2010B1934 BL19B2 ᨺᑕග⢊ᮎ X ⥺ගᅇᢡࢳ㟁ụ㟁ᴟ⏝ ࢩ㢮ఝయᮦᩱࡢᒁᡤᵓ㐀ゎᯒ A Structural Study of Prussian Blue Analogues for Lithium-Ion Battery Electrodes by Synchrotron X-Ray Powder Diffraction ᮅ ㍜ a , ಖ ᑘ a , ⣽㔝 ⱥ a , ࿘ ៅ a Daisuke Asakura a , Masashi Okubo a , Eiji Hosono a , and Haoshen Zhou a a 㻔⊂㻕⏘ᴗᢏ⾡⥲◊✲ᡤ a National Institute for Advanced Industrial Science and Technology 㻔AIST㻕 ᪂つࢳ㟁ụ㟁ᴟᮦᩱࡋ᭷ᮃ ࡞K 1.85 Mn 1.08 [Mn㻔CN㻕 6 ]ࢩ㢮ఝయ 㛵㐃≀㉁ࡅ࠾ ࠊ⬺ᤄධୗࡅ࠾ᵓ㐀ኚᨺᑕග⢊ᮎ X ⥺ᅇᢡࡗㄪ ⤖ࡢࡑࠋࡓᯝࠊ ࡢX ⥺ᅇᢡ ᐃࡣほ ࡉ࡞ࡓࡗࡀࢡከほ ࡉࠋࡓཎᅉ ࡋ ࠊ⬺ࡢᤄධకࡗ⏕ࡓࡌ⣧≀┦ ࠊヨᩱ‽ഛࡢᅽຊຠᯝ➼ࡀ⪃࠼ ࠋ᪉ ࠊK 2 M 2-y Fe y 㻔CN㻕 6 ࢩ㢮ఝయࡢ᱁Ꮚᐃ ࡣFe ᗘẚࡋῶᑡ ࠊࡋFe ࡀᅛ⁐ ࡋ࠸ࡇࡀ ࠋࡓࡋࢻ㸸 ࢺࢺゎᯒࠊ⬺ᤄධࠊᵓ㐀┦㌿⛣ ⫼ᬒ◊✲┠ⓗ㸸 ㏆ᖺ⮬ࠊ㌴⏘ᴗ࠸࠾ࢻ/㟁Ẽ⮬㌴ࡢᬑཬࡀᛴ㐍࠾ࡉࠊ࡞㧗ᛶ ⬟㸦ฟຊࠊ⯟⥆㊥㞳㸧᭷ࡋᏳ౯ ࡞Li 㟁ụ㻔Li-ion battery: LIB䠅ᮦᩱࡀồ࠸ࠋ㌴ ㍕⏝ LIB ࡢṇᴟᮦᩱࠊࡣ㧗㟁㸦ฟຊ㸧 ࠊ㧗ᐜ㔞ࠊ㧗ࢧࢡ≉ᛶࠊపࡢࢺࢫࢥ‶ࡍࡓᚲ せ࠶ࡀࡢ⾜⌧ࠊࡀ㓟≀ᮦᩱࡑࡀ㐩ᡂࡉ࠸ࡣゝࠊࡎ࠼㓟≀⣔௨እࡢ᪂ᮦᩱ ࡢ㛤Ⓨࡀᙉࡃᮃ࠸ࡢࡑࠋ᭷ຊ࡞ೃ⿵ࡦࡢࡘࡋ ࠊ㑄⛣㔠ᒓ᭷ᶵ㓄Ꮚ࡞ Metal Organic Framework ศ㢮 ࡉ ࢩ㢮ఝయ 㻔Prussian blue analogue: PBA ࠊA 2-x M y M’㻔CN㻕 6 nH 2 O 㻔A: 㔠ᒓࠊM, M’: 㑄⛣㔠ᒓ㻕䠅࠶ࡀ [1] ࠋPBA ࡣAB㻔CN㻕 3 ᆺࡢࢫࢺⓗ࡞ᵓ㐀 ࠊࡢ᭷ᶵᮦᩱẚሀ∼ࡘẚ㍑ⓗ㍍ 㔞ࡓࡗ࠸≉ᚩᣢࠋࡘ୰ K 1.85 Mn 1.08 [Mn㻔CN㻕 6 ]0.7H 2 O㻔KMM䠅[2] ࡣ ࡢPBA ㍍㔞 ࠶ ࠊ ࡢPBA ␗࡞ࡢ㑄⛣㔠ᒓࡀ㓟㑏ඖࡍ⪃࠼ࡢ ࠊᐇ⏝㐺 ࡋࡓᮦᩱゝ࠼ࠋᡃࡣࠎᐇ㝿 KMM ࡢ㟁ẼᏛ ᐃ㸦K ⬺㞳ࠊLi ᤄධ⬺㞳㸧⾜ࠊ࠸㔜㔞ᙜ ࡓࡢᨺ㟁ᐜ㔞 ࡀ190 mAh/g 㐩ࡍࡇࡀࡇࠋࡓࡗ࡞ࠊࡣ㌴㍕⏝⾜⌧ࡢᮦᩱ ࠶ LiCoO 2 ࡢ➼㓟≀⣔ᅇࠋࠊࡓKMM ࡣ〇㐀ࢺࢫࢥ㠃᭷࠶ ࠋ᪉ ࠊKMM ࡢᨺ㟁ࢧࢡ≉ᛶࡣప ࠋ࠸Li ⬺ࡢᤄධ 50 ࢧࢡ⾜࠺ ࠊᐜ㔞➨ࡀࢧ ࢡ ࡢ50㸣పୗࡋࡋ ࠋ࠺K ⬺㞳㐣⛬ࡢヨᩱᑐ ࠊࡋCu KD⥺※㻔Ȝ= 1.54 ύ䠅 ex-situ X ⥺ᅇᢡ ᐃ㻔x-ray diffraction: XRD䠅⾜⤖ࡓࡗᯝࠊK ⬺㞳๓ࡣ༢ᬗࠊK ⬺㞳ᮇ㐣⛬ࡣ༢ ᬗ❧᪉ᬗ ࡢ2 ┦ඹᏑ≧ែࡉࠊ K ⬺㞳ࡢᚋ❧ࡣ᪉ᬗࡢࡢ≧ែ࠶ࡇࡀ ࡢࡇࠋࡓࡗ࡞ᵓ㐀┦㌿⛣ࡗ 17㸣ࡢయ✚⭾ᙇࡌ⏕ࡀࠋLi ᤄධ㐣⛬ࡢࡇࡣ㏫ࡓ ࠋࡗࡀࡓࡋࠊLi ⬺ᤄධ⾜ࡈ࠺࡞ࡁయ✚ኚࡌ⏕ࡀࡓࢧࠊࢡ㔜ࡡࡘ ࠊ⢏ᏊࡀᶵᲔⓗᦆയࡋᨺ㟁ᐜ㔞ࡀపୗࡍ⪃࠼ ࠋࠊࡓග㟁Ꮚ࠾ࠊࡧ㌾ X ⥺྾ศගࡗࠊK ⬺㞳㐣⛬࠸࠾ Mn ࡣ2 ౯ĺ3 ౯㓟 ࡍࡇ☜ࡀㄆࡉࠋࡓKMM ࡣMn ࡢ⨨ࡍࢧࢺࡋ C 㓄㻔MnC 6 ඵ㠃య䠅ࠊN 㓄 㻔MnN 6 ඵ㠃య䠅 ࡢ2 ✀㢮࠶ࡀࠋ⯡ⓗ Mn 3+ ࡢඵ㠃యࡣࢸṍ㉳ࡋࡇࠊࡀ࠸ࡍK ⬺㞳ᚋ ࡢXRD ࢱ❧ࡣ᪉ᬗࡢࡢࡓࡗࡔࡑࠊࡒࡢඵ㠃య ࡀK ⬺㞳కࡗ」㞧ṍ ࡑࠊ┦ࡀẅࡉ㧗ᑐ⛠ᛶ⥔ࡀᣢࡉ࠸ணࡉ ࠋࡗࡀࡓࡋࠊᮏᮦᩱࡢపࢧࢡ≉ᛶ⌮ゎࡍࡓࠊࡣK ⬺㞳࠾ࠊ ࡧLi ᤄධ⬺㞳㐣⛬ ࡅ࠾ヲ⣽࡞ᵓ㐀ゎᯒࡀᚲせ࠶ࠋ㟁ẼᏛⓗ⤌ࡢᡂࡗ KMM ࡢᇶ