http://support.spring8.or.jp/Report_JSR/PDF_JSR_31A/2019A1760.pdf

2019A1760

BL19B2᪂つ Mg ஧ḟ㟁ụ⏝ṇᴟᮦᩱࡢ㛤Ⓨࢆ┠ⓗ࡜ࡋࡓ MgCo2-xMnxO4-Mg
䠄Mg0.33V1.67-yNiy䠅O4 ⣔ᅛ⁐యࡢ⤖ᬗ࣭㟁Ꮚᵓ㐀ゎᯒ
Crystal and Electronic Structure Analysis of MgCo2-xMnxO4-Mg
䠄Mg0.33V1.67-yNiy䠅O4 Solid Solution for Development of Novel CathodeMaterial of Mg Rechargeable Battery஭ᡭᮏ ᗣ a, ໭ᮧ ᑦᩯ a, ▼⏣ ┤ဢ a, ཎ⏣ ᗣᏹ b, ➲ᕝ ဴஓ b
Yasushi Idemotoa, Naoto Kitamuraa, Naoya Ishidaa, Yasuhiro Haradab, Tetsuya Sasakawaba

ᮾி⌮⛉኱, b䠄ᰴ䠅ᮾⰪaTokyo University of Science, bToshiba Co., Ltd.
᪂つ࣐ࢢࢿࢩ࣒࢘஧ḟ㟁ụṇᴟᮦᩱ࡜ࡋ࡚ zMgCo2-xMnxO4-䠄1-z䠅Mg䠄Mg0.33V1.67-yNiy䠅O4 ࢆ✀ࠎࡢ᪉ἲ࡛ྜᡂࡋࡓࠋRietveld ἲ࡟ࡼࡾ⤖ᬗᵓ㐀ࢆ⢭ᐦ໬ࡋࡓ⤖ᯝࠊྜᡂࡋࡓヨᩱࡣ❧᪉ᬗࡢࢫࣆࢿࣝᆺᵓ㐀ࢆ᭷ࡋ࡚࠾ࡾࠊ16d ࢧ࢖ࢺࢆ୰ᚰ࡜ࡍࡿඵ㠃యࡢ⤖ྜゅศᩓࡀࠊ㏫ඹỿἲ࡛ྜᡂࡋࡓヨᩱ࡛ࡣᑠࡉ࠸ࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ࣮࣮࢟࣡ࢻ㸸 ᅇᢡࠊ࣐ࢢࢿࢩ࣒࢘஧ḟ㟁ụࠊṇᴟᮦᩱࠊ⤖ᬗ࣭㟁Ꮚᵓ㐀⫼ᬒ࡜◊✲┠ⓗ㸸㏆ᖺࠊపⅣ⣲໬♫఍ࡢᐇ⌧ࡀႚ⥭ࡢㄢ㢟࡜࡞ࡗ࡚࠾ࡾࠊ⎔ቃ㈇Ⲵࡢపῶࡸ࢚ࢿࣝࢠ࣮ࡢ᭷ຠ฼
⏝ࢆ┠ⓗ࡜ࡋࡓ๰࣭⵳࢚ࢿࣝࢠ࣮ࡢ◊✲ࡀ⢭ຊⓗ࡟⾜ࢃࢀ࡚࠸ࡿࠋࡇࡢࡼ࠺࡞♫఍᝟ໃࢆཷࡅ࡚⵳㟁ụࡀᨵࡵ࡚╔┠ࡉࢀ࡚࠾ࡾࠊᑠᆺ㟁Ꮚᶵჾࡢ㟁※ࡔࡅ࡛࡞ࡃࠊ㟁Ẽ⮬ື㌴⏝࣭ᐃ⨨⏝኱ᆺ㟁※࡜ࡋ࡚ࡢ฼⏝ࡀᮇᚅࡉࢀ࡚࠸ࡿࠋࡑࡢࡓࡵࠊ⵳㟁ụ࡟ồࡵࡽࢀࡿᛶ⬟ࡶ㧗ࡃ࡞ࡗ࡚࠾ࡾࠊࡇࢀࡲ࡛୺ຊ࡛࠶ࡗࡓࣜࢳ࣒࢘࢖࢜ࣥ㟁ụࡼࡾࡶᏳ౯࡛㧗య✚࢚ࢿࣝࢠ࣮ᐦᗘࡢ㠉᪂㟁ụࡢ㛤Ⓨ࡟ᑐࡍࡿ♫఍ⓗࢽ࣮ࢬࡀ㧗ࡲࡗ࡚࠸ࡿࠋḟୡ௦⵳㟁ụࡢ 1 ࡘ࡜ࡋ࡚ࠊ1 ౯ࡢࣜࢳ࣒࢘࢖࢜ࣥࡢ௦ࢃࡾ࡟ 2 ౯ࡢ㝧࢖࢜ࣥࡢ཯ᛂࢆ฼⏝ࡋࡓ࣐ࢢࢿࢩ࣒࢘஧ḟ㟁ụࡀ࠶ࡆࡽࢀࡿࠋ࣐ࢢࢿࢩ࣒࢘ࡣࣜࢳ࢘
࣒࡟ẚ࡭࡚㈨※㔞ࡀ㇏ᐩ࡛࠶ࡾࠊ㈇ᴟ࡜ࡋ࡚⏝࠸ࡽࢀ࡚࠸ࡿ㔠ᒓ࣐ࢢࢿࢩ࣒࢘ࡢయ✚࢚ࢿࣝࢠ࣮ᐦᗘࡀ㧗࠸࡜࠸࠺฼Ⅼࡀ࠶ࡿࠋ୍᪉࡛ࠊ࣐ࢢࢿࢩ࣒࢘࢖࢜ࣥ㸦Mg2+㸧ࢆᤄධ࣭⬺㞳ྍ⬟࡞ṇᴟᮦᩱࡢሗ࿌౛ࡣࠊࢫࣆࢿࣝᆺᵓ㐀ࡢ MgCo2O4 ࡞࡝ࠊ㠀ᖖ࡟㝈ࡽࢀ࡚࠸ࡿ[1]ࠋࡇࡢࡼ࠺࡞⫼ᬒ࠿ࡽࠊᙜ◊✲ᐊ࡛ࡣ࣐ࢢࢿࢩ࣒࢘஧ḟ㟁ụ⏝᪂つṇᴟᮦᩱࡢ๰〇࡟ྲྀࡾ⤌ࢇ࡛
࠾ࡾࠊMgCo2O4 ࡢ Co ࢆ Ni, V, Mn ࡛⨨᥮ࡋࡓᮦᩱ࡟╔┠ࡋࠊṇᴟ≉ᛶࡢホ౯ࢆ⾜ࡗ࡚ࡁࡓ[2, 3]ࠋ
ࡑࡢ⤖ᯝࠊMgCo2O4 ࡢ Co ࢆ Mn ࡛㒊ศ⨨᥮ࡋࡓ MgCo2-xMnxO4䠄x=0.5䠅࡟࠾࠸࡚ࠊᨺ㟁ᐜ㔞⥔ᣢ⋡㸦ࢧ࢖ࢡࣝ≉ᛶ㸧ࡣప࠸ࡶࡢࡢࠊ㧗࠸࢚ࢿࣝࢠ࣮ᐦᗘࡀᚓࡽࢀࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊCoࢆ V ࡛⨨᥮ࡋࡓ≀㉁࡟ࡶ╔┠ࡋࠊMgV2O4 ࢆẕయ࡜ࡋ࡚ Mg ⤌ᡂࢆ㐣๫࡟ࡋࡓ Mg䠄Mg0.33V1.67-yNiy䠅
O4㸦y=0.1㸧ࡀඃࢀࡓࢧ࢖ࢡࣝ≉ᛶࢆ♧ࡍࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋᮏ◊✲࡛ࡣࠊࡇࢀࡽ୧ヨᩱࡢ≉ᚩࢆ⏕࠿ࡍࡓࡵࠊ᪂ࡓ࡟ zMgCo2-xMnxO4-䠄1-z䠅Mg䠄Mg0.33V1.67-yNiy䠅O4 ⣔ᅛ⁐య࡟╔┠ࡋࠊඃࢀࡓᐜ㔞⥔ᣢ⋡࡜㧗࢚ࢿࣝࢠ࣮ᐦᗘࢆᐇ⌧ࡍࡿ᪂ࡓ࡞ṇᴟᮦᩱࢆ๰〇ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋࡋ࠿ࡋࠊࡇࡢᅛ⁐యࡣ⤌ᡂࡔࡅ࡛࡞ࡃࠊྜᡂ᪉ἲ࡟ࡼࡗ࡚ࡶ X ⥺ᅇᢡࣃࢱ࣮ࣥࡀኚ໬ࡋ࡚࠾ࡾࠊ⤌ᡂ࣭ྜᡂ᮲௳ࠊṇᴟ≉ᛶࠊ⤖ᬗ࣭㟁Ꮚᵓ㐀ࡢ㛵ಀࡣ᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋࡑࡇ࡛ࠊࡇࡢᅛ⁐యࢆ␗࡞ࡿྜᡂ᪉ἲ࡛స〇ࡋࠊࡑࡢṇᴟ≉ᛶࢆホ౯ࡍࡿ࡜࡜ࡶ࡟ࠊᨺᑕග X ⥺ᅇᢡ ᐃࢆᐇ᪋ࡋࡓࠋᚓࡽࢀࡓᅇᢡࢹ࣮ࢱࢆ⏝࠸࡚⤖ᬗ࣭㟁Ꮚᵓ㐀ࢆ᫂ࡽ࠿࡟ࡋࠊ⤌ᡂ࣭ྜᡂ᮲௳࡜ṇᴟ≉ᛶࠊ⤖ᬗ࣭㟁Ꮚᵓ㐀ࡢ㛵ಀࡢゎ᫂ࢆヨࡳࡓࠋᐇ㦂㸸
zMgCo2-xMnxO4-䠄1-z䠅Mg䠄Mg0.33V1.67-yNiy䠅O4 ࢆ㏫ඹỿἲ࡜ᅛ┦ἲࠊ࣓࢝ࣀࢣ࣑࢝ࣝἲ࡟ࡼࡾྜᡂࡋࡓࠋ㏫ඹỿἲ࡛ࡣࠊྛ㔠ᒓ◪㓟ሷỈ⁐ᾮࢆᡤᐃẚ࡛ΰྜࡋࡓᚋࠊⅣ㓟ࢼࢺ࣒ࣜ࢘Ỉ⁐ᾮ࡟⁲ୗࡋࠊ⏕ࡌࡓỿẊ≀ࢆ↝ᡂࡍࡿࡇ࡜࡛┠ⓗࡢヨᩱࢆᚓࡓࠋ௚ࡢྜᡂἲ࡛ࡣࠊ࠶ࡽ࠿ࡌࡵ MgCo2-xMnxO4
࡜ Mg䠄Mg0.33V1.67-yNiy䠅O4 ࢆྜᡂࡋࠊࡇࢀࡽࢆཎᩱ࡜ࡋ࡚ᅛ⁐యࢆྜᡂࡋࡓࠋᚓࡽࢀࡓヨᩱ࡟ࡘ࠸䠉㻥㻡䠉
࡚ࠊ஦๓࡟ᐇ㦂ᐊ⣔ࡢ X ⥺ᅇᢡ ᐃ࡟ࡼࡾ┦ࡢྠᐃࢆ⾜࠸ࠊICP Ⓨගศගศᯒ࡟ࡼࡾ㔠ᒓᡂศࡢ⤌ᡂࢆỴᐃࡋࡓࠋࡲࡓࠊྛ≀㉁ࢆṇᴟᮦᩱ࡜ࡋ࡚ࠊ㖟ཧ↷ᴟ࡜㔠ᒓ࣐ࢢࢿࢩ࣒࢘㈇ᴟࢆ⏝࠸ࡓ୕㟁ᴟᘧࢭࣝࢆࢢ࣮ࣟࣈ࣎ࢵࢡࢫ࡛⤌ࡳ❧࡚ࠊᐃ㟁ὶࡢ඘ᨺ㟁ヨ㦂࡟ࡼࡾṇᴟ≉ᛶࢆホ౯ࡋࡓࠋ࡞࠾ࠊ
Mn ⨨᥮㔞 x, Ni ⨨᥮㔞 y ࡟ࡘ࠸࡚ࡣࠊྛ➃ᡂศࡢ᭱㐺⤌ᡂ䠄x=0.5, y=0.1䠅௜㏆࡛᭱㐺໬ࢆ⾜ࡗࡓࠋྜᡂࡋࡓ⢊ᮎࢆ༑ศ࡟⢊○ࡋࡓᚋࠊࣜࣥࢹ࣐ࣥ࢞ࣛࢫ㸦0.3 mmØ㸧〇ࡢ࢟ࣕࣆ࣮ࣛࣜ࡟඘ሸࡋࠊ
ᨺᑕග X ⥺ᅇᢡࣃࢱ࣮ࣥ㸦BL19B2㸧ࢆ ᐃࡋࡓࠋᚓࡽࢀࡓᅇᢡࣃࢱ࣮ࣥࢆ Rietveld ἲ㸦Rietan-FP㸧࡟ࡼࡾゎᯒࡋࠊ⤖ᬗᵓ㐀ࢆ⢭ᐦ໬ࡋࡓࠋࡲࡓࠊ᭱኱࢚ࣥࢺࣟࣆ࣮ἲ㸦Dysnomia㸧࡟ࡼࡾ㟁Ꮚᐦᗘศᕸࡢྍど໬ࢆ⾜ࡗࡓࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸
㏫ඹỿἲ࡟ࡼࡾୖグࡢᅛ⁐యࡢྜᡂࢆヨࡳࡓ⤖ᯝࠊ↝ᡂ᮲௳ࢆ᭱㐺໬ࡍࡿࡇ࡜࡟ࡼࡾࠊࢫࣆࢿࣝᆺᵓ㐀ࡢ໬ྜ≀ࡀ୺┦࡜ࡋ࡚ᚓࡽࢀࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊICP Ⓨගศගศᯒ࡟ࡼࡿ⤌ᡂศᯒࡢ⤖ᯝࠊྜᡂࡋࡓヨᩱࡢ㔠ᒓ⤌ᡂẚࡣᴫࡡ௙㎸ࡳ⤌ᡂ㏻ࡾ࡟ไᚚࡉࢀ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋ࣐ࢢࢿࢩ࣒࢘஧ḟ㟁ụࡢṇᴟᮦᩱ࡜ࡋ࡚㟁ᴟ≉ᛶࢆホ౯ࡋࡓ⤖ᯝࠊ㏫ඹỿἲ㸦↝ᡂ
ᗘ 500°C㸧࡟ࡼࡾྜᡂࡋࡓ x=0.5, y=0.1,
Fig. 1 Rietveld
refinement
patternofz=0.5 ࡢヨᩱ࡟࠾࠸࡚ึᅇᨺ㟁ᐜ㔞ࡀ⣙ 150
0.5MgCo1.5Mn0.5O4-0.5Mg䠄Mg0.33V1.57Ni0.1䠅O4
mAh g-1 ࡛࠶ࡾࠊẚ㍑ⓗⰋዲ࡞඘ᨺ㟁⥔ᣢ⋡
prepared by a reverse coprecipitation method.
ࢆ♧ࡍࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ
Plus marks show observed synchrotron X-ray
diffraction patterns and a solid line representsࡇࢀࡽࡢヨᩱ࡟ࡘ࠸࡚⤖ᬗᵓ㐀࡟㛵ࡍࡿcalculated intensities. Vertical marks indicateヲ⣽࡞▱ぢࢆᚓࡿࡓࡵࠊᨺᑕග X ⥺ᅇᢡࣃ
positions of allowed Bragg reflections. A curveࢱ࣮ࣥࢆ ᐃࡋࠊRietveld ゎᯒࢆ⾜ࡗࡓࠋࠊat the bottom is a difference between the୍౛࡜ࡋ࡚ࠊ㏫ඹỿἲ࡟ࡼࡾᚓࡽࢀࡓ
observed and calculated intensities in the same
0.5MgCo1.5Mn0.5O4-0.5Mg䠄Mg0.33V1.57Ni0.1䠅O4scale.
ࡢゎᯒࣃࢱ࣮ࣥࢆ Fig. 1 ࡟♧ࡍࠋᅇᢡࣆ࣮
ࢡࡣ❧᪉ᬗࡢࢫࣆࢿࣝᆺᵓ㐀࡟ᖐᒓ࡛ࡁࡓࡓࡵࠊ᪤ሗ࡟ᚑࡗ࡚✵㛫⩌ Fd-3m ࢆ⏝࠸࡚ゎᯒࢆ⾜ࡗࡓࠋࡲࡓࠊࡍ࡭࡚ࡢ࢝ࢳ࢜ࣥࡀᅄ㠃యࢧ࢖ࢺ䠄8a䠅࡜ඵ㠃యࢧ࢖ࢺ䠄16d䠅ࡢ୧᪉ࢆ༨᭷ࡍࡿྍ⬟ᛶࢆ⪃៖ࡋ࡚ࠊ༨᭷⋡ࡢ⢭ᐦ໬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ඘ᨺ㟁᫬࡟ Mg ࡢᣑᩓ⤒㊰࡜࡞ࡿᅄ㠃యࢧ࢖ࢺࡣ୺࡟ Mg ࡟ࡼࡗ࡚༨᭷ࡉࢀ࡚࠸ࡿࡶࡢࡢࠊ௚ࡢ࢝ࢳ࢜ࣥࡶᏑᅾࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡇࡢࡼ࠺࡞ഴྥࡣ௚ࡢ᪉ἲ࡛ྜᡂࡋࡓヨᩱ࡛ࡶぢࡽࢀࡓࠋࡉࡽ࡟ࠊ㏫ඹỿἲ࡟ࡼࡾྜᡂࡋࡓヨᩱ࡜௚ࡢヨᩱ࡜ẚ㍑ࡍࡿ࡜ࠊ16d ࢧ࢖ࢺࢆ୰ᚰ࡜ࡍࡿඵ㠃యࡢ⤖ྜゅศᩓ㸦⤖ྜゅࡢṍࡳ㸧ࡀ㏫ඹỿἲࡢヨᩱ࡛ࡣᑠࡉ࠸ࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ୍⯡࡟ࠊṍࡳࡣ඘ᨺ㟁≉ᛶ࡟ᙳ㡪ࢆཬࡰࡍ࡜⪃࠼ࡽࢀ࡚࠸ࡿࡓࡵࠊྜᡂ᪉ἲࢆ᭱㐺໬ࡍࡿࡇ࡜࡟ࡼࡾࠊࡼࡾඃࢀࡓ඘ᨺ㟁≉ᛶࢆ♧ࡍ≀㉁ࢆタィ࡛ࡁࡿ࡜⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ࠊ᭱኱࢚ࣥࢺࣟࣆ࣮ἲ࡟ࡼࡿゎᯒࢆ⾜ࡗࡓ⤖ᯝࠊྜᡂ᪉ἲࡀ㟁Ꮚᐦᗘศᕸ࡟ᙳ㡪ࢆཬࡰࡍࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡾࠊ㏫ඹỿἲ࡛ྜᡂࡋࡓヨᩱ࡟࠾࠸࡚ᅄ㠃యࢧ࢖ࢺ࡜㓟⣲ࢧ࢖ࢺࡢ㛫ࡢ㟁Ꮚᐦᗘࡀప࠸ࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ௒ᚋࡢㄢ㢟㸸௚ࡢ⤌ᡂࡢヨᩱ࡟ࡘ࠸࡚ࡶྠᵝࡢゎᯒࢆ⾜࠸ࠊ⤌ᡂࡸྜᡂ᮲௳ࡀ⤖ᬗ࣭㟁Ꮚᵓ㐀࡟ཬࡰࡍᙳ㡪ࢆ᫂ࡽ࠿࡟ࡋࠊṇᴟ≉ᛶ࡜ࡢ┦㛵㛵ಀࢆ᳨ウࡍࡿࠋࡇࢀ࡟ࡼࡾࠊඃࢀࡓ࣐ࢢࢿࢩ࣒࢘஧ḟ㟁ụ⏝ṇᴟᮦᩱࡢ๰〇ࢆヨࡳࡿࠋཧ⪃ᩥ⊩㸸
[1] S. Okamoto, T. Ichitsubo, T. Kawaguchi et al., Adv. Sci., 2, 1500072䠄2015䠅.
[2] Y. Idemoto, Y. Mizutani, C. Ishibashi et al., Electrochemistry, 87, 220䠄2019䠅.
[3] Y. Idemoto, N. Kawakami, N. Ishida et al., Electrochemistry, 87, 281䠄2019䠅.

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