JP2013538933A - グラフェンで金属と金属酸化物をカプセル化する方法とこれらの材料の使用方法 - Google Patents
グラフェンで金属と金属酸化物をカプセル化する方法とこれらの材料の使用方法 Download PDFInfo
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- JP2013538933A JP2013538933A JP2013509551A JP2013509551A JP2013538933A JP 2013538933 A JP2013538933 A JP 2013538933A JP 2013509551 A JP2013509551 A JP 2013509551A JP 2013509551 A JP2013509551 A JP 2013509551A JP 2013538933 A JP2013538933 A JP 2013538933A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 25
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- 239000002184 metal Substances 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 title claims description 19
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- 239000002105 nanoparticle Substances 0.000 claims abstract description 119
- 239000002245 particle Substances 0.000 claims abstract description 32
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- 150000002736 metal compounds Chemical class 0.000 claims abstract description 11
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 39
- 229910001416 lithium ion Inorganic materials 0.000 claims description 39
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 22
- 125000000524 functional group Chemical group 0.000 claims description 15
- 239000003093 cationic surfactant Substances 0.000 claims description 9
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 7
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 4
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- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
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- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- 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
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- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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- 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
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01—ELECTRIC ELEMENTS
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
(a)懸濁媒体と正の表面電荷をもつナノ粒子を含む懸濁液を提供する工程、
(b)該懸濁液に酸化グラフェン粒子を添加して該酸化グラフェン粒子をナノ粒子上に集積させる工程、及び
(c)ナノ粒子上に集積した酸化グラフェン粒子をグラフェンに変換させる工程、を含むグラフェン皮膜ナノ粒子の製造方法、
少なくとも一種の金属、半金属、金属化合物及び/又は半金属化合物を含むグラフェン被覆ナノ粒子、これらのグラフェン被覆ナノ粒子の電気化学セル及びスーパーキャパシタ中での使用方法、並びにこれらのナノ粒子を含むスーパーキャパシタ及び電気化学セルに関する。
【選択図】なし
Description
(a)懸濁媒体と少なくとも一種の成分Aを含む正の表面電荷をもつナノ粒子とを含む懸濁液を提供する工程、
(b)該懸濁液に酸化グラフェン粒子を添加して該酸化グラフェン粒子をナノ粒子上に集積させる工程、及び
(c)ナノ粒子上に集積した酸化グラフェン粒子をグラフェンに変換させる工程、を含むこれらのナノ粒子の製造方法と、
本発明のナノ粒子の電気化学セル中でリチウムイオンを吸収及び/又は放出する材料としての使用方法、並びに本発明のナノ粒子を含む電気化学セル及びスーパーキャパシタを提供する。
(a)懸濁媒体と少なくとも一種の成分Aを含む正の表面電荷をもつナノ粒子とを含む懸濁液を提供する工程、
(b)該懸濁液に酸化グラフェン粒子を添加して該酸化グラフェン粒子をナノ粒子上に集積させる工程、及び
(c)ナノ粒子上に集積した酸化グラフェン粒子をグラフェンに変換させる工程、を含む方法で製造できる。
酸化コバルトは、ポリビニルピロリドン(PVP)の存在下での酢酸コバルトとエチレングリコールの反応で製造した(A. M. Cao et al., J. Phys. Chem. B. 100 (2006) page 15858)。このために、2.24gのCo(CH3COO)2−4H2Oと1.5gのmMPVP(Mw=58000)を200mlのエチレングリコールに溶解して濁った溶液を得た。この混合物をマグネチックスターラーで攪拌し、アルゴン雰囲気下で170℃まで加熱した。30分後、数回の遠心分離/エタノール分散サイクルを実施して生成物を除き、500℃で2時間焼成した。
標準的なR2032ボタンセル中で電気化学的試験を行った。実施例1のグラフェン被覆Co3O4ナノ粒子と、Co3O4と、グラフェンとCo3O4の機械的混合物(91.5重量%のCo3O4と8.5重量%のグラフェン)を用いて作用電極を製造した。このために、これらの特定の活物質を、カーボンブラックとポリフッ化ビニリデン(PVDF)に、重量比で80(活物質):10(カーボンブラック):10(PVDF)の比率で混合し、銅箔上に塗布した(99.6%、グッドフェロー)。用いた対電極はリチウム箔であった。電解質は、エチレンカーボネート(EC)/ジメチルカーボネート(DMC)(体積比:1:1;Industries Ltd)中の1MのLiPF6溶液であった。これらのセルをアルゴンで充たされたグローブボックス中で組み立てた。
Claims (15)
- 金属と半金属、金属化合物、半金属化合物からなる群から選ばれる少なくとも一種の成分Aと少なくとも一層のグラフェン皮膜とからなるナノ粒子。
- ナノ粒子の総重量に対して、60〜97重量%の少なくとも一種の成分Aと3〜40重量%の皮膜としてのグラフェンを含む請求項1に記載のナノ粒子。
- 平均粒子径が1〜1000nmである請求項1または2に記載のナノ粒子。
- 上記少なくとも一種の成分Aがリチウムイオンを貯蔵及び/又は放出する金属と半金属、金属化合物、半金属化合物からなる群から選ばれる請求項1〜3のいずれか一項に記載のナノ粒子。
- 上記少なくとも一種の成分Aが、Sn、Ge、Si、Pb、Co3O4、CuO、SnO2、SnO、NiO、MoO2、TiO2、HfO2、ZrO2、ZnO、Al2O3、SiO2、Fe3O4、Fe2O3、LiFePO4、MnO2、及びRuO2、並びにLiを含有する酸化物及びMn、Ni及び/又はCoの複合酸化物(例えば、LiMnO2、LiCoO2、LiNiO2、LiMn0.5Ni1.5O4、及びLiMnO4)からなる群選ばれる請求項1〜4のいずれか一項に記載のナノ粒子。
- 請求項1〜5のいずれか一項に記載のナノ粒子を製造する方法であって、
(a)懸濁媒体と少なくとも一種の成分Aを含む正の表面電荷をもつナノ粒子とを含む懸濁液を提供する工程、
(b)該懸濁液に酸化グラフェン粒子を添加して該酸化グラフェン粒子をナノ粒子上に集積させる工程、及び
(c)ナノ粒子上に集積した酸化グラフェン粒子をグラフェンに変換させる工程、を含む製造方法。 - 上記ナノ粒子の正の表面電荷が、ナノ粒子表面の官能基での修飾及び/又は少なくとも一種のカチオン系界面活性剤のナノ粒子表面上での吸着及び/又は懸濁液のpHの調整でもたらされる請求項6に記載の方法。
- 上記官能基が正帯電官能基と正帯電官能基の前駆体から選ばれる請求項7に記載の方法。
- 上記官能基が、NR2とNR3 +(式中、Rは、それぞれ独立してHとC1−C6−アルキルおよびC1−C6−ヒドロキシアルキルから選ばれ、一個以上のRが複数のNR2及び/又はNR3 +基に結合していてもよい)から選ばれる請求項7または8に記載の方法。
- 上記少なくとも一種のカチオン系界面活性剤が、4級アンモニウム化合物の群から選ばれる請求項7〜9のいずれか一項に記載の方法。
- 上記懸濁液が水性懸濁媒体を含む請求項6〜10のいずれか一項に記載の方法。
- 少なくとも一種の還元剤の添加により上記酸化グラフェンがグラフェンに還元される請求項6〜11のいずれか一項に記載の方法。
- 不活性ガス雰囲気下で少なくとも1分間、上記酸化グラフェン被覆ナノ粒子を最高で600℃で加熱することにより上記酸化グラフェンがグラフェンに変換される請求項6〜11のいずれか一項に記載の方法。
- 電気化学セル中でのまたスーパーキャパシタ中での、リチウムイオン貯蔵及び/又は放出材料としての請求項1〜5のいずれか一項に記載のナノ粒子の使用方法。
- 請求項1〜5のいずれか一項に記載のナノ粒子を含む電気化学セル及びスーパーキャパシタ。
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KR20130106772A (ko) | 2013-09-30 |
KR101809771B1 (ko) | 2017-12-15 |
EP2569249B1 (de) | 2017-07-12 |
EP2569249A1 (de) | 2013-03-20 |
CN102917981B (zh) | 2016-01-20 |
JP2016185902A (ja) | 2016-10-27 |
CN102917981A (zh) | 2013-02-06 |
JP6403705B2 (ja) | 2018-10-10 |
WO2011141486A1 (de) | 2011-11-17 |
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