http://support.spring8.or.jp/Report_JSR/PDF_IAe_ALL/IAe_10B1862.pdf

2010B1862                       BL46XU⌮᝿㟁ᴟ⏺㠃ࢆ⏝࠸ࡓࣜࢳ࣒࢘࢖࢜ࣥ஧ḟ㟁ụṇᴟࡢ⾲㠃ᵓ㐀ኚ໬᳨ฟ࡟ࡼࡿ཯ᛂᶵᵓゎ᫂
Surface Structure of Lithium Battery Electrodes :using In-situ X-ray Diffraction and Epitaxial Thin-film㜿㒊 ┿▱Ꮚ a, ᖹᒣ 㞞❶ b, 㕥ᮌ ⪔ኴ b, KyungSu Kimb, ⢊⏕ Ᏺ b,༡ᔱᏹᫎ b, Ⳣ㔝 ஢ḟ b, ⏣ᮧ ࿴ஂ c, Ỉᮌ ⣧୍㑻 cMachiko Abea, Masaaki Hirayamab, Kouta Suzukib, KyungSu Kimb, Mamoru Komob,Hiroaki Minamishimab, Ryoji Kannob, Kazuhisa Tamurac, Junichiro Mizukicaaࢺࣚࢱ⮬ື㌴, b ᮾிᕤᴗ኱Ꮫ, c ᪥ᮏཎᏊຊ◊✲㛤Ⓨᶵᵓ
Toyota Motor Corporation, bDepartment of Electronic Chemistry, Tokyo Institute of Technology,cJapan Atomic Energy Agency, Synchrotron Radiation Research Centerࣜࢳ࣒࢘࢖࢜ࣥ஧ḟ㟁ụࡢṇᴟά≀㉁࡛࠶ࡿᒙ≧ᒾሷᆺ LiNi0.8Co0.15Al0.05O2 ࡣࠊ඘ᨺ㟁᫬࡟⾲㠃 ㏆ ഐ ࡜ ࣂ ࣝ ࢡ ࡛ ␗ ࡞ ࡿ ᣲ ື ࢆ ♧ ࡍ ࡇ ࡜ ࡀ ሗ ࿌ ࡉ ࢀ ࡚ ࠸ ࡿ [1] ࠋ ࡑ ࡇ ࡛ ᮏ ㄢ 㢟 ࡛ ࡣ
LiNi0.8Co0.15Al0.05O2 ࡜ྠᵝ࡟ᒙ≧ᒾሷᆺᵓ㐀࡛࠶ࡾࠊLiNi0.8Co0.15Al0.05O2 ࡜ẚ㍑ࡋ࡚㧗ᐜ㔞࡛࠶ࡿṇᴟᮦᩱ LiNi1/3Co1/3Mn1/3O2 ࡢ඘ᨺ㟁᫬ࡢ⾲㠃࡜ࣂࣝࢡࡢຎ໬ᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋࡑࡢࡓࡵ࡟ࣃࣝࢫ࣮ࣞࢨ࣮ሁ✚ἲ࡟࡚స〇ࡋࡓ LiNi1/3Co1/3Mn1/3O2 ࢚ࣆࢱ࢟ࢩࣕࣝⷧ⭷㟁ᴟࢆ⏝࠸࡚ࠊin-situ X ⥺⾲㠃ᅇᢡ ᐃࢆ⾜ࡗࡓࠋLiNi1/3Co1/3Mn1/3O2 ࡛ࡣ㟁Ẽ໬Ꮫ཯ᛂ࡟క࠸ࠊ཯ᑕࡢࢩࣇࢺࡸ཯ᑕᙉᗘࡢኚ໬ࡀ☜ㄆࡉࢀࠊLiNi1/3Co1/3Mn1/3O2 ࡣ Li ⬺ᤄධ࡟క࠸ᵓ㐀ኚ໬ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ࣮࣮࢟࣡ࢻ㸸 ࣜࢳ࣒࢘࢖࢜ࣥ஧ḟ㟁ụࠊ࢚ࣆࢱ࢟ࢩࣕࣝⷧ⭷ࠊX ⥺ᅇᢡ⫼ᬒ࡜◊✲┠ⓗ㸸㏆ᖺࠊࣁ࢖ࣈࣜࢵࢻ㌴ࠊࣉࣛࢢ࢖ࣥࣁ࢖ࣈࣜࢵࢻ㌴ࡸEV㌴ࡢᐇ⏝໬ࡀ㐍ࢇ࡛࠸ࡿࡀࠊ᭦࡞ࡿ㌴୧ᛶ⬟ྥୖࡢࡓࡵ࡟ࡣࣜࢳ࣒࢘࢖࢜ࣥ஧ḟ㟁ụࡢ㣕㌍ⓗ࡞≉ᛶྥୖࡀᮃࡲࢀ࡚࠸ࡿࠋḟୡ௦㟁ụࡢ㛤Ⓨ࡟ࡣࠊ㟁ᴟࠊ㟁ゎᾮ࡞࡝ᮦᩱ⮬㌟ࡢ≉ᛶྥୖࡀ㔜せ࡛࠶ࡿࡀࠊ㟁ᴟ࡜㟁ゎ㉁⏺㠃࡟࠾ࡅࡿ㟁Ⲵ⛣ືࠊ࢖࢜ࣥᣑᩓࠊ๪཯ᛂ➼ࡶࡲࡓ㟁ụ≉ᛶ࡟኱ࡁ࡞ᙳ㡪ࢆ୚࠼ࡿࠋࡋ࠿ࡋࠊᚑ᮶⏝࠸ࡽࢀ࡚ࡁࡓከ⤖ᬗ㟁ᴟ࡛ࡣ⢏⏺࡞࡝ࡢᙳ㡪࡟ࡼࡾᚊ㏿㐣⛬࡜࡞ࡗ࡚࠸ࡿ㟁ᴟ/㟁ゎ㉁⏺㠃࡛ࡢ཯ᛂ࡜ෆ㒊࡛㉳ࡇࡿᵝࠎ࡞཯ᛂࡀศ㞳࡛ࡁࡎࠊ཯ᛂᶵᵓࡢ⌮ゎࢆጉࡆ࡚࠸ࡿࠋࡑࡇ࡛㛤Ⓨࢆຍ㏿໬ࡉࡏࡿࡓࡵ࡟ࡣࠊ㟁ᴟ/㟁ゎᾮ⏺㠃࡟࠾ࡅࡿ㟁Ⲵ⛣ືࠊ࢖࢜ࣥᣑᩓࠊ๪཯ᛂ➼ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡀᚲせ࡛࠶ࡿ࡜⪃࠼ࡿࠋࡇࢀࡲ࡛࡟ᡃࠎࡣࠊ༢⤖ᬗᇶᯈୖ࡟࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗ࡉࡏࡓⷧ⭷ࢆṇᴟ࡟⏝࠸ࡓ㟁ụࢆస〇ࡋࠊBL14B1࡟࡚in-situ X⥺཯ᑕ⋡ ᐃࡸX⥺⾲㠃ᅇᢡ ᐃ࠿ࡽ㟁ᴟ/㟁ゎᾮ⏺㠃࡜ࣂࣝࢡ࡛㉳ࡁࡿ཯ᛂࡀ඲ࡃ␗࡞ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋ࡚ࡁࡓ[2]ࠋࡲࡓin-situ X⥺ᅇᢡ ᐃ࡛ࡣX⥺ධᑕゅࢆ⮫⏺ゅ௨ୗ࠿ࡽ⮫⏺ゅ㏆ഐࡢ⠊ᅖ࡛ไᚚࡍࡿࡇ࡜࡛X⥺ࡢ౵ධ῝ࡉࢆኚ໬ࡉࡏ࡚ࠊ᭱⾲㠃࠿ࡽ㟁ᴟෆ࡟⮳ࡿ⾲㠃ᵓ㐀ࢆ᳨ฟࡋࡓࠋࡑࡢ⤖ᯝࠊⷧ⭷⾲㠃࡜ࣂࣝࢡ࡛ࡣほ ࡉࢀࡓ஧ࡘࡢ཯ᑕࡢᙉᗘẚࡀ␗࡞ࡿࡇ࡜ࡸࣂࣝࢡࡢࡳ࡛ほ ࡉࢀࡓ཯ᑕࡀᏑᅾࡍࡿࡇ࡜ࡀศ࠿ࡾࠊ῝ࡉ᪉ྥࡢኚ໬ࢆᤊ࠼ࡿࡇ࡜ࡀ
ྍ⬟࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓ[3]ࠋᮏ◊✲࡛ࡣ㌴㍕⏝ࣜࢳ࣒࢘࢖࢜ࣥ஧ḟ㟁ụࡢṇᴟࡢ୍ࡘ࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿᒙ≧ᒾሷᆺ㓟໬
≀LiNi1/3Co1/3Mn1/3O2࡟╔┠ࡋࡓࠋLiNi1/3Co1/3Mn1/3O2ࡣ⇕Ᏻᐃᛶࡀ㧗࠸࡜࠸࠺≉㛗ࢆᣢࡘࡀ⪏ஂᛶ࡟ㄢ㢟ࡀ࠶ࡿࠋ㟁ᴟຎ໬ࡣ㟁Ẽ໬Ꮫ཯ᛂࡢ㛤ጞⅬ࡛࠶ࡿ㟁ᴟ࡜㟁ゎᾮ⏺㠃ࢆ㉳Ⅼ࡟ࡋ࡚㐍⾜ࡍࡿ࡜⪃࠼ࡽࢀࡿࡓࡵ⪏ஂᛶపୗࡢ࣓࢝ࢽࢬ࣒ࢆ⌮ゎࡍࡿ࡟ࡣࠊ㟁ụ཯ᛂୗ࡟࠾ࡅࡿ㟁ᴟࡢ⾲㠃ᵓ㐀ኚ໬ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࠋࡇࢀࡲ࡛࡟LiNi1/3Co1/3Mn1/3O2࡟㛵ࡍࡿ⾲㠃ᵓ㐀ኚ໬ࡢሗ࿌ ౛ ࡣ ࡞ ࠸ ࡓ ࡵ ࠊ ᮏ ㄢ 㢟 ࡛ ࡣ LiNi1/3Co1/3Mn1/3O2 ࡢ ⪏ ஂ ᛶ ࣓ ࢝ ࢽ ࢬ ࣒ ゎ ᫂ ࢆ ┠ ⓗ ࡜ ࡋ ࡚ ࠊ
LiNi1/3Co1/3Mn1/3O2࢚ࣆࢱ࢟ࢩࣕࣝⷧ⭷ࢆࣔࢹࣝṇᴟ࡜ࡋࡓin-situࢭࣝࢆస〇ࡋࠊX⥺⾲㠃ᅇᢡ ᐃ࡛ࠊ LiNi1/3Co1/3Mn1/3O2ⷧ⭷⾲㠃࣭ࣂࣝࢡࡢᵓ㐀ኚ໬ࢆࡑࡢሙほ ࡋࠊ᭱⾲㠃࠿ࡽ㟁ᴟෆ࡟⮳ࡿ⾲㠃ᵓ㐀ኚ໬ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆヨࡳࡓࠋᐇ㦂㸸
LiNi1/3Co1/3Mn1/3O2 ࢚ࣆࢱ࢟ࢩࣕࣝⷧ⭷ࡣࣃࣝࢫ࣮ࣞࢨ࣮ሁ✚ἲ࡟ࡼࡾ Nb ࢆ 0.5%ࢻ࣮ࣉࡋࡓ

Li ⬺ᤄධ᪉ྥ

-㻔118㻕

-SrTiO3 ༢⤖ᬗࡢ㻔110㻕㠃ୖ࡟స〇ࡋࠊ㻔118㻕㓄ྥࡋࡓ--- -ࡗࡓࠋ ᐃࡣ㠃┤ 118ࠊ㠃ෆ 114཯ᑕ࡟ࡘ࠸࡚⾜ࡗࡓࠋᇶᯈ㠃᪉఩ࢆ㍈࡜ࡋ࡚ᅇᢡィࢆ㉮ᰝࡍࡿࡓࡵ
࡟ࠊHࠊKࠊL ✵㛫ᗙᶆ⣔ࢆ⏝࠸ࡓࠋ❧᪉ᬗ SrTiO3㻔110㻕ᇶᯈ࡟ࡘ࠸࡚ࡣࠊἲ⥺᪉ྥ<110>㻔h=1, k=1, l=0㻕ࢆ L
㻔L = h+k㻕࡜ࡋࠊL ࡟ᆶ┤࡞᪉ྥ࡟ H 㻔K = l㻕ࠊK 㻔K =h-k㻕࡜ࡋࡓṇ᪉ᬗࡢ㻔H, K, L㻕tetra ࢆ⏝࠸ࡓࠋタᐃࡋࡓHࠊKࠊL ᗙᶆ⣔࡟࠾࠸࡚ࠊL=0 ࡢ᪉఩ࡣ㠃ෆ᪉ྥ
࡛࠶ࡾࠊL ࡢ್ࢆไᚚࡍࡿࡇ࡜࡛㠃ෆ཯ᑕ ᐃ᫬㻵㼚㼠㼑㼚㼟㼕㼠㼥ᒙ≧ᒾሷᆺࡢⷧ⭷㻔௨ୗࠊLNCM㻔118㻕࡜グࡍ㻕ࢆᚓࡓࠋFig.1㸬Schematic drawing of LNCM㻔118㻕ⷧ⭷ࡢ⭷ཌࡣ STEM ほᐹ࠿ࡽ 30 nm ࡛࠶ࡿࡇ࡜ࢆ☜ㄆࡋ࡚࠸ࡿࠋⷧ⭷ᶍᘧᅗࢆ Fig.1 ࡟♧ࡍࠋᚓࡽࢀࡓⷧ⭷ࢆṇᴟ࡟⏝࠸࡚ࠊ㈇ᴟ࡟ Liࠊ㟁ゎᾮ࡟ 1M-LiPF6 ࢆᨭᣢ㟁ゎ㉁࡜ࡋࡓ EC/DEC㻔3/7㻕㸺
Ethylene Carbonate㻔EC㻕㸪Diethyl Carbonate㻔DEC㻕㸼ࢆ⏝࠸࡚ in-situ ࢭࣝࢆస〇ࡋࡓࠋIn-situ ࢭ࡛ࣝࡣୖ㠃࡟ṇᴟࢆ⨨ࡁࠊධᑕ࡞ࡽࡧ࡟ᅇᢡ X ⥺ࡀ㏱㐣ྍ⬟࡟࡞ࡗ࡚࠸ࡿࠋࢭࣝᶍᘧᅗࢆ Fig.2 ࡟♧ࡍࠋIn-situ X ⥺ᅇᢡ ᐃࡣࠊBL46XU ࡟タ⨨ࡉࢀ࡚࠸ࡿ
HUBER 〇 8 ㍈ᅇᢡィࢆ⏝࠸࡚ヨᩱࡢゅᗘࢆㄪᩚࡋࠊⓎ⏕ࡋࡓ X ⥺ࡣᖜ 0.02 mm·㧗ࡉ 0.5 mm ࡢⓎᩓࢫࣜࢵࢺ࡛Ⓨᩓゅࢆไ㝈ࡋࠊヨᩱ୰࡛ᅇᢡࡉࢀࡓ
Fig.2㸬In-situ cell imageX⥺ࡣᖜ1.0 mm·㧗ࡉ0.2 mm ࡢཷගࢫࣜࢵࢺ࡛཰᮰ࡉࡏ࡚ NaI ࢩࣥࢳ࣮ࣞࢩࣙࣥ࢝࢘ࣥࢱ࣮ࢆ⏝࠸࡚㻝㻚㻱㻗㻜㻜᳨ฟࡋࡓࠋX ⥺ࡢ࢚ࢿࣝࢠ࣮ࡣ㟁ゎᾮࢆ㏱㐣ྍ⬟࡞ 15 keV ࡜ࡋࡓࠋ                  㻝㻚㻱㻙㻜㻝         Critical  angle      㟁ụ཯ᛂࡣ࣏ࢸࣥࢩࣙࢫࢱࢵࢺࢆ⏝࠸࡚㟁ᅽไ㻝㻚㻱㻙㻜㻞ᚚ࡛㐍⾜ࡉࡏࡓࠋ㛤ᅇ㊰㟁఩㻔OCV㻕ࠊ㟁ᅽ༳ຍᚋࡢ㻝㻚㻱㻙㻜㻟ྛ㐣⛬࡟࠾࠸࡚ࠊ⾲㠃୪ࡧ࡟ࣂࣝࢡᅇᢡ ᐃࢆ⾜㻝㻚㻱㻙㻜㻠㻝㻚㻱㻙㻜㻡㻝㻚㻱㻙㻜㻢
㻜㻚㻜㻝㻜㻚㻝㻝㻸㻛㼡㼚㼕㼠㻌㼛㼒㻌㼏㻖- -Fig.3㸬 L scan spectrum of the surface 114-

peak for the LNCM㻔118㻕

- -ࡢ X ⥺ධᑕゅࢆつᐃ࡛ࡁࡿࠋ㠃ෆ 114཯ᑕࡢ ᐃ࡟࠾࠸࡚ࠊL ࢫ࢟ࣕࣥ᫬ࡢᅇᢡᙉᗘኚ໬㻔Fig.3㻕࠿ࡽ᭱኱ᙉᗘࢆᚓࡽࢀࡓゅᗘ Lmax ࢆ⮫⏺ゅ࡜⪃࠼ࠊᴟࡵ࡚ X ⥺ධᑕ῝ࡉࡀᑠࡉ࠸㻔ᩘ nm ࡜ண᝿ࡉࢀࡿ㻕Lmax ௨ୗ࡜ࡍࡿࡇ࡜࡛ࠊ⾲㠃࡛ࡢᵓ㐀ኚ໬ࢆ᳨ฟࡋࡓࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸-- -Fig.4 ࡟㟁Ẽ໬Ꮫ཯ᛂ࡟క࠺ LNCM ࣂࣝࢡ 118 ཯ᑕࡢᅇᢡᅗᙧࢆ♧ࡋࠊFig.5 ࡟ LNCM ⾲㠃 114
཯ᑕࡢᅇᢡᅗᙧࢆ♧ࡍࠋᶓ㍈ࡣ㠃㛫㝸 d ࡟ኚ᥮ࡋ࡚࠸ࡿࠋOCV ࡢ᫬Ⅼ࡛ᅇᢡࣆ࣮ࢡࡣ 2 ࡘ࡟ศ㞳ࡋ࡚࠾ࡾࠊLNCM ⷧ⭷ࡣ 2 ✀㢮ࡢᵓ㐀ࢆᣢࡘ࡜⪃࠼ࡽࢀࡿࠋࣂࣝࢡ࡛ࡣ Li ⬺ᤄධࢆ⧞ࡾ㏉ࡍ࡟ࡘࢀ࡚ᅇᢡࣆ࣮ࢡࡀࣈ࣮ࣟࢻ࡟࡞ࡾࠊ」ᩘࡢᵓ㐀ࡢᏑᅾࡀ♧၀ࡉࢀࡓࠋ⾲㠃࡛ࡣึᮇ඘㟁 4.5V ᫬Ⅼ࡛ᅇᢡࣆ࣮ࢡࡀࣈ࣮ࣟࢻ࡟࡞ࡗ࡚࠾ࡾࠊ㟁ᴟෆࡼࡾࡶ᪩ࡃᵓ㐀࡟஘ࢀࡀ⏕ࡌࡓࠋᮏㄢ㢟࡟ࡼࡾࠊ඘ᨺ㟁཯ᛂ୰࡟࠾ࡅࡿ LiNi1/3Co1/3Mn1/3O2 㟁ᴟ⾲㠃ᣲືࢆ㏣㊧ࡍࡿࡇ࡜࡟ึࡵ࡚ᡂຌࡋࠊ⾲㠃࡛ࡣ㟁ᴟෆࡼࡾࡶ๻ⓗ࡞ᵓ㐀ኚ໬ࢆ♧ࡍࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋᮏᐇ㦂ࡢ⤖ᯝ࠿ࡽࠊ㟁ᴟ⾲㠃࡛ࡢᵓ㐀ኚ໬ࡀ඘ᨺ㟁ࢧ࢖ࢡࣝࢆ㔜ࡡࡿ࡞࠿࡛ᚎࠎ࡟ࣂࣝࢡ࡬㐍⾜ࡋ࡚࠸ࡃ࡜⪃࠼ࡽࢀࠊ⾲㠃࡟࠾ࡅࡿᵓ㐀ኚ໬ࡀ⪏ஂᛶపୗ࡟㛵㐃ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡿࠋ⾲㠃ฎ⌮࡞࡝ࡢᡭἲ࡟ࡼࡾࠊ⾲㠃ᵓ㐀ኚ໬ࢆᢚไࡍࡿࡇ࡜࡛⪏ஂᛶࡀྥୖࡍࡿྍ⬟ᛶࢆぢฟࡍࡇ࡜ࡀ࡛ࡁࡓࠋ

㻔b㻕

㻔a㻕

OCV

1d-3.5V
1d-3.0V㻵㼚㼠㻚㻔㼍㻚㼡㻚㻕㻵㼚㼠㻚㻔㼍㻚㼡㻚㻕

1c-4.5V

2c-4.5V
2d-3.0V
4d-3.0V

1c-4.0V
1c-4.5V

5c-4.5V㻝㻚㻠㻥㻝㻚㻠㻡㻝㻚㻠㻥㻝㻚㻠㻝㻝㻚㻠㻡㻝㻚㻠㻝㼐㻌㼢㼍㼘㼡㼑㻌㼐 㻌㻛㻌䊅㼐㻌㼢㼍㼘㼡㼑㻌㼐 㻌㻛㻌䊅-Fig.4㸬 In-situ XRD patterns of the bulk 118 peak for the-LNCM㻔118㻕 during the first charging㻌㻔a㻕 and charge
discharging 㻔b㻕㻔b㻕

OCV
1c-4.0V

1c-4.5V
1d-3.5V
1d-3.0V㻵㼚㼠㻚㻔㼍㻚㼡㻚㻕㻵㼚㼠㻚㻔㼍㻚㼡㻚㻕㻔a㻕

2c-4.5V
2d-3.0V

1c-4.5V
㻞㻚㻝㻝

㻞㻚㻜㻡

㻝㻚㻥㻥

㼐㻌㼢㼍㼘㼡㼑㻌㼐 㻛䊅4d-3.0V
5c-4.5V
㻞㻚㻝㻝

㻞㻚㻜㻡

㻝㻚㻥㻥

㼐㻌㼢㼍㼘㼡㼑㻌㼐 㻛䊅- -Fig.5㸬 In-situ XRD patterns of the surface 114 peak for the-LNCM㻔118㻕 during the first charging 㻔a㻕 and charge
discharging 㻔b㻕௒ᚋࡢㄢ㢟㸸ࡼࡾヲ⣽࡟ຎ໬࣓࢝ࢽࢬ࣒ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࡣࠊLiNi1/3Co1/3Mn1/3O2 ⷧ⭷ࡢ⾲㠃ฎ⌮ࢆ⾜ࡗࡓヨᩱ࡟ࡘ࠸࡚ࠊin-situ X ⥺⾲㠃ᅇᢡ ᐃࢆ⾜࠸ࠊ⾲㠃ᵓ㐀ኚ໬࡜⪏ஂᛶࡢ㛵ಀࢆ᫂ࡽ࠿࡟ࡍࡿᚲせࡀ࠶ࡿࠋཧ⪃ᩥ⊩㸸
[1] S. Muto, Y. Sasano, K. Tatsumi, T. Sasaki, K. Horibuchi, Y. Takeuchi, and Y. Ukyo, J. electrochem. Soc,156, 371, 㻔2009㻕.
[2] M. Hirayama, K. Sakamoto, T. Hiraide, D. Mori, A. Yamada, R. Kanno, N. Sonoyama, K. Tamura andJ.Mizuki, Electrochim. Acta, 53, 871, 㻔2007㻕.
[3] K. Sakamoto, H. Konishi, N. Sonoyama, A. Yamada, K. Tamura, J. Mizuki and R. Kanno, J. PowerSources, 174, 678, 㻔2007㻕.