxide is measured as a metal-containing method in the form of -33-200948721 in which the molar ratio of Na:Mn:Fe:Ni is 0.7:0.46:0.46:0.08. Sodium carbonate (Na2C03: manufactured by Wako Pure Chemical Industries, Ltd.: purity: 99.8%), manganese (IV) oxide (Mn02: manufactured by the company's High Purity Chemical Research Institute: purity: 9.9%), iron oxide (II, III) ) (Fe304: manufactured by the company's High Purity Chemical Research Institute: purity 99%), and nickel oxide II) (NiO: manufactured by the company's High Purity Chemical Research Institute: purity 99%), which is obtained by mixing in a dry ball mill for 4 hours to obtain a mixture of metal-containing compounds. The mixture of the obtained metal-containing compounds is oxidized. In the aluminum boat, the electric metal was heated in an air atmosphere and kept at 800 ° C for 2 hours to obtain the composite metal oxide E 1 1 of Example 11. (2) Evaluation of charge and discharge performance of the positive electrode active material as a sodium storage battery The composite metal oxide E11 of Example 11 was used as a positive electrode active material for a sodium storage battery, and a battery was fabricated, and a constant current charge and discharge test was carried out under the same conditions as in Comparative Example 1. The battery was repeatedly charged for 10 cycles. After the discharge, the discharge capacity retention rate of the first cycle was 90% with respect to the discharge capacity of the first cycle. Production Example (Production of laminated porous film) (1) Production of coating liquid for heat-resistant porous layer at 4200 After dissolving 272.7 g of calcium chloride in gram NMP, 13 2.9 g of p-phenylenediamine was added to completely dissolve. In the obtained solution, 243.3 g of p-xylylene dichloride was slowly added to carry out polymerization. The para-aramid polyamine was obtained, and then diluted with NMP to obtain a para-type aromatic polyamine solution having a concentration of 2.0% by weight. In the para-aromatic polyamine solution 200948721 obtained by 1 gram, 2 g of the first alumina powder (manufactured by Nippon Aerosil Co., Ltd., alumina C, average particle diameter 0.02 μm) and 2 g of the second alumina powder (Smikolandam, ΑΑ03, manufactured by Sumitomo Chemical Co., Ltd., average particle diameter 〇.3 μιη) As a dip, 4 g was added, and the mixture was treated three times with a micro-micronization apparatus, and then filtered with a metal mesh of 1000 mesh, and defoamed under reduced pressure to prepare a slurry-like coating liquid for a heat-resistant porous layer. . The weight of the alumina powder (tank) was 67% by weight based on the total weight of the para-aramid and the alumina powder. (2) Production and evaluation of laminated porous film As the porous film, a porous film made of polyethylene (film layer 12 μm, air permeability: 140 sec/100 cc, average pore diameter Ο.ίμιη, porosity: 50%) was used. On the PET film having a thickness of ΙΟΟμηι, the polyethylene porous film was fixed, and a slurry coating liquid for a heat resistant porous layer was applied onto the porous film by a bar coater manufactured by Tester Industries, Ltd. The porous film coated on the PET film is integrated, immersed in water in a weak solvent as it is, and a para-aramid porous film (heat-resistant porous layer) is precipitated, and then the solvent is dried and peeled off. In the PET film, a laminated porous film in which a heat resistant porous layer and a porous film were laminated was obtained. The thickness of the laminated porous film was 16 μm, and the thickness of the para-aramid porous film (heat resistant porous layer) was 4 μm. The laminated porous film had a gas permeability of 180 sec/100 cc and a porosity of 50%. The cross section of the heat-resistant porous layer of the laminated porous film was observed by a scanning electron microscope (SEM), and it was found that the comparatively small micropores having a size of about 〇3 μιη to 0.06 μηη and the comparison of about 0.1 μm to 1 μm were -35- 200948721 Large micropores. In addition, the evaluation of the laminated porous film was carried out as follows (A) to (C). (A) Thickness measurement 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 a thickness obtained by subtracting the thickness of the porous film from the thickness of the laminated porous film. ❹ (B) Measurement of the air permeability of the Glyph method The air permeability of the laminated porous film was measured in accordance with JIS P81 17, a digital timer type GRAY type gas permeability measuring instrument manufactured by the company Yasuda Seiki Co., Ltd. (C) Porosity The sample of the obtained laminated porous film was cut into a square having a length of 〇 10 cm, and the weight W (gram) and the thickness D (cm) were measured. The weight of each layer in the sample (Wi (g)) was obtained, and the volume of each layer was determined from the true specific gravity (true specific gravity i (g/cm3)) of the material of each layer, and the porosity was determined by the following formula. (volume%). Porosity (% by volume) = 100x{l-(Wl/true specific gravity 1+W2/true specific gravity 2+ · _ + Wn/true specific gravity n)/(l〇xl〇xD)} -36- 200948721 In the example, when the laminated porous film obtained in the production example is used as the separator, a sodium storage battery capable of preventing thermal cracking can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a powder X-ray diffraction pattern of a composite metal oxide C1. Fig. 2 is a powder X-ray diffraction pattern of a composite metal oxide E1. Fig. 3 is a composite metal oxide E2 Powder X-ray diffraction pattern 〇 Figure 4 is a powder X-ray diffraction pattern of composite metal oxide E3-37-