JPWO2019093513A1 - リチウムバナジウム酸化物結晶体、電極材料及び蓄電デバイス - Google Patents
リチウムバナジウム酸化物結晶体、電極材料及び蓄電デバイス Download PDFInfo
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- JPWO2019093513A1 JPWO2019093513A1 JP2019552421A JP2019552421A JPWO2019093513A1 JP WO2019093513 A1 JPWO2019093513 A1 JP WO2019093513A1 JP 2019552421 A JP2019552421 A JP 2019552421A JP 2019552421 A JP2019552421 A JP 2019552421A JP WO2019093513 A1 JPWO2019093513 A1 JP WO2019093513A1
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- Prior art keywords
- lithium
- degrees
- vanadium oxide
- peak
- oxide crystal
- Prior art date
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- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 125
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 title claims abstract description 104
- 239000007772 electrode material Substances 0.000 title claims description 12
- 238000003860 storage Methods 0.000 title claims description 12
- 150000001768 cations Chemical class 0.000 claims abstract description 16
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 103
- 229910052799 carbon Inorganic materials 0.000 claims description 82
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 57
- 229910001416 lithium ion Inorganic materials 0.000 claims description 57
- 238000003780 insertion Methods 0.000 claims description 17
- 230000037431 insertion Effects 0.000 claims description 17
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- 125000001475 halogen functional group Chemical group 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000011246 composite particle Substances 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 description 79
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 69
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 49
- 239000002131 composite material Substances 0.000 description 46
- 238000011282 treatment Methods 0.000 description 46
- 239000000543 intermediate Substances 0.000 description 43
- 239000002243 precursor Substances 0.000 description 25
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 25
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- 229920000642 polymer Polymers 0.000 description 24
- 229910052720 vanadium Inorganic materials 0.000 description 24
- 239000002041 carbon nanotube Substances 0.000 description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 238000009792 diffusion process Methods 0.000 description 18
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- 238000010438 heat treatment Methods 0.000 description 13
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- 238000007254 oxidation reaction Methods 0.000 description 13
- 238000000634 powder X-ray diffraction Methods 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 11
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- 238000010304 firing Methods 0.000 description 10
- 239000003446 ligand Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
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- 238000003795 desorption Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 7
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- 239000011149 active material Substances 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 6
- -1 lithium vanadate Chemical class 0.000 description 6
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- 239000007864 aqueous solution Substances 0.000 description 5
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- FSJSYDFBTIVUFD-XHTSQIMGSA-N (e)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O FSJSYDFBTIVUFD-XHTSQIMGSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
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- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GKQWYZBANWAFMQ-UHFFFAOYSA-M lithium;2-hydroxypropanoate Chemical compound [Li+].CC(O)C([O-])=O GKQWYZBANWAFMQ-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011817 metal compound particle Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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Abstract
Description
まず、本発明のリチウムバナジウム酸化物結晶体(以下、本リチウムバナジウム酸化物結晶体という)は、リチウムイオンが可逆的に挿入及び脱離可能な材料である。本リチウムバナジウム酸化物結晶体は、例えば蓄電デバイスの電極材料としての用途に好適である。蓄電デバイスとしてはリチウムイオン二次電池やハイブリッドキャパシタが挙げられる。
本リチウムバナジウム酸化物結晶体は、図4に示すX線回折結果をもたらす結晶構造を有する。図4は、本リチウムバナジウム酸化物結晶体をシミュレーションに基づく粉末X線回折で分析した結果を示すグラフである。図4に示すように、従来(図1参照)と比べて、入射角2θが32.2度付近に鋭敏なピークが現れる点は同じである。尚、32.2度付近とは32.2±0.7度をいう。
長距離秩序を有し、リチウムイオンの脱離時にはVO4が四面体配位構造を有する従来のバナジン酸リチウム結晶体(以下、中間体という)に対し、CC−CV(Constant Current Constant Voltage)処理を行うことにより、本リチウムバナジウム酸化物結晶体は得られる。中間体は、リチウム源とバナジウム源の混合工程と熱処理工程を経て得られる。カーボンとの複合体を生成する場合には、中間体の作製過程内の混合工程で更にカーボン源を添加すればよい。
まず、中間体の製造方法について説明する。中間体は、混合工程、分散工程、ポリマー鎖形成工程、除去工程及び結晶化工程を経る。混合工程では、バナジウム源とリチウム源を含む金属粒子源、導電性炭素材料、錯体配位子、および重合剤とが混合された混合溶媒を作製する。分散工程では、炭素材料の表面に金属粒子源を付着させ、バナジン酸リチウムの前駆体を生成する。ポリマー鎖形成工程では、炭素材料上に付着したバナジン酸リチウムの前駆体にポリマー鎖を形成する。除去工程では、ポリマー鎖を形成したバナジン酸リチウムの前駆体が付着した炭素材料を加熱し、ポリマー鎖を除去する。結晶工程では、バナジン酸リチウムの前駆体が付着した炭素材料を焼成し、バナジン酸リチウムと炭素材料の複合材料を得る。
これにより得られた中間体に対してCC−CV処理を行うことによって本リチウムバナジウム酸化物結晶体とカーボンとの複合体が得られる。CC−CV処理は、中間体を負極としたハーフセルを作製し、このハーフセルに定電流及び定電圧の印加する処理である。
以下、本発明の実施例を示すが、本発明は実施例に限定されるものではない。まず、以下の製造方法により、中間体としてバナジン酸リチウムとカーボンナノチューブ(CNT)の複合材料(Li3VO4/CNT)を生成した。
このCC−CV処理の前後の生成物を粉末X線回折により分析した。その結果を図15及び図16に示す。図15はCC−CV処理前の中間体を分析した結果であり、図16はCC−CV処理後の最終生成物を分析した結果である。
CC−CV処理前の中間体、即ち従来のリチウムバナジウム酸化物結晶体とカーボンの複合体と、中間体をCC−CV処理することにより得た本リチウムバナジウム酸化物結晶体のリチウムイオン拡散係数を評価した。
次に、CC−CV処理前の中間体、即ち従来のリチウムバナジウム酸化物結晶体とカーボンの複合体と、中間体をCC−CV処理することにより得た本リチウムバナジウム酸化物結晶体の充放電ヒステリシスを評価した。充放電ヒステリシスの評価に際し、両ハーフセルに対し、電圧範囲は、0.1−2.5V(vs. Li/Li+)であり、電流値は0.01Ag−1(gはバナジン酸リチウム当たり)とした。その結果を図19及び図20に示す。
次に、CC−CV処理前の中間体、即ち従来のリチウムバナジウム酸化物結晶体とカーボンの複合体と、中間体をCC−CV処理することにより得た本リチウムバナジウム酸化物結晶体とカーボンとの複合体のレート特性を評価した。
Claims (10)
- カチオンがディスオーダー化された結晶構造を有すること、
を特徴とするリチウムバナジウム酸化物結晶体。 - 化学式Li3VO4で表されること、
を特徴とする請求項1記載のリチウムバナジウム酸化物結晶体。 - X線回折の結果で表される結晶構造は、
入射角2θが32.2度付近にピークが現れ、
更に当該32.2度付近のピークよりも低角の範囲にはピークが無いか、
またはピークがあっても、当該32.2度付近のピークよりも低角の範囲に存在する全てピークの回折強度は当該32.2度付近のピークの回折強度よりも小さいこと、
を特徴とする請求項1又は2記載のリチウムバナジウム酸化物結晶体。 - 前記32.2度付近のピークよりも低角の範囲に現われるピークの回折強度は、前記32.2度付近のピークの回折強度を100とすると50以下であること、
を特徴とする請求項3記載のリチウムバナジウム酸化物結晶体。 - LiO6配位構造とVO6配位構造が並んで成り、
前記32.2度付近のピークよりも低角の範囲の長距離秩序の全て又は一部が崩れてランダムになっていること、
を特徴とする請求項1乃至4の何れかに記載のリチウムバナジウム酸化物結晶体。 - LiO6配位構造とVO6配位構造が並んで成り、
少なくとも一部のVO6配位構造がリチウムイオンの挿入及び離脱に関わらず、八面体配位を維持していること、
を特徴とする請求項1乃至5の何れかに記載のリチウムバナジウム酸化物結晶体。 - LiO6配位構造とVO6配位構造が並んで成り、
少なくとも一部のVO6配位構造がリチウムイオンの挿入及び離脱に応じて、八面体配位と六面体配位を採ること、
を特徴とする請求項1乃至6の何れかに記載のリチウムバナジウム酸化物結晶体。 - 請求項1乃至7の何れかに記載のリチウムバナジウム酸化物結晶体を含むことを特徴とする電極材料。
- 前記リチウムバナジウム酸化物結晶体とカーボンとが複合化されて成る複合体粒子を有し、
前記複合体粒子のX線回折の結果で表される結晶構造は、
入射角2θが32.2度付近にピークが現れ、
更に当該32.2度付近のピークよりも低角の範囲にはピークが無いか、
またはピークがあっても、当該32.2度付近のピークよりも低角の範囲に存在する全てピークの回折強度は当該32.2度付近のピークの回折強度よりも小さく、
更に当該32.2度付近のピークよりも低角の範囲にブロードなハローパターンが現われていること、
を特徴とする請求項8記載の電極材料。 - 請求項8又は9記載の電極材料を正極又は負極に用いたこと、
を特徴とする蓄電デバイス。
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