JP2012006821A - リチウムマンガン酸化物−炭素ナノ複合体及びその製造方法 - Google Patents
リチウムマンガン酸化物−炭素ナノ複合体及びその製造方法 Download PDFInfo
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 78
- PQCYXHTUDKAWAG-UHFFFAOYSA-N [C+4].[O-2].[Mn+2].[Li+] Chemical compound [C+4].[O-2].[Mn+2].[Li+] PQCYXHTUDKAWAG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims abstract description 65
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 36
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 239000002041 carbon nanotube Substances 0.000 claims description 23
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 23
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 20
- 239000002134 carbon nanofiber Substances 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- 239000011572 manganese Substances 0.000 claims description 16
- 229910052596 spinel Inorganic materials 0.000 claims description 15
- 239000011029 spinel Substances 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 238000004146 energy storage Methods 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 229910013553 LiNO Inorganic materials 0.000 claims description 3
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims 2
- 239000004917 carbon fiber Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 abstract description 48
- 239000011259 mixed solution Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 9
- 238000007600 charging Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000009530 blood pressure measurement Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000000306 component Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910012735 LiCo1/3Ni1/3Mn1/3O2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- SAEVTEVJHJGDLY-UHFFFAOYSA-N dilithium;manganese(2+);oxygen(2-) Chemical compound [Li+].[Li+].[O-2].[O-2].[Mn+2] SAEVTEVJHJGDLY-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- -1 etc. Inorganic materials 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000013169 thromboelastometry Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- 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
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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
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- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
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Abstract
【解決手段】本発明によると、リチウムイオン溶液とマンガンイオン溶液を混合し、上記リチウムイオンとマンガンイオンが混合された溶液に炭素素材を分散させ、上記炭素素材が分散された溶液を一定の温度に維持して炭素素材の表面にリチウムマンガン酸化物を形成し、リチウムマンガン酸化物−炭素ナノ複合体を製造する製造方法が提示される。また、リチウムマンガン酸化物が数ナノメートルの厚さで炭素素材にコーティングされたリチウムマンガン酸化物−炭素ナノ複合素材が提供される。また、リチウムマンガン酸化物を数ナノメートルの厚さで炭素素材にコーティングすることができる製造装置が提供される。
【選択図】図1
Description
MnO2+2H2O→Mn4++4OH−
8Mn4++4Li++36OH−→4LiMn2O4+18H2O+O2
LiMn2O4ナノ粒子が分散されたリチウムマンガン酸化物−炭素ナノ複合体を合成するためにマイクロ波水熱工程(microwave hydrothermal process)を用いた。
Claims (16)
- リチウムイオン溶液とマンガンイオン溶液を混合する段階と、
前記リチウムイオンとマンガンイオンが混合された溶液に炭素素材を分散させる段階と、
前記分散された炭素素材の表面にリチウムマンガン酸化物を合成する段階を含むリチウムマンガン酸化物−炭素ナノ複合体の製造方法。 - 前記リチウムマンガン酸化物を合成する段階において、一定の温度を維持するために熱を供給する、請求項1に記載のリチウムマンガン酸化物−炭素ナノ複合体の製造方法。
- 前記リチウムマンガン酸化物の厚さ、前記リチウムマンガン酸化物の合成量及びリチウムマンガン酸化物のリチウムとマンガンの割合のうち何れか1つを調節するためにリチウム量、マンガン量、炭素素材量、反応時間及び反応温度の何れか1つ以上を調節する、請求項1に記載のリチウムマンガン酸化物−炭素ナノ複合体の製造方法。
- 前記リチウムマンガン酸化物の合成を調節するために合成する間、温度と圧力の何れか1つ以上を調節する、請求項1に記載のリチウムマンガン酸化物−炭素ナノ複合体の製造方法。
- 前記炭素素材はカーボンブラック、炭素ナノチューブ(CNT;Carbon Nano Tube)、炭素ナノファイバー(CNF;Carbon Nano Fiber)、蒸気成長炭素繊維(VGCF;VaporGrownCarbonFiber)、グラファイト(Graphite)及びグラフェン(Graphene)の何れか1つである、請求項1に記載のリチウムマンガン酸化物−炭素ナノ複合体の製造方法。
- 前記リチウムイオンは1価リチウムイオンである、請求項1に記載のリチウムマンガン酸化物−炭素ナノ複合体の製造方法。
- 前記リチウムイオン溶液はLiOH、LiNO3及びLiClの何れか1つである、請求項1に記載のリチウムマンガン酸化物−炭素ナノ複合体の製造方法。
- 前記マンガンイオンは7価マンガンイオンである、請求項1に記載のリチウムマンガン酸化物−炭素ナノ複合体の製造方法。
- 前記マンガンイオン溶液はKMnO4及びNaMnO4の何れか1つである、請求項1に記載のリチウムマンガン酸化物−炭素ナノ複合体の製造方法。
- 炭素素材と、
前記炭素素材の表面に形成されたナノサイズのリチウムマンガン酸化物を含む高出力エネルギー保存装置用電極を製造するためのリチウムマンガン酸化物−炭素ナノ複合体。 - 前記炭素素材に形成されたリチウムマンガン酸化物は10ナノメートル以下のサイズを有する、請求項10に記載の高出力エネルギー保存装置用電極を製造するためのリチウムマンガン酸化物−炭素ナノ複合体。
- 前記炭素素材に形成されたリチウムマンガン酸化物はリチウムマンガン酸化物−スピネル構造である、請求項10に記載の高出力エネルギー保存装置用電極を製造するためのリチウムマンガン酸化物−炭素ナノ複合体。
- 前記炭素素材はカーボンブラック、炭素ナノチューブ(CNT;Carbon Nano Tube)、炭素ナノファイバー(CNF;Carbon Nano Fiber)、蒸気成長炭素繊維(VGCF;VaporGrownCarbonFiber)、グラファイト(Graphite)及びグラフェン(Graphene)の何れか1つである、請求項10に記載の高出力エネルギー保存装置用電極を製造するためのリチウムマンガン酸化物−炭素ナノ複合体。
- 前記リチウムマンガン酸化物はLiMn2O4である、請求項10に記載の高出力エネルギー保存装置用電極を製造するためのリチウムマンガン酸化物−炭素ナノ複合体。
- リチウムイオン溶液とマンガンイオン溶液を収容し、リチウムマンガン酸化物を炭素ナノ複合体に合成するための密閉チャンバと、
前記密閉チャンバの内部に熱を供給するための熱供給ユニットと、
前記熱供給ユニットの供給熱を制御するために、前記密閉チャンバの内部の温度、圧力の何れか1つ以上を測定する温度−圧力測定ユニットと、
前記測定された温度と圧力に応じて、温度、圧力の何れか1つ以上を制御する温度−圧力制御ユニットを含むリチウムマンガン酸化物−炭素ナノ複合体の製造装置。 - 前記熱供給ユニットはマイクロウエーブ走査装置である、請求項15に記載のリチウムマンガン酸化物−炭素ナノ複合体の製造装置。
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JP2012099436A (ja) * | 2010-11-05 | 2012-05-24 | Univ Of Tokyo | 電池用正極材、その製造方法及び非水電解液二次電池 |
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WO2014077247A1 (ja) * | 2012-11-13 | 2014-05-22 | 日本ケミコン株式会社 | 電極材料の製造方法、電極材料及び該電極材料を備えた蓄電デバイス |
JP2018035035A (ja) * | 2016-08-31 | 2018-03-08 | 学校法人 関西大学 | 炭素量子ドットの製造方法及びその方法で得られる炭素量子ドット |
KR102017421B1 (ko) * | 2018-04-26 | 2019-09-02 | 서울과학기술대학교 산학협력단 | 원-포트(One-pot) 합성법을 통한 금속 산화물 코팅 및 금속 도핑된 양극 소재의 제조방법 및 이를 통해 제조된 양극 소재 |
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